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POC 2012 Organizing, Scientificand International Advisory Committees

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Message from the Conference Chair 7

Message from our Premier Sponsor 9

Welcome to Qatar 11

Discover Qatar! 12

Our Proud Sponsors 14

Our Keynote Lecturer: Dr. Robert H Grubbs 19

POC 2012 Session Chairs 20

Schedule of Events 24

Oral Presentation 32

Poster Presentations 114

Index 197

Table of Contents

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POLYOLEFINS (32-41)Olefin polymerization with metallocene and “post metallocene” derivatives of zirconium. J. Bercaw

Single site catalysis for olefin polymerisation, polyolefin depolymerisation and related reactions. J. Basset

Approaching olefin polymerization from first principle. T. Ziegler

Stereoselective (co)polymerizations of styrene with single-site mono-component and binary lanthanidocene catalysts. J. Carpentier

Influence of combination of fillers and fibers on the morphological, thermal and mechanical properties of recycled polymers. M. Al-Maadeed

New polymers by metallocene catalysed ofefin polymerization. W. Kaminsky

The activation of soluble olefin polymerization catalysts. M. Bochmann

Comprehensive approach from active sites to particle for the next generation Ziegler-Natta catalysts. M. Terano

Single site catalyst molecular design and multicomponenet catalyst engineering for production of non-commodity polyolefins; case study. A. Razavi

ORTHOGONAL CHEMISTRY: ORGANIC AND POLYMER SYNTHESIS (43-52)Efficient and catalyst free polymer functionalization and coupling. R. K. O’Reilly

Functionalized polymers for functional materials. R. B. Grubbs

Synthesis of new functionalized polythiophenes for organic biosensors. C. Suspène

Metal-catalyzed multicomponent polymerization – a new method for the construction of conjugated materials. D. C. Leitch

Phase transfer activation of Grubbs’ ROMP catalyst systems. R. Tuba

Macromolecular material design via modular synthetic strategies. C. Barner -Kowollik

Starch-derived 1,4-3,6:dianhydrohexitol stereoisomers: Versatile platform for the design of original polymers using robust, efficient and orthogonal chemistries. E. Drockenmuller

Three-dimensional DNA nanostructures as blocks in polymer self-assembly. C. J. Serpell

Molecular desin of main-chain chiral quaternary ammonium polymers for asymmetric catalysis application. S. Itsuno

Novel synthetic strategies to functionalized macromolecules. C. J. Hawker

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POLYMERS IN ENERGY (54-61)The Polymer-Like Solid Electrolyte Interphase on Carbon Electrodes in Lithium -Ion Batteries. P. Novák

Redox-active organic structures vs Li : a possible alternative design ˝greener˝ Li -ion batteries. P. Poizot

Organic Batteries with Various Types of Charge Storage Configuration. K. Oyaizu

Repairable BIOMIMETIC soft materials. M. A. Firestone

Design Rules for Fuel Cell Membranes. G. Maier

Polymer solar cells: an attempt of near infrared dye sensitization. S. Ito

Insight into the synthesis, design and processing of narrow bandgap organic semiconducting polymers for solar cell fabrication. G. C. Bazan

Functional macromolecules: from design to applications. J. M. J. Fréchet

Amphiphilic conjugated block copolymers for efficient bulk heterojunction solar cells. C. Suspène

MACROMOLECULAR ENGINEERING WITH BIOMOLECULES (63-71)Using the chemical information in DNA to control structure. N. C. Seeman

Functional self-assembled architectures from polymers and proteins. R. J. M. Nolte

DNA-programmed assembly and coupling of molecular wires. C. B. Rosen

Supramolecular chemistry with DNA: Towards biological and materials application. H. F. Sleiman

Functional supramolecular polymers and their hybrids with covalent polymers. S. I. Stupp

DNA block copolymers: from drug delivery to nanoelectronics. A. Herrmann

Enzyme responsive micellar nanoparticles from novel peptide - and oligonucleotide- polymer amphiphiles. M. E. Hahn

DNA-dendron hyabrid: A new buliding block for functional systems. Z. Yang

Self-assembly and optically triggered disassembly of dendron-virus complexes. M. Kostiainen

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POLYMERS FROM RENEWABLE RESOURCES (73-81)Cellulose nanomaterials – molecular design of biological nanofibers for the purpose of large-scale industrial applications. L. A. Berglund

Plant oils: The perfect renewable resource for polymer science?! M. A. R. Meier

Natural triterpenoids as renewable nanos: Formation of helical nano-fibers, nano-vesicles, nano-spheres and dynamic soft-materials. B. G. Bag

Novel green materials from biobased resin systems and lignin hybrid: Processing an applications. M. Misra

Design and development of hydrolytically - degradable poly (quinic Acid carbonate)s for orthopedic applications. J. M. Streff

Bioplastics and green materials from renewable resources: What is new! A. K. Mohanty

Embracing the era of renewably sources materials: a family of high performance polymers and fibers from dupont. J. V. Kurian

An overview of environmental benefits for polymers made from renewable resources. M. K. Patel

Synthesis and possible medical application of injectable macromers derived from fatty acids. J. Skrobot

RESPONSIVE AND SMART POLYMERS (83-92)Polymer mechanochemistry: Using force to direct molecular reactivity. C. W. Bielawski

Polymer architectures and nanostructures generated via living radical polymerization. M. J. Monteiro

Rational design & synthesis of “intelligent” star polymers for cytoplasmic delivery of therapeutic nucleic acids. M. E. H. El-Sayed

Synthesis of well-defined photo - crosslinked polymeric nanocapsules by surface - initiated raft polymerization. X. Huang

Precise heirarchial self-assembly of multicompartment micelles. A. H. Gröschel

Supramolecular approaches to stimuli-responsive polymers. S. J. Rowan

Multifunctional polymeric catalysts and reagents. P. H. Toy

Responsive polymer solubility as a tool in synthesis. D. E. Bergbreiter

Concealed qualities - polymers with an upper critical solution temperature in water. J. Seuring

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POLYMERS AS THERAPEUTICS (94-102)Monomers based on methacrylic acid bisphosphonates for polymer drug delivery. F. Caruso

Polymer therapeutics for celiac disease. J. Leroux

The art of falling apart: Exploiting nanomaterial disassembly for medicine and pharmacy. A. Almutairi

Monomers based on methacrylic acid bisphosphonates for polymer drug delivery. S. Kachbi

Synthesis and evaluation of biodegradable hydrogels based on hyperbranched polyester for alveolar bone treatment. F. Rasoul

Multifunctional polymeris for theranostics and tissue engineering. M. Weck

Managing serum potassium with RLY5016. An insight into polymer drug development at Relypsa. E. Connor

Nanoscopic polymer objects of unique shapes and morphologies and well - defined structures and dimensions as controlled drug delivery devices. K. L. Wooley

ADVANCES IN POLYMER SYNTHESIS (104-113)Synthesis of functional materials through combination of controlled polymerization techniques and efficient polymer analogous reactions. B. Voit

Non-covalent synthesis of functional supramolecular systems. E. W. Meijer

Polystyrene composites of single-walled carbon nanotubes. W. T. Ford

Novel polesters based on cyclobutanediol: Energy efficient synthesis of bisphenol a-free materials. D. J. Burke

Olefin metathesis polymerization from alkynes. T. Choi

Design and synthesis of conjugated polymers and hybrid materials. S. Valiyaveettil

Precision synthesis in chain-growth condensation polymerization. T. Yokozawa

Development of Novel polymer-supported macmillan catalysts with ionic bond for asymmetric reaction. N. Haraguchi

Synthesis of functional smart polymers. D. Kuckling

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14th IUPAC Conference on Polymers and Organic Chemistry Doha, 2012

POC 2012 Organizing CommitteeHassan S. Bazzi,Chair Benjamin CieslinskiHala S. Al-Easa Hala El-DakakDave Seapy Chelsea KreiterAshfaq Bengali Crystal YetterEdward Brothers

POC 2012 Scientific CommitteeHassan S. Bazzi Joseph KurianBrigitte Voit Hiroyuki NishideHanadi F. Sleiman Abbas RazaviCraig J. Hawker David E. BergbreiterKaren L. Wooley Jan C. KwakHala S. Al-Easa

POC 2012 International Advisory CommitteeHassan S. Bazzi (Qatar) Marcus Weck (USA)Karen L. Wooley (USA) E.W. (Bert) Meijer (Netherlands)Hanadi Sleiman (Canada) Ned Seeman (USA)David E. Bergbreiter (USA) Patrick Toy (Hong Kong)Warren Ford (USA) Shinichi Itsuno (Japan)Julian X. X. Zhu (Canada) Karel Jerabek (Czech Republic)Christopher John Barrett (Canada) Brigitte Voit (Germany)Christopher W. Bielawski (USA) Craig Hawker (USA)Pietro Tundo (Italy) Sharon L. Haynie (USA)Philip Hodge (UK) Hiroyuki Nishide (Japan)Abbas Razavi (Belgium) Suresh Valiyaveettil (Singapore)

POC 2012 International Advisory CommitteeHala S. Al-Easa (Qatar)(POLYMERS FROM RENEWABLE RESOURCES)

Jan C. Kwak (Qatar)(RESPONSIVE AND SMART POLYMERS)

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Message from the Conference Chair

Dear Delegates,

Welcome to the 14th International Union of Pure and Applied Chemistry Conference on Polymers and Organic Chemistry (POC 2012).

Qatar is the first Arab country to host this IUPAC meeting since its inception in 1982, and the honor of hosting such a prestigious scientific event is fitting for a nation that has experienced 15 years of impressive growth, especially in higher education. This conference advances the country’s goal of building an economy based on knowledge, and such progress runs parallel to the nation’s industrial, educational and economic development.

Qatar is one of the world’s most rapidly advancing centers for scientific and technological research. Through the work of premier universities, and thanks to partnerships with leading organizations in the industrial, commercial and government sectors, Qatar has become a thriving marketplace for ideas, information and scholarship.

As Qatar strives to realize its vision for tomorrow, the work of researchers here in Qatar, and that of their collaborators abroad, contributes to a promising and prosperous future for Qatar, the region and the world.

Our conference would not be possible without the generous patronage of our premier sponsor, Qatar Petrochemical Company (QAPCO). QAPCO’s support of this meeting demonstrates its commitment to expanding Qatar’s knowledge base. I am also very grateful to our sponsors, Qatar Fertiliser Company (QAFCO), Qatar University, the Qatar Foundation, Texas A&M University at Qatar and Qatar Airways. We are grateful for their support of endeavors such as POC 2012 that bring prominence and prestige to Qatar and its academic and scientific communities.

This no doubt will be an outstanding conference that will be a platform to discuss the latest research in the fields of polymers and organic chemistry, to promote the role of Qatar as a leading nation in the production of polymers, and to support one of the largest industry sectors in Qatar, the production of polyolefins.

Best wishes for an outstanding conference, and welcome to Doha!

Sincerely,

Hassan S. Bazzi, Ph.D. Chair, 14th IUPAC POC 2012Chair, Science ProgramTexas A&M University at QatarDoha, QatarBazzi@tamu.edu

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Message from our Premier Sponsor

Welcome to the 14th International Union of Pure and Applied Chemistry Conference on Polymers and Organic Chemistry.

Qatar Petrochemical Company (QAPCO) is honored to be the Premier Sponsor of this conference, as we believe now is the perfect time to highlight the current research being undertaken in the field of Polymers and Organic Chemistry. It is also a privilege to be able to work in partnership with Texas A&M University at Qatar as it provides a wonderful opportunity for Industry and Academia to collaborate so that the theoretical aspects discussed at Conference can be successfully put in production.

For our international guests, may I also take this opportunity to welcome you to Qatar, the home of hospitality and I hope that you will enjoy your stay with us. Through the strong guidance and wise leadership of H.H. Sheikh Hamad bin Khalifa Al Thani, Qatar has become a country that understands the power of education and has embraced the future of learning by establishing high quality Universities to fully develop the human capital of the country.

QAPCO is committed to supporting this quest for learning and is helping to build the modern State of Qatar through a Quality Qatarization initiative that works hand in hand with all educational establishments to enhance the knowledge and skills of Qatari Nationals preparing them to be the future leaders and engineers of the Country.

Over the past thirty years, QAPCO has greatly contributed to the growth and development of the Country and of the Petrochemical Industry in Qatar, and it has established itself as one of the leading national industrial companies, with an ambitious strategy based on the best utilization of the country’s hydrocarbon reserves.

To sustain our achievements for the future, QAPCO is continuing to invest in Research & Development as a key strategic priority, through innovative collaboration projects with our university partners, especially in the development of environmentally friendly and energy saving composite materials based on QAPCO produced polymers and recycled plastics.

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By extending commitment beyond the manufacturing boundaries and by providing customers with valuable support services – from logistics to developing specific product grades – QAPCO has gained a highly commendable reputation worldwide now serving nearly 8000 customers spread over 145 countries to efficiently market products of QAPCO and its strategic partners. This has been achieved by expanding its Global Marketing Network and providing consistent quality and customer service. QAPCO now stands high as a sustainable Industry leader, fulfilling its Corporate Social Responsibility to continually improve Health, Safety and Environmental standards in the workplace and develop the full potential of our most valuable asset, the knowledge, skills and innovative talent of our people.

Once again I welcome you to the 14th IUPAC Meeting.

Thank you.

Dr. Mohammed Al-Mulla Vice Chairman & Chief Executive Officer

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Message from our Premier Sponsor

TopographyQatar is an independent state in the Southern Arabian Gulf surrounded by Saudi Arabia, Bahrain, the United Arab Emirates and Iran. The country is situated midway along the western coast of the Arabian Gulf between latitudes 24.27° - 26.10° North and longitude 50.45° - 51.40° East. It is approximately 11,437 square kilometers on a low-lying limestone peninsula projecting northward about 160 kilometers into the Gulf. Beaches and sand dunes are predominantly found along the eastern coast, especially at Khor Al-Udeid and Mesaieed. The shoreline of the mainland is a zigzag with many fjords and bays which are known locally as Khor(s).

Qatar’s coastline is mostly flat. Reefs and shoals extend to as much as 48-80 km in some places. The coast, for the most part, is uninhabited extensive tracts of sand. Populated coastal areas have groves of date palms. Doha is the Arabic term for a small circular bay, such as those found at Mesaideed, Ad Doha, Dohat El-Hussein, Dohat Zekrit, and Salwa.

TransportationWhile visiting Qatar, the best way to get around on your own is by taxi. There are two services that we recommend that are reliable, safe and fair. The first is run by the national transport company and the taxi service is called Karwa. The Karwa taxis are easy to identify with their blue-green cars and travel all throughout Doha at a very reasonable price. The second is a private car service called Fox limousine.

To request a taxi or limousine, call one of the following numbers.Karwa 4458-8888 Fox Limousine 4462-2777

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The CornicheThe waterfront promenade encircling Doha Bay, the Doha Corniche is a major thoroughfare and entertainment area of Qatar. Every morning joggers get their exercise, and every evening the Corniche and its connecting park fill with families enjoying the magical downtown lights. Cafes and coffee shops can be found alongside the traditional fishing Dhows amongst the seven kilometer stretch.

Museum of Islamic ArtNestled on a man-made island in the middle of Doha harbor, this stunning I.M. Pei designed museum is a unique storehouse dedicated to all facets of Islamic art. The finest examples of manuscripts, ceramics, and textiles from every Muslim country in the world fill the galleries. Included in the free admission is access to the extensive libraries, along with the best view of the West Bay and the Corniche.

Souq WaqifRecently restored to its former glory, this major outdoor market is the place to go for tourists and locals alike for spices, handicrafts, and souvenirs. Along the narrow alleys filled with varied shops and art galleries are a collection of restaurants representing cuisines from all over the world. The nearby Fanir Islamic Center and its piercing spiral mosque is a great place to learn about Islam and the Arabic people.

While in Qatar, take some time and visit some of the many beautiful and fascinating wonders of the Middle East.

Discover Qatar!

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City CenterThe Renaissance Hotel is conveniently connected to one of Doha’s modern malls. City Center offers a wide selection of stores, cafés and restaurants. Activities, such as the Ice Skating Rink, Grand Cinema and other organized events can be found within City Center.

The PearlOver 32 new kilometers of coastline was created when Qatar began building its first artificial island residential area. The Pearl features a large range of luxury villas, apartments, five-star hotels and over two million square meters of international retail, restaurants, cafes and entertainment. Eight other private islands will be for sale to private owners. The Pearl is home to the finest shopping and dining in all of Qatar.

Inland SeaLocally called Khor al-Daid, this massive inland sea is connected to the Arabian Gulf by a narrow inlet that shares the southern border with Saudi Arabia. Located over an hour’s drive south of Qatar, an additional half-hour dune bashing through the entrance of the Empty Quarter is required to reach the shallow blue sea. Filled with hammour, small sharks, and porpoises, it is one of the most popular weekend getaways in Qatar.

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Discover Qatar!

Qatar Fertiliser Company S.A.Q. (QAFCO)The Jewels of Growth

Since its inception in 1969 QAFCO has steered its way successfully and steadily developed over the years. Accordingly QAFCO has become one of the main producers and exporters of ammonia and urea in the world.

With a sizable annual production capacity of 3.8 million MT of ammonia and 4.3 million MT of urea from 6 Ammonia and 5 Urea plants, QAFCO is now the world’s largest single-site producer of both ammonia and urea. Currently, QAFCO exports ammonia and urea to more than 35 nations across the globe.

QAFCO as well as boosting its fertiliser production it has gone into a new product areas and joint ventures including a urea formaldehyde plant, which went on stream in September 2003, and a melamine plant inaugurated in October 2010. With a production capacity of 60,000 MT per year the melamine plant is the largest melamine plant in the Middle East and one of the largest melamine plants in the world.

QAFCO boasts three ISO Certifications: ISO 9001: 2000, ISO 14001: 2004,. and OHSAS 18001 standards.

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Qatar University

Since its inception in 1973, Qatar University (QU) has served as Qatar’s most prominent and sole national institution of higher education. With nearly 8,000 students and a 13:1 student-teacher ratio, the university serves as a national beacon for higher education and academic excellence. QU currently hosts seven colleges – Arts and Sciences, Business and Economics, Education, Engineering, Law, Pharmacy, and Shari’a and Islamic Studies.

The university is committed to providing high-quality education in areas of national priority. It prides itself on the quality of its students and alumni, and is committed to ensuring that campus life is an enriching environment for encouraging academic excellence, volunteerism, civic responsibility and leadership.

Qatar University is pleased to be part of this very significant conference which is being held for the first time in Doha since its inception in 1982. We are equally pleased to be one of the sponsors of this event alongside other key institutions and companies in Doha.

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Qatar Foundation - Unlocking Human Potential

Qatar Foundation for Education, Science, and Community Development is a private, non-profit organization that is supporting Qatar on its journey from carbon economy to knowledge economy by unlocking human potential for the benefit of not only Qatar, but the world. Founded in 1995 by His Highness Sheikh Hamad Bin Khalifa Al-Thani, Amir of Qatar, QF is chaired by Her Highness Sheikha Moza bint Nasser.

QF carries out its mission through three strategic pillars: education, science and research, and community development. QF’s education pillar brings world-class universities to Qatar to help create an education sector in which young people can develop the attitudes and skills required for a knowledge economy. Meanwhile, its science and research pillar builds Qatar’s innovation and technology capacity by developing and commercialising solutions through key sciences. Finally, its community development pillar helps foster a progressive society while also enhancing cultural life, protecting Qatar’s heritage and addressing social needs.

For a complete list of QF’s initiatives and projects, visit http://www.qf.org.qa

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Qatar University

Qatar Airways is the national airline of the State of Qatar and one of the aviation industry’s big success stories. Operations began in 1994 when the airline was a small regional carrier servicing a handful of routes. The airline was re-launched in 1997 under the mandate of the country’s leader The Emir, His Highness Sheikh Hamad bin Khalifa Al Thani, who outlined a vision to turn Qatar Airways into a leading international airline with the highest standards of service and excellence.

The airline, which is 50 per cent government-owned and 50 per cent under the private sector, has developed under the leadership of Chief Executive Officer Akbar Al Baker, appointed CEO in 1996, who has been instrumental in turning Qatar Airways into an award-winning carrier and the best in the world.

Under Al Baker’s stewardship, Qatar Airways has matured into a leading force in regional and global aviation, earning many admirers around the world for its excellent standards of service.

In June 2011, Qatar Airways achieved a remarkable feat, just 14 years after its relaunch, being named Airline of the Year 2011 in the annual Skytrax World Airline Awards with over 18 million travellers worldwide casting their votes.

From Qatar Airways’ hub in Doha, the country’s capital, the airline has developed a global network of over 100 destinations with a modern fleet of over 100 passenger and cargo aircraft.

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Texas A&M University at QatarEngineering a World of Difference

Texas A&M University at Qatar offers bachelor’s and master’s degrees in engineering at Education City, a 2,400-acre, multi-university campus in Doha, Qatar. The curricula offered at Texas A&M at Qatar are materially identical to those offered at the main campus in College Station, Texas, and courses are taught in English in a co-educational setting.

The reputation for excellence is the same, as is the commitment to equipping engineers to lead the next generation of engineering advancement.

More than 500 students are enrolled, and since 2007, more than 200 Aggies have received undergraduate degrees in chemical, electrical, mechanical or petroleum engineering. Graduate studies programs began in fall 2011, and the campus’s first master’s degrees are anticipated in May 2013.

Faculty from around the world are attracted to Texas A&M at Qatar to provide this educational experience and to participate in research activities, now valued at over $96 million, that address issues important to the State of Qatar.

Texas A&M at Qatar is wholly funded by Qatar Foundation for Education, Science and Community Development. Education City also has branches of Carnegie Mellon, Cornell, Georgetown, Northwestern, and Virginia Commonwealth universities.

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Our Keynote Lecturer

Dr. Robert H. Grubbs is the Victor and Elizabeth Atkins Professor of Chemistry at the California Institute of Technology, Pasadena, California, USA, where he has been a faculty member since 1978. Before moving to Caltech, he was at Michigan State University from 1969 to 1978 achieving the rank of Associate Professor.

B.S., Chemistry, University of Florida, Gainesville, Florida, 1963; M.S., Merle Battiste, 1965. Ph.D., Ronald Breslow, Chemistry, Columbia University, New York, New York, 1968. NIH Postdoctoral Fellow, James P. Collman, Chemistry, Stanford University, 1968-69.

The research group of Grubbs is involved in the design, synthesis, and mechanistic studies of complexes that catalyze basic organic transformations. The major focus of the group over the past few years has been on the olefin metathesis reaction. To optimize the utility of this reaction, new catalysts have been developed that are extremely tolerant of organic functional groups. Due to their high-activity, functional group tolerance, and ease of use, these ruthenium based catalysts have found wide applications in organic and polymer synthesis. He has 500+ publications and 115+ patents based on his research.

Professor Grubbs awards have included Alfred P. Sloan Fellow (1974-76), Camille and Henry Dreyfus Teacher-Scholar Award (1975-78), Alexander von Humboldt Fellowship (1975), ACS National Award in Organometallic Chemistry (1988), Arthur C. Cope Scholar Award (1990), ACS Award in Polymer Chemistry (1995), Nagoya Medal of Organic Chemistry (1997), Fluka Reagent of the Year (1998), Mack Memorial Award (1999), Benjamin Franklin Medal in Chemistry (2000), ACS Herman F. Mark Polymer Chemistry Award (2000), ACS Herbert C. Brown Award for Creative Research in Synthetic Methods (2001), ACS Arthur C. Cope Award (2002), ACS Award for Creative Research in Homogeneous or Heterogeneous Catalysis (2003), Richard C. Tolman Medal (Southern California Section ACS - 2003), ACS Tetrahedron Prize for Creativity in Organic Chemistry (2003), Pauling Award Medal (2003), Bristol-Myers Squibb Distinguished Achievement Award in Organic Synthesis (2004), Kirkwood Medal (2005) (New Haven Section, ACS), Paul Karrer Gold Medallion (2005) (University of Zurich), August-wilhelm-von-Hofmann-Denkmunze (2005) (German Chemical Society), Nobel Prize in Chemistry (2005), Havinga Medal (2006) (Leiden University), Golden Plate Award (2006) (Academy of Achievement), and Tetrahedron Most Cited Paper 2003-2006 Award (“Olefin Metathesis”), Tetrahedron Letters Most Cited Paper 2005-2008 Award (“A Neutral, Water-Soluble Olefin Metathesis Catalyst Based on an N-Heterocyclic Carbene Ligand”), ACS Award for Creative Invention (2009), Gold Medal of the American Institute of Chemists (2010), ACS Roger Adams Award in Organic Chemistry (2011). He was elected to the National Academy of Sciences (1989), Fellow of the American Academy of Arts and Sciences (1994), the Honorary Fellowship of the Royal Society of Chemistry (2006), Fellows of the American Chemical Society (2009), ACS Polymer Division Fellow (2010).

Dr. Robert H. Grubbs“Courtesy of Caltech”

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Professor David E. Bergbreiter

Professor Craig J. Hawker

Department of Chemistry Texas A&M University,College Station, TX, USA

Department of Chemistry and BiochemistryUniversity of California Santa BarbaraSanta Barbara, CA, USA

POC 2012 Session Chairs

Professor David E. Bergbreiter is a Professor of Chemistry and a Presidential Professor for Teaching Excellence at Texas A&M University in College Station, Texas. Since his initial appointment at Texas A&M in 1974, he has carried out research in organic synthesis, physical organic chemistry, organometallic chemistry, catalysis, and polymer surface chemistry. His group has made seminal contributions in studies of enolate and related azaallyl anion chemistry, in polymer surface chemistry, in studies of responsive polymers and in studies of recoverable, separable catalysts. These studies have included the development of hyperbranched and covalent layer-by-layer syntheses of ‘smart’ responsive grafts, the first report of ‘smart’ catalysts, and the design of thermomorphic systems where the phase solubility properties of polymers are used to advantage in Green chemistry and catalysis.

Craig J. Hawker, FRS received his BSc (1984) degree from the University of Queensland, Australia his PhD (1988) degree from the University of Cambridge, followed by a post-doctoral fellowship with Professor Jean M.J. Fréchet at Cornell from 1988 to 1990. In 2005 he moved from the IBM Almaden Research Center to the University of California, Santa Barbara where he is the Alan and Ruth Heeger Chair of Interdisciplinary Science and a Professor in the Materials, Chemistry and Biochemistry departments. He is also the Director of the Materials Research Laboratory, founding Director of the Dow Materials Institute and visiting Chair Professor at King Fahd University of Petroleum and Minerals. His research activities focus on synthetic polymer chemistry, nanotechnology and materials science where he integrates fundamental synthetic studies with the development of nanostructured materials. He holds more than 45 patents, has published over 300 papers and has received a number of awards for his work. In 2010 he was named as a Fellow of the Royal Society.

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Dr. Joe Kurian

Professor Hiroyuki Nishide

DuPont CompanyWilmington, DE, USA

Department of Applied ChemistryWaseda UniversityTokyo 169-8555, Japan

Joe received a Ph.D. in Polymer Science from the University of Akron in Ohio, USA, working under the guidance of Professor Joseph P. Kennedy. He joined DuPont Nylon, in 1990, as a Polymer Research Chemist. At DuPont, he worked in a variety of roles including polymer and fiber research, new product development, process optimization, manufacturing and new business development. In 1995, he started pioneering research work in 3GT polymer developing polymer grade 1,3-propanediol, polymerization technologies, fiber technologies and applications know-how. He created and led a highly successful Sorona® polymer team and then worked as the Technology/Business Development Manager for the commercialization of Sorona®. He is an innovator with over 60 filed US patents (40 granted) and 50 journal publications and has received several awards for Sorona® polymer and renewably sourced materials work. Joe has led renewably sourced materials work across various DuPont Business Units [www.renewable.dupont.com]. In 2007, he was nominated for the Design Magazine’s “Engineer of the Year” Award. He is a passionate supporter of science activities, including the Science Olympiad and Science Fairs.

Hiroyuki Nishide is a Professor at Department of Applied Chemistry, Waseda University, Tokyo, Japan, and Professor at Department of Nanobio Materials and Electronics, Gwangju Institute of Science and Technology, Korea. He received his PhD in 1975, and has been visiting researcher at Free University Berlin and Polytechnic University New York. He has conducted research in the field of syntheses and applications of functional polymers, recently focusing on the organic polymers for rechargeable batteries and photovoltaic cells. He has published more than 500 journal articles, and is the Editorial Board member of Macromolecular Chemistry and Physics, Polymers for Advanced Technologies, and Green Chemistry. He is Past-President of the Society of Polymer Science, Japan, Vice-President of Japan Union of Chemical Science and Technology, and President of the Federation of Asian Polymer Societies.

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Dr. Abbas Razavi

Professor Hanadi Sleiman

Total Petrochemicals Research FeluyFeluy, Belgium

Department of ChemistryMcGill UniversityMontreal, Canada

the chemistry department of the Technical University of Munich (TUM), Munich, Germany under the supervision of the Nobel laureate Ernst Otto Fischer and Professor Max Herberhold. After a variety of academic posts, in September 1987 he started his industrial career at the Research and Technology Center (RTC) of Fina Oil and Chemicals Inc. in LaPorte, Texas, USA as senior research associate. In 1990 he moved to Petrofina Belgium and worked at the Fina Research Center in Feluy/Belgium as Senior Research Manager. In 2005, after the formation of the company TOTAL, he was appointed at the department of Global R&D Petrochemicals as International manager for metallocene where he worked until June 2011 until his retirement. Currently he is a member of Total Professors Association (TPa). He is inventor and co-inventor of hundreds of patents, author of over 150 publications in academic and technical journals and invited lecturer at over 70 conferences.

Hanadi Sleiman received her PhD from Stanford University under the guidance of L. McElwee-White. Following a CNRS postdoctoral stay in supramolecular chemistry, in the laboratory of Jean-Marie Lehn at the Université Louis Pasteur in France, she joined the faculty of McGill University in 1999, where she is currently Professor of chemistry and Dawson Scholar (McGill’s Canada Research Chair). The Sleiman research group focuses on developing the supramolecular chemistry of DNA, towards applications in biology and in nanoscience. Some of the research areas include: the design of DNA cages and nanotubes to serve as biological host molecules, the use of DNA to position functional components, such as transition metals and nanoparticles into 2D- and 3D-structures, the use of metal complexes to stabilize DNA structures of expanded molecularity for antitumor therapies and the creation of DNA-mimetic polymers. Sleiman was named Cottrell Scholar of the Research Corporation in 2002. She received the Principal’s Prize (2002) and the Leo Yaffe Award (2004) for excellence in teaching at McGill, was named William Dawson Scholar in 2004 (McGill’s Canada Research Chair), received the NSERC Discovery Accelerator Award in 2008, and the 2009 Strem Award in Inorganic Chemistry of the Canadian Society for Chemistry.

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Professor Dr. Brigitte Voit

Professor Karen L. Wooley

Leibniz-Institut für Polymerforschung Dresden e.V.Dresden, Germany

Department of ChemistryTexas A&M UniversityCollege Station, TX, USA

Brigitte Voit received her PhD in Macromolecular Chemistry in 1990 from University Bayreuth, Germany, in the field of photoactive polymers. At Eastman Kodak in Rochester, USA, she was introduced into the field of hyperbranched polymers. Subsequently, she joined the Technische Universität München continuing the work on dendritic polymers. She received her habilitation degree in Macromolecular Chemistry in 1996. In 1997 Brigitte Voit was appointed head of the Institute of Macromolecular Chemistry at the Leibniz Institute of Polymer Research (IPF) Dresden, as well as professor for “Organic Chemistry of Polymers“ at the University of Technology Dresden (TUD). In addition, since 2002, she is heading the IPF Dresden as Managing Director and Chief Scientific Officer (Scientific Director). Her major research interest is in the synthesis of new functional polymer architectures by various synthetic approaches covering topics like dendritic polymers, functional block and graft copolymers, as well as thermo- and photo labile polymers.

Karen L. Wooley, a University Distinguished Professor, holds the W. T. Doherty-Welch Chair in the Department of Chemistry at Texas A&M University. She received a B.S. in chemistry from Oregon State University in 1988 and a Ph.D. in polymer/organic chemistry from Cornell University in 1993. She then began an academic career at Washington University in St. Louis, Missouri, was promoted in 1999 to full professor, and was installed as a James S. McDonnell Distinguished University Professor in Arts & Sciences in 2006. In 2009, she relocated to Texas A&M University. Research areas include degradable polymers, unique macromolecular architectures and complex polymer assemblies, anti- biofouling materials, and well-defined nanostructured materials for medical applications. Karen serves as an Editor for the Journal of Polymer Science, Part A: Polymer Chemistry. She directs a NHLBI-supported Program of Excellence in Nanotechnology, serves on the National Institutes of Health NANO study section, and also serves on the Scientific Advisory Panel for the NIH Nanomedicine Development Centers.

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Friday, January 6, 20128:00 AM – 6:00 PM Registration

4:00 PM – 4:55 PM Opening ReceptionSponsored by TOTAL

4:55 PM – 5:00 PM Dr. Hassan S. Bazzi, Chair, POC 20125:00 PM – 5:10 PM H.E. Dr. Mohammed bin Saleh Al-Sada

Minister of Energy and Industry, Chairman and Managing Director of Qatar Petroleum

5:10 PM – 5:15 PM Dr. Mohamed Y. Al-Mulla, Vice Chairman & CEO, QAPCO5:15 PM – 6:00 PM Keynote Lecture: Robert H. Grubbs

Saturday, January 7, 2012

POLYOLEFINSMorning Session Speaker Title

8:00 – 8:30 J. Bercaw Olefin polymerization with metallocene and “post metallocene” derivatives of zirconium

8:30 – 9:00 J. Basset Single site catalysis for olefin polymerisation, polyolefin depolymerisation and related reactions

9:00 – 9:20 T. Ziegler Approaching olefin polymerization from first principle9:20 – 9:40 J. Carpentier Stereoselective (co)polymerizations of styrene with single-site

mono-component and binary lanthanidocene catalysts9:40 – 10:00 M. Al-Maadeed Influence of combination of fillers and fibers on the

morphological, thermal and mechanical properties of recycled polymers

10:20 – 10:50 W. Kaminsky New polymers by metallocene catalysed olefin polymerization10:50 – 11:20 M. Bochmann The activation of soluble olefin polymerization catalysts11:20 – 11:50 M. Terano Comprehensive approach from active sites to particle for the next

generation Ziegler-Natta catalysts11:50 –12:20 A. Razavi Single site catalyst molecular design and multicomponenet

catalyst engineering for production of non-commodity polyolefins; case study

ORTHOGONAL CHEMISTRY: ORGANIC AND POLYMER SYNTHESISMorning Session Speaker Title

8:00 – 8:30 R. K. O’Reilly Efficient and catalyst free polymer functionalization & coupling8:30 – 9:00 R. B. Grubbs Functionalized polymers for functional materials9:00 – 9:20 C. Suspène Synthesis of new functionalized polythiophenes for organic

biosensors9:20 – 9:40 D. C. Leitch Metal-catalyzed multicomponent polymerization – a new

method for the construction of conjugated materials9:40 – 10:00 R. Tuba Phase transfer activation of Grubbs’ ROMP catalyst systems10:20 – 10:50 C. Barner-

KowollikMacromolecular material design via modular synthetic strategies

Schedule of Events

25

10:50 – 11:20 E. Drockenmuller

Starch-derived 1,4-3,6:dianhydrohexitol stereoisomers: Versatile platform for the design of original polymers using robust,

efficient and orthogonal chemistries11:20 – 11:40 C. J. Serpell Three-dimensional DNA nanostructures as blocks in polymer

self-assembly11:40 – 12:10 S. Itsuno Molecular design of main-chain chiral quaternary ammonium

polymers for asymmetric catalysis application12:10 – 12:30 C. J. Hawker Novel synthetic strategies to functionalized macromolecules

12:30 – 1:30 PM Lunch1:30 – 3:30 PM Poster Session6:00 - 8:00 PM Saturday Dinner Oral Presentation Awards

Sponsored by Journal of Polymer Science Part A

Sunday, January 8, 2012

POLYMERS FROM RENEWABLE RESOURCESAfternoon session Speaker Title

1:30 – 2:00 L. A. Berglund Cellulose nanomaterials – molecular design of biological nanofibers for the purpose of large-scale industrial applications

2:00 – 2:30 M. A. R. Meier Plant oils: The perfect renewable resource for polymer science?!2:30 – 2:50 B. G. Bag Natural triterpenoids as renewable nanos: Formation of helical

nano-fibers, nano-vesicles, nano-spheres and dynamic soft-materials

2:50 – 3:10 M. Misra Novel green materials from biobased resin systems and lignin hybrid: Processing an applications

3:10 – 3:30 J. M. Streff Design and development of hydrolytically-degradable poly(quinic Acid carbonate)s for orthopedic applications

3:50 – 4:20 A. K. Mohanty Bioplastics and green materials from renewable resources: What is new!

4:20 – 4:50 J. V. Kurian Embracing the era of renewably sources materials: a family of high performance polymers and fibers from dupont

4:50 – 5:20 M. K. Patel An overview of environmental benefits for polymers made from renewable resources

5:20 – 5:40 J. Skrobot Synthesis and possible medical application of injectable macromers derived from fatty acids

MACROMOLECULAR ENGINEERING WITH BIOMOLECULESMorning Session Speaker Title

8:00 – 8:30 N. C. Seeman Using the chemical information in DNA to control structure8:30 – 9:00 R. J. M. Nolte Functional self-assembled architectures from polymers and

proteins9:00 – 9:20 C. B. Rosen DNA-programmed assembly and coupling of molecular wires9:20 – 9:50 H. F. Sleiman Supramolecular chemistry with DNA: Towards biological and

materials application

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10:20 – 10:50 S. I. Stupp Functional supramolecular polymers and their hybrids with covalent polymers

10:50 – 11:20 A. Herrmann DNA block copolymers: from drug delivery to nanoelectronics

11:20 – 11:40 M. E. Hahn Enzyme responsive micellar nanoparticles from novel peptide- and oligonucleotide- polymer amphiphiles

11:40 – 12:00 Z. Yang DNA-dendron hyabrid: A new buliding block for functional systems

12:00 – 12:30 M. Kostiainen Self-assembly and optically triggered disassembly of dendron-virus complexes

12:30 – 1:30 PM Lunch

POLYMERS FROM RENEWABLE RESOURCESAfternoon session Speaker Title

1:30 – 2:00 L. A. Berglund Cellulose nanomaterials – molecular design of biological nanofibers for the purpose of large-scale industrial applications

2:00 – 2:30 M. A. R. Meier Plant oils: The perfect renewable resource for polymer science?!2:30 – 2:50 B. G. Bag Natural triterpenoids as renewable nanos: Formation of helical

nano-fibers, nano-vesicles, nano-spheres and dynamic soft-materials

2:50 – 3:10 M. Misra Novel green materials from biobased resin systems and lignin hybrid: Processing an applications

3:10 – 3:30 J. M. Streff Design and development of hydrolytically-degradable poly(quinic Acid carbonate)s for orthopedic applications

3:50 – 4:20 A. K. Mohanty Bioplastics and green materials from renewable resources: What is new!

4:20 – 4:50 J. V. Kurian Embracing the era of renewably sources materials: a family of high performance polymers and fibers from dupont

4:50 – 5:20 M. K. Patel An overview of environmental benefits for polymers made from renewable resources

5:20 – 5:40 J. Skrobot Synthesis and possible medical application of injectable macromers derived from fatty acids

RESPONSIVE AND SMART POLYMERSAfternoon session Speaker Title

1:30 – 2:00 C. W. Bielawski Polymer mechanochemistry: Using force to direct molecular reactivity

2:00 – 2:30 M. J. Monteiro Polymer architectures and nanostructures generated via living radical polymerization

2:30 – 2:50 M. E. H. El- Sayed

Rational design & synthesis of “intelligent” star polymers for cytoplasmic delivery of therapeutic nucleic acids

2:50 – 3:10 X. Huang Synthesis of well-defined photo-crosslinked polymeric nanocapsules by surface-initiated raft polymerization

3:10 – 3:30 A. H. Gröschel Precise heirarchial self-assembly of multicompartment micelles3:50 – 4:20 S. J. Rowan Supramolecular approaches to stimuli-responsive polymers

27

4:20 – 4:50 P. H. Toy Multifunctional polymeric catalysts and reagents

4:50 – 5:20 D. E. Bergbreiter

Responsive polymer solubility as a tool in synthesis

5:20 – 5:40 J. Seuring Concealed qualities-polymers with upper critical solution temperature in water

7:00 – 9:00 PM Gala Banquet Dinner(Business or National Dress)

Awards Presentation

Monday, January 9, 2012

POLYMERS AS THERAPEUTICSMorning Session Speaker Title

8:00 – 8:30 F. Caruso Monomers based on methacrylic acid bisphosphonates for polymer drug delivery

8:30 – 9:00 J. Leroux Polymer therapeutics for celiac disease9:00 – 9:20 A. Almutairi The art of falling apart: Exploiting nanomaterial disassembly for

medicine and pharmacy9:20 – 9:40 S. Kachbi Monomers based on methacrylic acid bisphosphonates for

polymer drug delivery9:40 – 10:00 F. Rasoul Synthesis and evaluation of biodegradable hydrogels based on

hyperbranched polyester for alveolar bone treatment10:20 – 10:50 M. Weck Multifunctional polymeris for theranostics and tissue engineering10:50 – 11:20 E. Connor Managing serum potassium with RLY5016. An insight into

polymer drug development at Relypsa11:20 – 11:50 K. L. Wooley Nanoscopic polymer objects of unique shapes and morphologies

and well-defined structures and dimensions as controlled drug delivery devices

ADVANCES IN POLYMER SYNTHESISMorning Session Speaker Title

8:00 – 8:30 B. Voit Synthesis of functional materials through combination of controlled polymerization techniques and efficient polymer

analogous reactions8:30 – 9:00 E. W. Meijer Non-covalent synthesis of functional supramolecular systems9:00 – 9:20 W. T. Ford Polystyrene composites of single-walled carbon nanotubes9:20 – 9:40 D. J. Burke Novel polyesters based on cyclobutanediol: Energy efficient

synthesis of bisphenol-a free materials9:40 – 10:00 T. Choi Olefin metathesis polymerization from alkynes10:20 – 10:50 S. Valiyaveettil Design and synthesis of conjugated polymers and hybrid

materials10:50– 11:20 T. Yokozawa Precision synthesis in chain-growth condensation polymerization11:20 – 11:40 N. Haraguchi Development of Novel polymer-supported macmillan catalysts

with ionic bond for asymmetric reaction11:40 –12:00 D. Kuckling Synthesis of functional smart polymers

28

29

THE SYNTHESIS OF LARGE AND SMALL MOLECULES USING OLEFIN METATHESIS CATALYSTS

ROBERT H. GRUBBS, CALIFORNIA INSTITUTE OF TECHNOLOGYPASADENA, CA, U.S. A.

Ruthenium based olefin metathesis catalysts have provided new routes to olefins that appear in a variety of structures. Their functional group tolerance and ease of use allow their application in the synthesis of multifunctional bioactive molecules that are being explored as pharmaceutical agents. The same systems are also useful for the synthesis of an array of new materials from multifunctional polymers to supramolecular systems. Of particular interest are brush polymer systems that phase separate into ordered structures. The long-range order of these periodic structures is controlled by the selection and ordering of the block components. We are exploring the factors that control the spacing and attempting to develop a detailed picture of the phase separation process. The catalysts can also be used to construct telechelic polymers and in the production of composite materials. Underlying these developments has been the discovery of active catalysts with controlled selectivity through the synthesis of new ligands that control the geometry of the intermediate carbene and metallacycle complexes. A recent finding has been a ligand system that controls the geometry of the double bond that is formed in the metathesis process. A particularly efficient catalyst that will dimerize olefins to the Z geometry in high yields has been developed. These systems also generate a family of high Z polymers.

“Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials, R. H. Grubbs, Adv. Synth. Catal. 2007, 349, 34-40.“Synthesis of Telechelic Polyisoprene via Ring-Opening Metathesis Polymerization in the Presence of Chain Transfer Agent.” R. M. Thomas, R. H. Grubbs, Macromolecules 2010, 43 (8), 3705-3709.“Synthesis and Direct Imaging of Ultrahigh Molecular Weight Cyclic Brush Polymers.” Y. Xia, A. J. Boydston, R. H. Grubbs, Angew. Chem. Int. Ed. 2011, 50, 1-5.“Z-Selective Homodimerization of Terminal Olefins with Ruthenium Metathesis Catalyst”. B. Keitz, K. Endo, M. Herbert, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133 (25), 9686-9688.

Keynote Lecturer

30

Session Lectures

31

32

OLEFIN POLYMERIZATION WITH METALLOCENE AND “POST METALLOCENE” DERIVATIVES OF ZIRCONIUM

Theo Agapie, 1 Muhammad Atqullah,2 Steven Baldwin,1 John Bercaw,1,2 Hans Brintzinger,3 Emmannuel Despagnet-Ayoub,1 Suzanne Golisz,1 Sara Klamo, Rachel Klet,1 Taylor Lenton,1 Ian

Tonks,1 and Matthew Winston1

1Chemistry Department, California Institute of Technology, Pasadena, CA 911252King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia 3Fachbereich

Chemie, Universität Konstanz, D-78457 Konstanz, Germany

bercaw@caltech.edu

Extensive investigations of the origins of tacticity control for propylene polymerizations with ansa-zirconcene-based catalysts have provided a good understanding of the important stereo-electronic effects that dictate the preferred enantioface for enchainment of the a-olefin. Less well understood are the factors that determine molecular weights. Thus, measurements of the rates for initiation, chain propagation and chain transfer are needed. Some initial experiments along these lines have been performed. Rates for polypropylene initiation, and propagation have been determined at low temperatures for the well defined catalyst initiator [(h5-C5H5)(h

5-C5Me5)ZrCH2CMe3]+[CH3B(C6F5)3]-, and kinetic deuterium isotope effects for the rates of enchainment of CL2=CHCH3 (L = H, D) have been measured. The identities of cationic species generated from zirconocene precatalysts, when treated with [Ph3C]+[B(C6F5)4]- in the presence of diisobutylaluminum hydride, have been established, and their reactions under propylene polymerization conditions have been investigated[1].

Post metallocene zirconium and titanium catalysts with tridentate bis(phenolate)-donor (donor = pyridine, furan, and thiophene) “LX2” pincer ligands have been investigated as propylene and ethylene polymerization catalysts[2]. Ethylene polymerizations, in both homogeneous and silica-supported modes, have been conducted. Analogous pincer ligands having thiophenolate, anilide, and phospha-anilide X type ligands, as well as those having N-heterocylic carbene L type donors have been prepared, and their performance as ligands on zirconium, titanium, and vanadium catalysts for olefin polymerizations has been explored.

[1] Baldwin, S. M.; Bercaw, J. E.; Brintzinger, H. H J. Am. Chem. Soc. 2010, 132, 13969-13971.

[2] Agapie, T.; Henling, L. M.; DiPasquale, A. G.; Rheingold, A. L.; Bercaw, J. E. Organometallics 2008, 27, 6245-6256.

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Polyolefins

SINGLE SITE CATALYSIS FOR OLEFIN POLYMERISATION, POLYOLEFIN DEPOLYMERISATION

AND RELATED REACTIONSJean-Marie Basset1

1Kaust Catalytic Center, King Abdullah University of Science and Technology University, 23955-6900 Thuwal, Saudi Arabia

&Laboratoire de Chimie Organométallique de Surface, University of Lyon, UMR5265 C2P2 CNRS-

CPE-UCBL, 69616 Villeurbanne France

E-mail: jeanmarie.basset@kaust.edu.sa

Catalysis is the number one technology in chemical industry and petroleum refining: 95 percent of all products (volume) are synthesized by means of catalysis. The advantages of catalytic processes are due to the mild reaction conditions, their cost efficiency, and their environmentally friendly character. Nevertheless sometimes catalysis is not selective enough, which increases products involved in green house effects (like CO2, NOx or particles). New reactions are needed (for example, methane, which is abundant in the world, is not selectively transformed into valuable products). A predictive approach of catalysis is emerging due to the spectacular progresses made in the synthesis of well-defined materials. The Nano-control of active site via a pluridisciplinary approach is one of the ways to address this issue of catalytic “environmental” or “energy” performances. It is now possible to achieve the rational design and synthesis of well-defined materials with the expected structure, acidity, porosity in the field of oxides, carbon based materials or zerovalent mono and pluri metallic particles of given size and composition. The grafting of organometallic compounds onto these materials results in the synthesis of “single site” catalysts both on oxide or metallic nanoparticles. The full characterisation of the grafted organometallic complexes results from the use of a variety of techniques coming from surface science and molecular chemistry: in situ IR, in situ 1H, 13C NMR, 2D NMR, EXAFS, Surface Microanalysis, determination of the stoichiometry of surface reactions. The detailed knowledge of the structure of the active site which results from this careful determination allows one to determine elementary steps of heterogeneous catalysis and a structure activity relationship can be achieved in several cases. A new generation of catalysts, new catalytic reactions, improvement of existing catalysts, related to energy, environment and polymer materials have been discovered on these single site catalysts. Examples will be given in the field of direct transformation of ethylene to propylene, Ziegler-Natta depolymerisation, supported metallocenes and polymerisation, Alkane metathesis, Methane coupling to ethane, Methane-olysis of alkanes, Metathesis of olefins, dehydrogenation of paraffin’s. In particular in the field of polymerisation on well defined single site catalysts the specific role of the support will be explained in a very comprehensive way.

Vidal, V.; Theolier, A.; Thivolle-Cazat, J.; Basset, J. M.Science,1997, 276(5309),, 99-102.Avenier, P.; Lesage, A.; Taoufik, M; Basset J.-M.; et al.J. Am. Chem. Soc. 2007, 129, (1), 176-186.Millot, N.; Soignier, S.; Santini Catherine, C.; Baudouin, A.; Basset J.-M. J. Am. Chem. Soc. , 2006, 128, (29), 9361-70.Millot Nicolas; Soignier Sophie; Santini Catherine C.; et al. J. Am. Chem. Soc. 2006 Volume: 128 Issue: 29 Pages: 9361-9370 Polyolefins

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APPROACHING OLEFIN POLYMERIZATION FROM FIRST PRINCIPLE

Tom Ziegler

Department of Chemistry University of Calgary, Calgary, Alberta Canada T2N1N4.

Ziegler@ucalgary.ca.

Olefin polymerization is one of the most important industrial processes in which transition metal catalysts play a key role. In this process monomers with an olefinic double bond are stitched together into long polymers with single carbon-carbon bonds. The first part of the talk illustrates how a combination of quantum mechanical methods and statistical approaches can be used to elucidate the nature of the active site in olefin polymerization catalysts. The last part of the talk demonstrates how theoretical models can be used to simulate polymer growth and help in the design of new catalysts.

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STEREOSELECTIVE (CO)POLYMERIZATIONS OF STYRENE WITH SINGLE-SITE MONO-COMPONENT

AND BINARY LANTHANIDOCENE CATALYSTS Jean-François Carpentier,1 Evgueni Kirillov,1 Yann Sarazin,1 Michael Duc,2 Abbas Razavi2

1Organometallics and Catalysis, University of Rennes – CNRS, 35042 Rennes, France 2Total Petrochemicals Research, Feluy, Belgium

E-mail: jcarpent@univ-rennes1.fr

While many polystyrene (PS) architectures are known and can be generated almost at will by judicious choice of the initiating/catalytic system, coordinative-insertive catalysis promoted by well-defined metal complexes has enabled the preparation of stereoregular PS. Thus, several homogeneous systems are now known for the preparation of highly syndiotactic PS (sPS).[1] Also, a handful of single-site initiators based on group 3 or 4 metals were recently introduced for the isospecific preparation of PS (iPS), thus showing considerable improvement over the traditional heterogeneous and anionic systems which only gave isotactic-enriched PS.[1b]

Our group has had a longstanding interest in the controlled polymerization of styrene to generate (co)polymers with specifically tailored architectures. We have thus shown that {Me2C(Cp)(Flu)}- and rac-{Me2C(Ind)2}-based neutral allyl ansa-lanthanidocenes (Cp = cyclopentadienyl; Flu = 9-fluorenyl; Ind = 2-indenyl) constituted remarkable single-site, single-component initiators for the highly syndio- (up to 99 % rrrr pentads)[2] and isoselective (up to 99 % mmmmmm heptads)[3] polymerization of styrene, respectively. Moreover, those catalysts showed unique abilities to copolymerize stereoselectively styrene with other monomers, namely ethylene and isoprene, leading to new materials with peculiar thermo-mechanical properties.

More recently, in attempts to improve the suitability of these stereoselective catalysts for larger-scale applications, we have become interested in the reversible chain transfer polymerization, performed in the presence of a transition metal catalyst and an excess of a comparatively inexpensive chain transfer agent (CTA, such as ZnEt2, Mg(nBu)2 or AlR3).

[4] In such system, provided the chain transfer between growing (P*) and dormant (P) polymer chains carried respectively by the transition and main group metals is fast and reversible (ktransfer >> kprop), the number of polymer chains generated by catalytic center is no longer 1 (as in a living polymerization) but is instead equal to the number of molecules of CTA introduced in the reaction medium. Scope and limitations of this strategy to the production of sPS and iPS with binary systems made of a lanthanidocene catalyst and an alkyl-metal CTA will be described.[5]

[1] a) Ishihara, N.; Seimiya, T.; Kuramoto, M.; Uoi, M. Macromolecules 1986, 19, 2464. b) Rodrigues, A.-S.; Kirillov, E.; Carpentier, J.-F. Coord. Chem. Rev. 2008, 252, 2115. [2] a) Kirillov, E.; Lehmann, C. W.; Razavi, A.; Carpentier, J.-F. J. Am. Chem. Soc. 2004, 126, 12240; b) Rodrigues, A.-S.; Kirillov, E.; Lehmann, C. W.; Roisnel, T.; Vuillemin, B.; Razavi, A.; Carpentier, J.-F. Chem. - Eur. J. 2007, 13, 5548; c) Rodrigues, A.-S.; Kirillov, E.; Vuillemin, B.; Razavi, A.; Carpentier, J.-F. Polymer 2008, 39, 2039-2045. d) Perrin, L.; Sarazin, Y.; Kirillov, E.; Carpentier, J.-F.; Maron, L. Chem. - Eur. J. 2009, 15, 2773; e) Perrin, L.; Kirillov, E.; Carpentier, J.-F.; Maron, L. Macromolecules 2010, 43, 6330. [3] a) Rodrigues, A.-S.; Kirillov, E.; Roisnel, T.; Razavi, A.; Vuillemin, B.; Carpentier, J.-F. Angew. Chem. Int. Ed. 2007, 46, 7240. (b) Annunziata, L.; Rodrigues, A.-S.; Kirillov, E.; Sarazin, Y.; Okuda, J.; Perrin, L.; Maron, L.; Carpentier, J.-F. Macromolecules 2011, 44, 3312. [4] For recent reviews on reversible chain growth polymerization of olefins, see: a) Kempe, R. Chem.- Eur. J. 2007, 13, 2764; b) Sita, L. R. Angew. Chem. Int. Ed. 2009, 48, 2464. [5] a) Sarazin, Y.; de Frémont, P.; Annunziata, L.; Duc, M.; Carpentier, J.-F. Adv. Synth. Cat. 2011, 353, 1367. b) Annunziata, L.; Duc, M.; Carpentier, J.-F. Macromolecules 2011, 44, 7158.

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INFLUENCE OF COMBINATION OF FILLERS AND FIBERS ON THE MORPHOLOGICAL, THERMAL AND

MECHANICAL PROPERTIES OF RECYCLED POLYMERS

Mariam AlMaadeed

Materials Technology Unit, Qatar University, Qatar

E-mail: m.alali@qu.edu.qa

Recycled polymers have a positive impact on the environment, but their properties deteriorate after recycling. Enhancing these polymers by additives to modify their properties is a very challenging procedure. Each additive has its own strengths and limitations, both from required properties and from an environmental point of view. The addition can reduce the crystallinity of the polymer, hindering the mobilization of the macromolecular chain and prevent ordering. Depending on the type of the filler and its adhesion to the polymer, there can be a modification to the properties of the composite.

Examples of date palm fibers, mica, glass fibers, and blends with other polymers, will be presented to show the effect of adhesion, load percentage and filler types on the activation energy, thermal stability, mechanical stability and morphology of the distribution. A balance between the required properties and life cycle assessment will be discussed.

SEM photo of the fractured surface of recycled polypropylene based hybrid composites of date palm wood flour/glass fibre after tensile testing.

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NEW POLYMERS BY METALLOCENE CATALYSED OLEFIN POLYMERIZATION

Walter Kaminsky

Chemistry Department, University of Hamburg, GermanyE-mail: kaminsky@chemie.uni-hamburg.de

Metallocene/methylaluminoxane (MAO) and other single site catalysts are highly active for the production of precisely designed polyolefins and engineering plastics. Especially zirconocene complexes have opened a frontier in the area of new polymer synthesis and processing. By changing the ligand structure, these catalysts allow the synthesis of isotactic, isoblock, syndiotactic, stereoblock, or atactic polypropylenes as well as new copolymers with superior properties such as film clarity, tensile strength and lower extractables [1].

In recent years there is much interest on short and long chain branched polyolefins and on copolymers with an alternating structure. The copolymerization of ethene or propene with oligomers or long chained 1-olefins by metallocene catalysts leads to materials, which show two different melting points, one for the backbone chain the other for the side chain. Long chain branched polypropylenes can easier processed by a high melt solidification compared to short chain branched polypropylenes. This is an advantage for the production of blow films and coating. The long chain branches have a great influence on the entanglement and on the viscosity [2]. Alternating ethene/propene copolymers are characterized by very low glass transition temperatures.

Metallocene catalysts are excellent tools for the polymerization of cycloolefins such as cyclopentene, norbornene, and their substituted compounds. In contrast to the polymerization by Ziegler-Natta catalysts, were ring and double bond opening occurs simultaneously, by metallocenes exclusively double bond opening is observed. While the tactic homopolymers of cycloolefins cannot be processed, because of there high melting points, there is much interest in the copolymers of norbornenes with ethene, respectively. These cycloolefin copolymers (COC) are amorphous with an useful glass transition temperature between 80 – 200°C, a high transparency, a low density, and a low adsorption of water.

Exceptionally strong materials can be synthesized by in-situ polymerization with single site catalysts in the presence of nanofiller. Metallocene/MAO catalysts are soluble in hydrocarbons and therefore they can cover perfectly the surface of particles or fibers. By addition of ethene or propene, a polyolefin film is formed, covering the nanoparticles, layered silicates, or fibers such as carbon nanotubes. The resulting polyethylene and polypropylene nanocomposites cause a tremendous boost of physical and chemical properties such as improved stiffness, high gas barrier properties, significant flame retardancy, and high crystallization rates. Polyolefin nanocomposites produced by in-situ generation show better mechanical properties than materials, produced by mechanical blending [3].

[1] Kaminsky, W. Macromol. Chem. Phys. 2008, 209, 457-466.[2] Stadler, F.J.; Arican-Conley, B.; Kaschta, J.; Kaminsky, W.; Muenstedt, H. Macromolecules 2011, 44, 5053-5063.[3] Kaminsky, W.; Funck, A.; Klinke, C. Top Catal. 2008, 48, 84-90.

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THE ACTIVATION OF SOLUBLE OLEFIN POLYMERIZATION CATALYSTS

Manfred Bochmann

Wolfson Materials and Catalysis Centre, School of Chemistry, University of East Anglia, Norwich NR4 7TJ, UK.

Email: m.bochmann@uea.ac.uk

Polymerization catalysts based on soluble catalysts precursors offer excellent activities and are able to generate a wide range of polymeric materials with well-controlled properties. 1This talk will provide an overview of aspects of catalyst activation, their behaviour in solution, and recent progress with modelling the growing polymer chain. The interplay of all these factors is an example of how even weak interactions can cooperate to lower the transition state energy and greatly increase catalyst performance.2,3

While activators based on weakly coordinating anions give high activities and well-defined active species, industry prefers catalyst activation with methylaluminoxane (MAO), a much less well understood system. We will discuss investigations aimed at identifying the species responsible for the metallocene activation by MAO, the interaction of MAO with donors, and the question to “free” and “associated” trimethylaluminium in the MAO structure.

References:

1. Reviews: (a) M. Bochmann, “The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts”, Organometallics 2010, 29, 4711 – 4740. (b) M. Bochmann, “Kinetic and Mechanistic Aspects of Metallocene Polymerisation Catalysts”, J. Organomet. Chem. 2004, 689, 3982-3998.2. C. Alonso-Moreno, S. J. Lancaster, J. A. Wright, D. L. Hughes, C. Zuccaccia, A. Correa, A. Macchioni, L. Cavallo, M. Bochmann, “Ligand Mobility and Solution Structures of the Metallocenium Ion Pairs [Me2C(Cp)(fluorenyl)MCH2SiMe3+···X–] [M = Zr, Hf; X = MeB(C6F5)3, B(C6F5)4]”, Organometallics 2008, 27, 5474 – 5487.3. K. P. Bryliakov, E. P. Talsi, A. Z. Voskoboynikov, S. J. Lancaster, M. Bochmann, “Formation and Structures of Hafnocene Complexes in MAO and AlBui3/[CPh3][B(C6F5)4] Activated Systems”, Organometallics 2008, 27, 6333 – 6342.

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COMPREHENSIVE APPROACH FROM ACTIVE SITES TO PARTICLE FOR THE NEXT GENERATION

ZIEGLER – NATTA CATALYSTSMinoru Terano

Japan Advanced Institute of Science and Technology1-1, Asahidai, Nomi, Ishikawa, 923-1292, JAPAN

Phone: +81-761-51-1620, E-mail: terano@jaist.ac.jp

Traditional Ziegler-Natta catalysts have been playing the most important role for the industrial polyolefin production despite the world-wide research efforts on homogeneous metallocene and post-metallocene catalysts. Especially, the isotactic polypropylene has beenalmost completely covered by the catalysts.

The developments of the catalysts have been conducted by the independent research oneach of the targets. The search of donors were for active sites ( activity, isospecificity andhydrogen response ) and that of preparation methods were for particle ( B. D., plant operation ). However, the comprehensive design of the catalysts including both of the active sites and the particle are indespensable for the next break- through on the industrial olefin polymerization catalysts.

This paper shows the comprehensive approach from the active sites to the particle onthe traditional Ziegler-Natta catalysts. The effects of micro-dispersion states of Ti species on the catalyst performances were investigated using TiCl3 and CpxTiCl4-x-based model catalysts having a variety of Ti contents.

New aspects on the olefin homo- and co-polymerizations using these 2 types of thecatalysts will also be reported.

[1] Kouzai, I.; Liu, B.; Wada T.; Terano, M. Macromol. Reac. Eng. 2007, 1, 160-164.[2] Wada, T.; Taniike, T.; Kouzai, I.; Takahashi, S.; Terano, M. Macromol. Rapid Commun. 2009, 30, 887-891.

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SINGLE SITE CATALYST MOLECULAR DESIGN AND MULTICOMPONENT CATALYST ENGEERING FOR

PRODUCTION OF NON-COMMODITY POLYOLEFINS; CASE STUDIES

Vincenzo Bellia,1 Olivier Miserque,1 Dominique Vereecke,1 Christian Lamotte1, Catherine Den Daw,1 Kai Hortmann,1 liliane Peters,1 Martine Slawinsky,1 Margo Lopez,2 Vladimir Marin,2 Manal

Farah,3 Hind Mamlouk,3 Abbas Razavi,1,2,3 June2011

1Total Petrochemical Research Centre Feluy, Zone Industrielle C, Seneffe B-7181, Belgium.

2Total Petrochemical Research Centre, 1700 Battleground road, LaPorte, TX, 77571, USA. 3Total Research Centre Qatar Doha Qatar

abbasrazavvi@skynet.be

Chirotopic single site catalysts related polypropylene exhibit large diversity in their polymer chain microstructures far exceeding the chain tactic varieties observed with the polypropylene obtained with multiple site, heterogeneous TiCl3 based Ziegler-Natta type catalysts. The “flexible” organic ligand environment in former permits substitution modifications that impacts enantio- and regio-selective behavior of the active transition metal and stereochemistry of olefin insertion / propagation reactions. By applying different ligand modification possibilities as tools for molecular catalyst design, numerous metallocene catalysts with varying geometry, combing C2, Cs or C1 symmetries with proper steric bulk of the substituents, have been designed, synthesized and employed in polymerization of propylene to syndiotactic- , isotactic and stereo block type polypropylene extensively in the last two decades [1]. By employing the same or similar designer molecules we investigated the ethylene-propylene copolymerization behavior of the resulting catalysts to elaborate their capabilities and shortcomings in producing polypropylene based copolymers with properties of commercial interest.

Similar approach is attempted for polyethylene based single site catalysts. By investigating the impact of metallocene catalyst’s substitution arrangements and aperture angles on polyethylene chain architecture and polymers, physical and mechanical properties, potentials and limitations of catalyst molecular design for the production of “perfect” polyethylene resins for a variety of applications is highlighted [2]. Finally, it is presented in a plausible manner, how the heterogenization process, a challenging and but essential step in single site catalyst preparation for most industrial processes could be turned into myriad of opportunities for engineering multi- component catalyst for the preparation of bi- or multi-phasic resins in a single reactor industrially [3].

[1] (a) Site Selective Ligand Modification and Tactic Variation in Propylene Chains produced with Metallocene Catalysts. Razavi, A.; Thewalt, U. Coordination Chemistry Reviews 250 2006, 155 –169. (b) Computational Design of C2-Symmetric Metallocene-Based Catalysts for the Synthesis of High Molecular Weight Polymers from Ethylene/Propylene Copolymerization. Tebikie, W. Dongqi, W.; Razavi, A.; Ziegler, T. Organometallics, 2008, 27 (24), 6434–6439 (c) In Silico Design of C1- and Cs-Symmetric Fluorenyl-Based Metallocene Catalysts for the Synthesis of High-Molecular-Weight Polymers from Ethylene/Propylene Copolymerization. Tebikie, W.; Dongqi, W.; Razavi, A.; Ziegler. T. Organometallics, 2009, 28 (5), 1383–1390.

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[2] (a) Process for preparing and using a supported metallocene-alumoxane catalyst. A. Razavi, G. Debras (Fina Research); US. Pat. Appl., US1999/296034A (04/21/1999); PCT. Int. Appl. US6218330B1 (04/17/2001). (b) Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution. A. Razavi (Fina Research); US. Pat. Appl., US1997/797800A (02/07/1997); PCT. Int. Appl. US5914289A (06/22/1999). (c) Process for preparing and using meso/racemo-[Bis(Indenyl)Ethane]Zirconium Dichloride compounds. A. Razavi (Fina Research); US. Pat. Appl., US1997/948224A (10/09/1997); PCT. Int. Appl. US6103656A (08/15/2000).

[3] (a) Impact copolymer in single reactor. A. Razavi, (Total Petrochemicals RES Feluy); US Pat. Appl., 12/065,462 (08/07/2008); PCT. Int. Appl. US2009/0118447A1 (05/07/2009). (b) Polyolefins prepared from a metallocene and a new single site catalyst components in a single reactor. A. Razavi, (Total Petrochemicals RES Feluy); EP Pat. Appl. WO2005EP55398A (10/20/2005); PCT. Int. Appl. WO 2006/045738A1 (5/04/2006). (h) Polyolefins prepared from two single site catalysts components in single reactor. A. Razavi, (Total Petrochemicals RES Feluy); EP Pat. Appl. WO2005EP55395A (10/20/2005); PCT. Int. Appl. WO 2006/045736A1 (5/04/2006).

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43

EFFICIENT AND CATALYST FREE POLYMER FUNCTIONALIZATION AND COUPLING

Rachel K O’Reilly

Department of Chemistry, University of Warwick, Coventry, CV4 7AL

E-mail: R.K.O-Reilly@warwick.ac.uk

Reactions denoted ‘Click reactions’ and applications using these chemistries in some way are seemingly limitless; one has only to look at the myriad of articles and review papers written on Click chemistry to appreciate how far the term echoes throughout the chemical, biological and materials fields. Since its introduction in 2001 by Sharpless et al., the concept has found wide ranging implications across many and diverse areas of chemistry. In polymer science, the ability to readily modify polymer chain ends, or link two or more polymer chains together represents an important and not insignificant task, and thus the Click philosophy and family of reactions have found extensive application in polymer science.

Whilst Click is a concept rather than any given reaction, arguably the copper-catalyzed azide-alkyne Huisgen 1,3 dipolar cycloaddition (CuAAC) has become the de facto standard for many applications where Click reactions are required, and thus has become almost synonymous with the term ‘Click reaction’. Although it undoubtedly fulfils all of the requirements in the original definition of a Click reaction, it is not without its limitations, the primary one being the requirement for a metal catalyst, the subsequent complete removal of which can be problematic, particularly for biomedical applications. There is also no single Cu(I) complex that has been identified as a suitable ‘off the shelf’ optimal catalyst or precatalyst for CuAAC reactions under all conditions, thus requiring tailoring of the reaction conditions for each situation where CuAAC is used, particularly when the reaction is carried out in organic rather than aqueous media.

Alternative reactions to CuAAC that do not require a metal catalyst and that have been labeled as Click reactions in the literature include the Diels-Alder and several thiol-based reactions. A reaction that fulfils all of the requirements of a Click reaction, although has attracted much less attention, is the fast, atom efficient, catalyst free, air insensitive and quantitative inverse electron demand Diels-Alder between tetrazines and strained alkenes or acetylenes. This presentation will explore the application this robust and mild coupling chemistry for the functionalization and coupling of polymers and self-assembled nanostructures.

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FUNCTIONALIZED POLYMERS FOR FUNCTIONAL MATERIALSRobert B. Grubbs1,2

1Department of Chemistry, Stony Brook University, Stony Brook, NY 11794 2Center for Functional Nanomaterials, Brookhaven National Laboratory,Upton, NY 11793

E-mail: robert.grubbs@stonybrook.edu

Living polymerization techniques enable the preparation of macromolecules capable of self-assembly so that placement of monomer functionality is controllable on longer length scales. Due to their high level of functional group tolerance, controlled radical polymerization techniques have proven indispensable for the synthesis of new polymers and copolymers. These techniques have been especially useful in enabling the introduction of monomer units bearing functional groups with reactivity orthogonal to the propagating radicals involved in chain growth. We have used nitroxide-mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation-chain transfer (RAFT) polymerization for the preparation of block copolymers that have designed properties resulting from the specific functional groups present and their location along the polymer chain.

In one specific system, we have synthesized block copolymers with alkyne-functional blocks as precursors for the preparation of cobalt nanoparticles by direct NMP, ATRP, or RAFT polymerization of alkyne-functional monomers [6] or by the coupling of alkynes to polymers of 4-bromostyrene, which were prepared by NMP [7]. In a second set of investigations, we have prepared amphiphilic block copolymers designed to assemble into thermally responsive micelles in water by ATRP and NMP from poly(ethylene oxide)-based macroinitiators [8]. The synthesis and characterization of these and related block copolymer-based materials will be discussed

[6] (a) Grubbs, R. B. J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 4323-4336; (b) Sessions, L. B.; Mîinea, L. A.; Ericson, K. D.; Glueck, D. S.; Grubbs, R. B. Macromolecules 2005, 38, 2116-2121; (c) Mîinea, L. A.; Sessions, L. B.; Ericson, K. D.; Glueck, D. S.; Grubbs, R. B. Macromolecules 2004, 37, 8967-8972. [7] Sessions, L. B.; Cohen, B. R.; Grubbs, R. B. Macromolecules 2007, 40, 1926-1933. [8] (a) Wegrzyn, J. K.; Stephan, T.; Lau, R. N.; Grubbs, R. B. J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 2977-2984; (b) Aubrecht, K. B.; Grubbs, R. B. J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5156-5167; (c) Sundararaman, A.; Stephan, T.; Grubbs, R. B. J. Am. Chem. Soc. 2008, 130, 12264-12265; (d) Cai, Y.; Aubrecht, K. B.; Grubbs, R. B. J. Am. Chem. Soc. 2011, 133, 1058-1065.

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SYNTHESIS OF NEW FUNCTIONALIZED POLYTHIOPHENES FOR ORGANIC BIOSENSORS

Clément Suspène,1 Abderrahim Yassar,2 Gilles Horowitz2

1ITODYS, Université Paris Diderot, 75205 Paris Cedex 13, France2LPICM, Ecole Polytechnique, CNRS, 91128 Palaiseau Cedex, France

E-mail: clement.suspene@univ-paris-diderot.fr

New generations of low power, low cost, and portable sensing devices are needed for homeland

security and monitoring of agricultural, medical, and manufacturing environments. Leading candidates include sensors made of organic field-effect transistors, which are based on the simple change of the output signals in response to the binding of analytes. [1]The advantages of OFET sensors comprise low power consumption and the ease of high precision of electrical measurements. Sensors based on organic materials have already demonstrated the ability to detect numerous analytes of interest in vapour systems,[2] and the recent adaptation to aqueous environments indicates their potential for complex biological detection.[3]

Conjugated polymers have long been considered as fluorescent, electrochemical biosensors and chemiresistor materials. The integration of molecular recognition elements into their structure is attractive; however, these materials are limited by design and synthetic methods for the functionalization of organic semiconductors with bio-receptors. In this communication we report a new methodology for the synthesis of well-defined new regioregular polythiophenes functionalized with biological recognition elements such as biotin, through a simple and efficient approach using GRIM polymerisation. The functional acidic groups required for the anchoring of the bio-probes are randomly distributed into P3HT in proportions that can be tuned.

[1] Sokolov, A. N.; Roberts, M. E.; Bao, Z. Mater. Today 2009, 12 (9), 12–20.[2] Crone, B.; Dodabalapur, A.; Gelperin, A.; Torsi, L.; Katz, H. E.; Lovinger, A. J.; Bao, Z. Appl. Phys. Lett. 2001, 78, 2229–2231.[3] Roberts, M. E.; Mannsfeld, S. C. B.; Queraltó, N.; Reese, C.; Locklin, J.; Knoll, W.; Bao, Z. Proc. Natl. Acad. Sci. 2008, 105 (34), 12134–12139.

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METAL-CATALYZED MULTICOMPONENT POLYMERIZATION - A NEW METHOD FOR THE CONSTRUCTION OF CONJUGATED MATERIALS

David C. Leitch,1 Bruce A. Arndtsen*1

1Chemistry Department, McGill University, Montreal, QC, Canada, H2T 2E3

E-mail: david.leitch@mail.mcgill.ca

The development of methods to efficiently access new classes of polymers remains a central goal in materials research. Among the variety of materials that have been discovered, conjugated polymers have myriad potential applications, ranging from chemical sensors to solar energy harvesters. Nevertheless, a challenge remains in how to efficiently assemble such polymers, especially those with complex structures, as they are typically generated via the initial assembly of the repeat unit(s), which themselves can take multiple synthetic steps. In order to address this challenge, we have developed a palladium-catalyzed multicomponent polymerization reaction. This approach exploits transition metal catalysis as a tool to assemble several simple monomers in a controlled manner, providing a method to generate polymers with complex repeat units in a single reaction (see Figure). The application of this catalytic polymerization methodology to the efficient synthesis of new conjugated polymers, including the generation of libraries of conjugated materials, will be presented.

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PHASE TRANSFER ACTIVATION OF GRUBBS’ ROMP CATALYST SYSTEMS

Robert Tuba,1 Hassan S. Bazzi,1 John A. Gladysz2

1Department of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar,2Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-

3012, USAE-mail: robert.tuba@qatar.tamu.edu

Polynorbornene – which can be synthesized by ring opening methathesis polymerization (ROMP) with Grubbs’ catalyst – is used in the automotive and appliance industries mainly as vibration and noise isolators and produced on a scale of thousands of tons per year. Grubbs’ first and second generation alkene metathesis catalysts have been extensively studied mechanistically. A phosphine must first dissociate, giving a fourteen valence electron intermediate, to initiate the catalytic cycle. It was found that in the catalytic cycle the reverse phosphine reassociation step competes with the subsequent alkene binding step in the coordination sphere of the catalyst, slowing the observed rate constant. One option to improve the activity of the catalyst system is to supress the reassociation step by the lowering the free dissociated phosphine concentration in the reaction mixture. This can be achieved for example by fluorous/organic solvent biphasic catalytic systems when the dissociated phosphine has a higher affinity for the fluorous phase and the fourteen-valence-electron intermediate active species and substrates are liphophilic. Thus, following the dissociation the fluorophilic phosphine remains in the fluorous phase while the “activated” catalytic cycle is running in the organic phase.

Grubbs’ second generation alkene metathesis catalyst and the fluorous analog (H2IMes)((Rf8-(CH2)2)3P)(Cl)2Ru(=CHPh) (1, Rf8 = (CF2)7CF3) catalyze the ROMP of norbornene at essentially identical rates (CDCl3, RT). However, dramatic accelerations can be observed with 1 in the presence of the fluorous solvent perfluoro(methylcyclohexane) (PFMC). It is proposed that the PFMC scavenges the fluorous phosphine Rf8(CH2)2)3P (PFMC/toluene partition coefficient >99.7:<0.3), allowing alkenes to more effectively compete for the active catalyst. However, this phenomenon is seen only when 1 (partition coefficient 39.6:60.4) is added as a PFMC as opposed to CDCl3 solution. Analogous effects are observed with a 7-oxanorbornene-based N-butylsuccinimide. The molecular weights, polydispersities, glass transition temperatures, and cis/trans C=C linkage ratios of the polynorbornene produced under monophasic and biphasic conditions are generally comparable.

Scheme 1. Two approaches to phase transfer activation of ROMP with catalyst 1.The bottom protocol gives dramatically faster polymerization than monophase conditions (CDCl3).

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MACROMOLECULAR MATERIAL DESIGN VIA MODULAR SYNTHETIC STRATEGIES

Christopher Barner-Kowollik

Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany.

christopher.barner-kowollik@kit.edu

The present lecture will describe how modular synthetic strategies in polymer chemistry can be employed to not only construct highly defined complex macromolecular architectures, yet also be used in applications ranging from bonding/debonding on demand networks to nano-porous material design. The specific chemistries to be addressed include fast, quantitative and mild ligation via (hetero) Diels-Alder chemistries, mechanistic switches from living radical protocols (RAFT) to ring opening polymerization producing sulfur free architectures, spin trap systems as well as the use of efficient photo-chemistries to ligate variable enes and dienes in a spatially resolved fashion. It will be demonstrated how the reversibility of pericyclic reactions (‘dynamic covalent chemistry’) can be employed to periodically alter the physical characteristics of macromolecular materials with regard to intrinsic viscosity, color, configuration as well as micro- and nano-structure. The modification of nano-objects – including fullerenes and single-walled carbon-nanotubes – via pericyclic reactions will additionally be addressed. Moreover, the use of modular ligation for the build-up of highly defined α,ω-H-orthogonal-donor/acceptor systems for single chain assembly emulating the folding behavior of biomacromolecuels will be highlighted, showing a possible pathway for the construction of entirely synthetic protein-like entities. The synthetic efforts will be underpinned by the in-depth characterization of the obtained macromolecules via hyphenated techniques including SEC-ESI-MSn and LACCC-SEC.

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STARCH-DERIVED 1,4-3,6:DIANHYDROHEXITOL STEREOISOMERS: VERSATILE PLATFORM FOR THE DESIGN

OF ORIGINAL POLYMERS USING ROBUST, EFFICIENT AND ORTHOGONAL CHEMISTRIES.

Imen Abdelhedi Miladi,1 Samir Beghdadi,2 Céline Besset,2 Hatem Ben Romdhane,1 JulienBernard,2 Eric Drockenmuller,2,3

1 Laboratoire de Chimie Organique Structurale-Synthèse et Etudes Physicochimiques, Faculté dessciences de Tunis, Université de Tunis El Manar, 2092 El Manar Tunis, Tunisia

2Université Lyon 1, INSA-Lyon, Ingénierie des Matériaux Polymères, 69622 Ville urbanne, France3Institut Universitaire de France

E-mail: eric.drockenmuller@univ-lyon1.fr

The polymer chemistry community has recently devoted tremendous efforts for thedevelopment of new polymer materials with advanced properties using robust efficient and orthogonal processes [1]. Also, a strong interest toward sustainable materials derived from biomass feedstock has emerged as a consequence of fossil resources depletion and rising costs. In this scope, starch-derived 1,4:3,6-dianhydrohexitol stereoisomers (i.e. isosorbide, isomannide, and isoidide) are particularly interesting difunctional building blocks (Scheme 1) [2].

Scheme 1. Isosorbide, isomannide and isoidide 1,4:3,6-dianhydrohexitol stereoisomers.

Taking advantage of robust, efficient and orthogonal reactions as well as the hydroxyl groupsreactivity, several symmetric and asymmetric monomers (Scheme 2) could be prepared andpolymerized by step growth polymerization processes (e.g. copper(I)-catalyzed azide-alkynecycloaddition [3], thiol-ene or Heck coupling) or by living/controlled radical polymerization (e.g.RAFT polymerization). This lecture will sum up our latest findings on the synthesis andcharacterization of stereocontrolled bio-sourced dianhydrohexitol-based monomers and polymers. Aparticular attention will be paid to the structure/properties relationship of these materials with aspecial focus on the effect of triazole ring’s regiochemistry and stereochemistry of the 1,4:3,6-dianhydrohexitol moiety.

Scheme 2. Library of stereocontrolled 1,4:3,6-dianhydrohexitol-based monomers.

[1] Iha, R. K.; Wooley, K. L.; Nystrom, A. M.; Burke, D. J.; Kade, M. J.; Hawker, C. J. Chem. Rev. 2009, 109, 5620–5686.[2] Fenouillot, F.; Rousseau, A.; Colomines, G.; Saint-Loup, R.; Pascault, J-P. Prog. Polym. Sci. 2010, 35, 578-622.[3] (a) Besset, C.; Binauld, S.; Ibert, M.; Fuertes, P.; Pascault, J-P.; Fleury, E.; Bernard, J.; Drockenmuller, E.Macromolecules 2010, 43, 17-19. (b) Besset, C.; Bernard, J.; Fleury, E.; Pascault, J-P.; Cassagnau, P.; Drockenmuller, E.;Williams, R. J. J. Macromolecules 2010, 43, 5672-5678. (c) Besset, C.; Pascault, J-P.; Fleury, E.; Drockenmuller, E.;Bernard, J. Biomacromolecules 2010, 11, 2797-2803.

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THREE-DIMENSIONAL DNA NANOSTRUCTURES AS BLOCKS IN POLYMER SELF-ASSEMBLY

Christopher J. Serpell,1 Hanadi F. Sleiman1

1Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, Canada

E-mail: christopher.serpell@mail.mcgill.ca

Self-assembled block copolymer nanostructures are one of the major classes of nanomaterials; in particular their impressive drug delivery functions have been extensively demonstrated [1]. However, since distribution of nanomaterials within the body is heavily influenced by the geometric parameters of the introduced species [2], and activity at the target cells is often a function of controlled multivalency [3], a greater level of anisotropic programmability and detailed structural control would enable the potency of block copolymer drug delivery systems to be more fully realised. Moreover, even low levels of polydispersity can put a query over clinical approval. Conversely, 3D-DNA nanostructures are fully programmable and monodisperse, and can be used both as molecular containers [4] for potentially bioactive species, and as scaffolds for precise positioning of molecules [5] such as targeting ligands.

By creating block copolymers in which one block is a 3D DNA nanostructure, it becomes possible to arrange the other blocks with total control over their location and orientation (depending on the polymer), providing complete spatial freedom, in addition to the traditional handles of block copolymer self-assembly: not only can morphology be controlled by judicious selection of blocks and length optimisation, but also by fine-tuned geometric control. The resulting constructs represent a new class of block copolymer with precise definition in three dimensions, in contrast to existing isotropic 3D dendrimers, 2D brush copolymers, and 1D linear block copolymers.

We report new micelle-based methods for the synthesis of DNA-polymer conjugates and their hybridization to 3D DNA nanostructures. The combination of these technologies results in geometrically controlled microphase-separated morphologies (Figure 1) and DNA-derived functionality, for applications in drug delivery and nanofabrication.

Figure 1 – Micelle formation by block co-polymers containing 3D-DNA nanostructures.

[1] A. S. Mikhail, C. Allen, J. Contr. Rel., 2009, 138, 214[2] D. A. Scheinberg, C. H. Villa, F. E. Escorcia, M. R. McDevitt, Nature Rev. Clin. Onc., 2010, 7, 266.[3] L. L. Kiessling, J. E. Gestwicki, L. E. Strong, Angew. Chem. Int. Ed., 2006, 45, 2348 – 2368[4] P. K. Lo, P. Karam, F. A. Aldaye, C. K. McLaughlin, G. D. Hamblin, G. Cosa, H. F. Sleiman, Nature Chem., 2010, 2, 319-328[5] T. Tørring, N. V. Voigt, J. Nangreave, H. Yan, K. V. Gothelf, Chem. Soc. Rev., 2011, DOI: 10.1039/C1CS15057J

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MOLECULAR DESIGN OF MAIN-CHAIN CHIRAL QUATERNARY AMMONIUM POLYMERS

FOR ASYMMETRIC CATALYSIS APPLICATIONShinichi Itsuno, Md. Masud Parvez, Naoki Haraguchi

Department of Environmental & Life Sciences, Division of Molecular ChemistryToyohashi University of Technology, Toyohashi, 441-8580 Japan

E-mail: itsuno@ens.tut.ac.jp

Chiral organocatalysts have recently attracted a considerable amount of attention in the fieldof asymmetric synthesis. Although highly efficient chiral quaternary ammonium salts asorganocatalysts have been developed, we sometimes encounter problems in their separation from the reaction mixture maily due to their amphiphilic property. In comparison with the transition metalcatalyst, relatively large amount of the organocatalyst is required to complete the reaction. In order to overcome the separation issue, numbers of polymer-immobilized catalysts have been prepared.[1,2] All the reported examples involved the polymeric catalysts possessing the organocatalyst moieties on their side chain.

We have developed novel type of main-chain chiral quaternary ammonium polymers, whichcan be an efficient catalyst in asymmetric reactions including alkylation of glycinate Schiff base. Weproposed two different types of the main-chain chiral quaternary ammonium salt polymers. The firstexample involves the chiral polymers containing cinchona quaternary ammonium salt in its mainchain. The hydrocinchonidine dimer was allowed to react with dihalide to form poly(quaternaryammonium salt) 1 in high yield.

Another type of the main-chain chiral quaternary ammonium salt polymers 2 involves thepolymers composed of ionic bonds in their main-chain. Since we found that quaternary ammoniumsulfonate is stable enough to attach a quaternary ammonium organocatalyst into sulfonated polymer,we applied this ionic bond formation to prepare main-chain ionic polymers. Ion exchange reactionbetween quaternary ammonium salt dimer and disulfonate smoothly occurred to obtain the chiral ionic polymer 2 in high yield.[3] Repeating units of the chiral polymer 2 were bonded with ionic bond.

Avobe mentioned polymers showed excellent catalytic activity in the asymmetric alkylationreaction to yield the corresponding amino acid derivative in quantitative conversion with high level of enantioselectivity. The polymeric catalsyst was easily separated from the reaction mixture and reused many times without loss of the catalytic activity.

[1] Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis; S. Itsuno, Ed. Wiley, (2011).[2] Itsuno, S.; Parvez, M. M.; Haragchi, N. Polym. Chem., 2011, 2, 1942-1949.[3] Itsuno, S.; Paul, D. K.; Salam M. A.; Haraguchi, N. J. Am. Chem. Soc., 2010, 132, 2864–2865

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NOVEL SYNTHETIC STRATEGIES TO FUNCTIONALIZED MACROMOLECULES

Craig J. Hawker

Materials Department, University of California, Santa Barbara, CA, 93106

E-mail: hawker@mrl.ucsb.edu

New synthetic strategies that are robust, efficient and occur under mild reaction condition are required to prepare multi-functional materials which in turn are required to meet the ever increasing demand for materials with improved performance. A number of examples will be given where a select range of robust chemistries are employed for the synthesis of functional macromolecules.

To illustrate the potential of this strategy, novel azulene building blocks, prepared via the cycloaddition of thiophene-S,S-dioxides and fulvenes, allow for incorporation of the seven-membered ring of the azulene nucleus directly into the backbone of conjugated materials. This unique mode of incorporation gives remarkably stable, stimuli-responsive materials on exposure to acid. This simple doping/dedoping strategy provides for effective optical band gap control and on/off switching of fluorescence, reminiscent of polyaniline.

In addition, we have introduced a new strategy for the facile synthesis of orthogonally functionalized hybrid dendritic-linear delivery systems, incorporating reactive groups at the chain ends as well as internally, through a combination of ‘amine-epoxy’ and ‘thiol-yne’ click chemistry. Starting from bis-amino-PEG, a 4th generation dendritic scaffold having chain end amino groups, a single FITC or Alexa dye and 20 internal coumarin units could be prepared. Even with this high loading of coumarin units (~25 wt%), confocal microscopy on living cells revealed that upon membrane binding and internalization of the scaffold, intracellular enzymes cleaved the coumarin payload, allowing release into the cytoplasm. As a result, both the dendritic scaffold and the release of its payload can be monitored simultaneously inside living cells.

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54

THE POLYMER-LIKE SOLID ELECTROLYTE INTERPHASE ON CARBON ELECTRODES IN LITHIUM-ION BATTERIES

Petr Novák and Pallavi Verma

Paul Scherrer Institute, CH-5232 Villigen PSI, SwitzerlandE-mail: petr.novak@psi.ch; novakp@ethz.ch

In lithium-ion batteries both the negative and positive electrodes are made from electronically conductive matrix materials which are able to reversibly accommodate (insert) variable quantities of lithium ions. So far, electroactive insertion materials used in commercial lithium-ion cells are based on lithiated carbon (LiC6) and lithium transition metal oxide LiMO2, typically on the basis of cobalt, nickel, and manganese. The electrode potential of most of the electroactive materials is far beyond the thermodynamic stability window of the most commonly used organic electrolytes. Hence reductive and oxidative electrolyte decomposition occurs. Typically propylene, ethylene, hydrogen, and (in some electrolytes) CO2 are generated during electrochemical electrolyte reduction. Gas evolution increases the cell internal pressure, which may result in raised safety risks and reduced cycle stability. Fortunately a polymer-like protective layer called the Solid Electrolyte Interphase (SEI) forms normally at the surface of carbon negative electrode materials, preventing further reductive electrolyte decomposition. The SEI is crucial for the behavior of the entire battery, thus, the primary focus of the talk will be on the formation, modification, and characterization of the SEI.

Though the “natural” SEI layer electronically passivates the surface of the electrode material, and ensures cyclability by virtue of Li-ion conduction; it is normally inhomogeneous, partially soluble, and does not prevent exfoliation of graphite in propylene carbonate (PC) based electrolyte (important for low temperature applications). Hence, approaches to form an “artificial” SEI will be discussed. More specifically, the surface of graphite is chemically modified before electrochemical cycling, to tune its morphology and reactivity for controlled SEI properties. Two methods of surface modification developed by us are: chemical grafting followed by terminal functional group reduction, and tuning reactivity of surface groups existing on graphite.

Grafting is used for covalent immobilization of organic moieties on the surface of graphite. It allows control over SEI morphology, decreases charge consumption for SEI formation, and prevents exfoliation of graphite in PC based electrolyte. The reactivity of the grafted layer is further tuned by a consecutive reduction step. The resulting material exhibits further decreased charge consumption for SEI formation. Owing to the covalent nature of attachment the surface layers formed by this method are stable throughout cycling. However, the modification obtained by grafting is multilayered rather than monolayered and hence adversely affects the practical specific energy of the material.

To minimize surface layer thickness, the surface groups already existing on graphite were modified by chemical pretreatments. Chemically pre-reduced graphites show less irreversible charge loss, whereas chemically pre-oxidized graphites show higher irreversible charge loss. Treatment of graphite by n-butyl lithium resulted in exclusively edge covered particles. This material exhibits good reversible cycling in PC based electrolyte as well as homogeneous and flexible SEI. Cyclability of this material in standard electrolyte was improved by stabilizing the surface chemical composition by use of ethylene carbonate as additive.

Surface modification methods are ideal for tuning surface properties of electrode materials, which enables a precise control over SEI. Challenges like safety, cycling efficiency, and loss of specific charge can be surmounted by this approach.

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REDOX-ACTIVE ORGANIC STRUCTURES VS LI:A POSSIBLE ALTERNATIVE TO DESIGN “GREENER”

LI-ION BATTERIESPhilippe Poizot,1 Franck Dolhem2

1Laboratoire de Réactivité et Chimie des Solide UMR CNRS 6007, University of Picardie, 33 rue Saint-Leu, 80039 Amiens cedex, France

2Laboratoire des Glucides UMR CNRS 6218, University of Picardie, 33 rue Saint-Leu, 80039 Amiens cedex, France

E-mail: philippe.poizot@u-picardie.fr

One of the major challenges of this century is to identify and secure sustainable energy supplies while reducing GHGs emissions. In the broad field of energy conversion and its modern management, the particular case of electrical energy appears highly sensitive due to its indispensable functionality for a wide range of fundamental applications for industrialized societies. Thus, decarbonizing the logistic chain of the electrical sector constitutes probably one of the basic stages towards a sustainable development. One technological challenge in this field relies on designing advanced batteries to store more electrical energy while being environment-friendly. The Li-ion battery technology constitutes a reliable system for electricity storage displaying particularly high energy density and design flexibility. Widely used in “nomadic” electronic devices, such batteries also appear to be an important element to mitigate the CO2 releases i) as a promising power source for advanced electric vehicles and ii) as a potential buffer energy storage system to manage the intermittent renewable energy resources (both on- and off-the-grid). Thus the world production of Li-ion batteries is expected to keep on growing. However, whatever the considered technology, common electrode reactions involve redox-active inorganic matter especially metal-based electroactive obtained from non-renewable resources (ores) whereas typically synthesized by ceramic route. At large-scale perspectives, the environmental impact of such Li-ion batteries could be noticeable. Decreasing the consumption of non-renewable resources, the amount of waste produced or the energy consumption is on the verge of becoming mandatory, and improving the environmental footprint of rechargeable batteries (LIBs, in particular) will probably be required for a near future [1].

A possible alternative can be foreseen in the use of organic active materials. Indeed, switching from inorganic to organic matter-based electrode materials thus gives them the true possibility of being prepared from renewable resources and eco-friendly processes coupled with a simplified recycling management [2]. Most of organics are also typical fuels that can be easily consumed by combustion at medium temperatures producing heat (energy recovery) but also Li-based ashes able to be re-introduced into the battery production chain. However, looking back on the historic developments of electrode materials for Li-based batteries and in comparison with inorganic compounds that benefit from decades of intensive years of research, the use of organics was just sporadically studied and mainly as cathodic materials (discharge state). For the past few years, we have been revisiting selected organic structures based on organic molecules containing stabilized carbonyl/carboxyl functionalities in order to identify stable and efficient redox-active organic structures reacting at both high and low potentials vs. Li to allow a large enough output voltage of the cell. Emphasis is also put on the use of modern green chemistry concepts, starting with a renewable natural precursor for the synthesis of electroactive molecules (when possible), which brings new dimensions in terms of materials lifecycle costs and sustainability in general.

[1] Dewulf, J.; Van der Vorst, G.; Denturck, K.; Van Langenhove, H.; Ghyoot, W.; Tytgat, J.; Vandeputte, K. Resour., Conserv. Recycl. 2010, 54, 229–234.[2] Poizot, P.; Dolhem, F. Energy Environ. Sci. 2011, 4, 2003–2019.

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ORGANIC BATTERIES WITH VARIOUS TYPES OF CHARGE STORAGE CONFIGURATIONKenichi Oyaizu, Takashi Sukegawa, Wonsung Choi, Hiroyuki Nishide

Department of Applied Chemistry, Waseda University, Tokyo 169-8555

E-mail: oyaizu@waseda.jp

Redox gradient-driven charge transfer processes in a layer of non-conjugated polymers populated with numerous redox sites by electron self-exchange reactions lead to substantial electric conduction by the improvement of electro-neutralization with electrolyte counterions, based on the mesoscale design of the polymer/electrode interface. Using organic robust radicals such as TEMPO and 2,2,5,5-tetramethyl-3-pyrolin-1-oxyl as the redox sites which are characterized by large heterogeneous electrode reaction rate constants (k0 = 10-1 cm/s) and large second-order electron self-exchange rate constants (kex = 107 – 8 M-1s-1), a general concept of enhancing the power capability of various wet-type electronic devices such as rechargeable batteries, redox capacitors, and dye-sensitized solar cells, is presented.

Fig. 1 High-density redox polymers as “soft” electronic interface for organic batteries.

[1] Choi, W.; Harada, D.; Oyaizu, K.; Nishide, H. J. Am. Chem. Soc. 2011, in press.

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REPAIRABLE BIOMIMETIC SOFT MATERIALSScott M. Brombosz1, Simonida Grubjesic, Söenke Seifert2, Millicent A. Firestone1

1Materials Science Division, Argonne National Laboratory, Argonne, IL USA 604392X-ray Sciences Division, Argonne National Laboratory, Argonne , IL USA 60439

E-mail: firestone@anl.gov

Proteins facilitate many key cellular processes, including signal recognition, ion transport, and energy transduction. The ability to harness this evolutionarily-optimized functionality could lead to the development of protein-based systems useful for advancing alternative energy storage and conversion. The future of protein-based materials (and ultimately devices), however, requires the development of materials that will stabilize, order and control the activity of the proteins. The full realization of the potential of protein-based functional materials in the fabrication of devices, however also requires architectures that ensure assembly of the proteins into high density, ordered arrays for signal amplification and addressability, components for interfacing with traditional materials or device platforms, and a means to achieve adequate mechanical strength and chemical resistance without detriment to the biological components. Lastly, and most significantly, synthetic strategies for incorporating reversible crosslinks, allowing for the removal and replacement of inactive proteins must also be considered since the functional lifetime of proteins are limited.

Recently we have developed a synthetic approach for the preparation of a durable biomimetic chemical hydrogel that can be reversibly swollen in water. The matrix has proven ideal for the stable encapsulation of both water- and membrane-soluble proteins. The material is composed of an aqueous dispersion of a diacrylate end-derivatized PEO-PPO-PEO macromer, a saturated phospholipid and a zwitterionic co-surfactant that self-assembles into a multilamellar physical gel at room temperature as determined by X-ray scattering. The addition of a water soluble PEGDA co-monomer and photoinitator does not alter the self-assembled structure and UV irradiation serves to crosslink the acrylate end groups on the macromer with the PEGDA forming a network within the aqueous domains as determined by FT-IR. The physical gel converts to an elastic self-supporting chemical gel. Storage under ambient conditions (air at room temperature) causes dehydration of the hydrogel, to 5 wt %, which can be reversed by swelling in water (to achieve 85 wt % water content). The fully water swollen gel remains self-supporting but converts to a non-lamellar structure. As water is lost the chemical gel regains its lamellar structure. Incubation of the hydrogel in nonpolar organic solvents that do not dissolve the uncrosslinked lipid component (hexane) allow for swelling without loss of structural integrity. In this presentation our recent efforts directed at incorporating reversible crosslinks employing Diels-Alder chemsitry will be discussed.

This work was supported by the Office of Basic Energy Sciences, Division of Materials Sciences, United States Department of Energy under Contract No. DE-AC02-06CH11357 to the UChicago, LLC.

[1] Grubjesic, S.; Lee, B.; Seifert, S.; Firestone, M. A. Soft Matter (2011) DOI 10.1039/c1sm06364b

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DESIGN RULES FOR FUEL CELL MEMBRANESGerhard Maier,1 Markus Groß,1 Tim Fuller,2 Craig Gittleman,2 Sean MacKinnon,3 Cortney

Mittelsteadt4

1Polymaterials AG, Kaufbeuren, Germany2GM Fuel Cell Activities, Honeoye Falls, NY, USA

3Industrial Materials Institute, National Research Council Canada, Boucherville, Quebéc, Canada4Giner Electrochemical Systems, Newton, MA, USA

E-mail: g.maier@polymaterials.de

Fuel cells are considered a potential alternative to batteries for portable electronics, internal combustion engines for cars, and even boilers and generators for stationary applications. More and more technical problems are being solved on the pathway to commercial success. However, depending on the specific application, there are still improvements required concerning the proton conducting membranes in PMFCs.

Many different polyelectrolytes have been synthesized over the past decades for application as proton conducting membrane in fuel cells. While many of them (polymers as well as membranes) are well studied, it is often hard to identify the specific benefits and drawbacks of one chemical structure over another. Based on observations of the effects of certain chemical structures as well as the architecture of the polymer chains on membrane properties such as proton conductivity, water uptake, and durability, this presentation will try to point out guidelines for the improvement of polyelectrolytes for fuel cell membranes [1]. These guidelines concern polymer properties such as block structures, microphase separated morphologies, the type of the attachment of the acidic groups to the polymer chain, the effect of hydrophobicity and others. The effects of these polymer properties on the behavior of the membrane will be described an attempts at explanations for these observations will be made.

Applying the concepts described above, proton conducting membranes with performance in hydrogen/air fuel cells comparable to or exceeding that of fluorinated membranes even at relative humidity as low as of 50% can be produced.

[1] Gross, M.; Maier, G.; Fuller, T.; MacKinnon, S.; Gittleman, C. A. Design rules for the improvement of the performance of hydrocarbon-based membranes for proton exchange membrane fuel cells (PEMFC). In Handbook of Fuel Cells: Advances in Electrocatalysis, Materials, Diagnostics and Durability, Vielstich, W.; Gasteiger, H. A.; Yokokawa, H., Eds.; John Wiley & Sons, New York, 2009; Vol. 5, Chapter 18.

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POLYMER SOLAR CELLS: AN ATTEMPT OF NEAR INFRARED DYE SENSITIZATION

Shinzaburo Ito, Hideo Ohkita, Hiroaki Benten, Satoshi Honda

Department of Polymer Chemistry, Kyoto University, Katsura, Nishi-kyo, Kyoto 615-8510, Japan

E-mail: sito@photo.polym.kyoto-u.ac.jp

Polymer-based solar cells have made great progress during the past decade. Owing to their potential advantages such as lightweight, flexible, low cost, and high-throughput production, polymer solar cells are now attracting extensive academic and commercial interest, and expected to provide an effective solution for the problem of energy resource and environmental preservation in the next generation of human society.

Figure 1 shows the progress of energy conversion efficiency (PCE) of polymer solar cells, clearly indicating very rapid growth owing to key inventions. In particular, new polymeric materials such as low band-gap polymers have been developed, consequently, the efficiency is improved year by year, and very recently a value over 10% has been already reported.

This great progress of polymer solar cells is triggered by the development of bulk heterojunction (BHJ) structure.

Figure 2 shows a schematic drawing of a BHJ cell, which is prepared by blending a conjugated polymer (poly(3 - hexylthiophene): P3HT) and a fullerene derivative, PCBM. This binary blend is phase-separated with a nanometric scale, in which the successive energy conversion processes, that is, photo-excitation, exciton diffusion, electron transfer, charge separation and charge transport to the electrodes, take place with very high efficiency in the wide range of time scale from femto-second to milli-second.

To achieve higher photovoltaic efficiency, it is absolutely necessary to harvest sun light at longer wavelengths in near infrared (NIR) region. Therefore, many synthetic works have been intensively performed to explore new low-band-gap polymers having strong absorption bands in the NIR.

In this paper, another way is proposed, that is, dye-sensitized BHJ polymer solar cell, which can harvest NIR light effectively by addition of a dye molecule, silicon phthalocyanine (SiPc) into P3HT/PCBM composites. SiPc was selectively allocated at the boundary region of the interface, where hole transfer and electron transfer processes with high efficencies were observed from the excitated state of dye molecules.1,2

[1] Honda, S.; Yokoya, S.; Ohkita, H.; Benten, H.; Ito, S. J. Phys. Chem. C, 2011, 115, 11306-11317. [1] Honda, S.; Ohkita, H.; Benten, H.; Ito, S. Adv. Energy Mater., 2011, 1, 588-598.

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INSIGHT INTO THE SYNTHESIS, DESIGNAND PROCESSING OF NARROW BANDGAP ORGANIC SEMICONDUCTING POLYMERS

FOR SOLAR CELL FABRICATION

James T. Rogers,1 Kristin Schmidt, 1 Jeff Peet, 1 Corey Hoven, 1 Greg Welch, 1 Yanming Sun, Thuc-Quyen Nguyen, 1 Michael F. Toney, 2 Alan J. Heeger, 1 Edward J. Kramer, 1

Guillermo C. Bazan1

1Departments of Chemistry & Biochemistry and Materials, University of California, Santa Barbara, CA 93106

2Stanford Synchrotron Radiation Lightsource, Menlo Park, CA 94025E-mail: bazan@chem.ucsb.edu

High charge separation efficiency combined with the reduced fabrication costs associated with solution processing (printing and coating) and the potential for implementation on flexible substrates make “plastic” solar cells a compelling option for tomorrow’s photovoltaics. The control the donor/acceptor morphology in bulk heterojunction materials as required for achieving high power conversion efficiency is therefore of primary concern. We showed that by incorporating a few percent by volume of high boiling point additives, the power conversion efficiency of photovoltaic cells is substantially improved. This approach has been widely adopted as a choice method for improving the performance of a wide range of narrow bandgap conjugated polymers; however the exact mechanism of action by which the morphology is modified remains incompletely understood. A series of polymers was thus designed to specifically probe how film formation is modified and structural characterization tools, such as TEM, conductive and photoconductive AFM, and GIWAXS were incorporated in the study. Guidelines have thus appeared to help guide the choice of additive as a function of polymer molecular structure. GIWAXS studies show a direct relationship between device performance and the polymorph, correlation length, and orientation of conjugated polymer crystallites. Such insight is difficult to obtain by other techniques and points out that additives not only act to change the general spatial distribution of donor and acceptor components in the BHJ active layer, as previously observed.

More recently the dependence of the solar cell performance on the polymer molecular weight and structural defects, such as end groups, has been examined. These studies led to the design of a new class of materials with intermediate dimensions that are precisely defined and lack batch to batch variations. New processing conditions, particularly on the choice of additives, are required to obtain performances, which are amongst the highest for intermediate sized donor molecules. These methods of fabrication will be discussed, together with structural studies that correlate device performance with the structural order of the semiconducting layers.

References:

(i) Rogers, J. T.; Schmidt, K.; Toney, M. F.; Kramer, E. J.; Bazan, G. C. Advanced Materials 2011, 23, 2284.(ii) Tong, M.; Cho, S.; Roger, J. T.; Schmidt, K.; Hsu, B. B. J.; Moses, D.; Coffin, R. C.; Kramer, E. J.; Bazan, G. C., Heeger, A. J. Advanced Functional Materials 2010, 20, 3959.(iii) Peet, J.; Kim, J.Y.; Coates, N.E.; Ma, W.L.; Moses, D.; Heeger, A.J.; Bazan, G.C., Nature Materials 2007, 7, 497.

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AMPHIPHILIC CONJUGATED BLOCK COPOLYMERS FOR EFFICIENT BULK HETEROJUNCTION SOLAR CELLSJinwoo Choi,1 Luciano Miozzo,2 Clément Suspène,3 Ramona Gironda,1,2 Denis Tondelier,1 Bernard

Geffroy,1,4 Yvan Bonnassieux,1 Abderrahim Yassar1

1LPICM, Ecole polytechnique, CNRS, 91128 Palaiseau Cedex, France2Department of Materials Science, University of Milano-Bicocca, Milano, Italy

3ITODYS, Université Paris Diderot, 75205 Paris Cedex 13, France4CEA Saclay, DSM/IRAMIS/SPCSI/LCSI, 91191 Gif Sur Yvette, France

E-mail: abderrahim.yassar@polytechnique.edu

Bulk heterojunction (BHJ) solar cells based on blend of conjugated polymer/fullerene systems offer promises for the realization of a low-cost, printable, portable and flexible renewable energy source. Currently, organic solar cells achieve power conversion efficiency of up to 8%.[1] Over the past decade, research has focused on regioregular poly(3-hexylthiophene) (P3HT) as the standard electron-donating material in polymer solar cells, with important progress having been made in understanding the device science and the associated improvements in device efficiency.[2] The performance of these conjugated polymers relies crucially on their morphology on the nanometer scale. An emerging approach to manipulate the nanoscale morphology of the BHJ is to develop new copolymer materials, random or block, with tunable morphology.[3]

In this communication, we report a new methodology for the synthesis of well-defined new regioregular co-polythiophenes functionalized with hydrogen bonding units, through a simple and efficient approach using GRIM polymerization. The functional ester or acid groups required to enhance morphological control of the BHJ are introduced into the conjugated backbone either in a random or block fashion. The photovoltaic properties of these copolymers were investigated in BHJ device with PC60BM. The performances of BHJ solar cells based on these new materials will be presented, in particular for the best one exhibiting a power conversion efficiency (PCE) of 4.2%, an open-circuit voltage (Voc) of 0.60 V, a short-circuit current density (Jsc) of 13.0 mA.cm-2 and a fill factor (FF) of 0.60. Their electrical characterizations as well as PCE will be discussed and correlated with the molecular structure of functionalized copolymers.

[1] 8.3% on an active surface area of 1.1 cm2 was achieved by Heliatek and independently confirmed by the Fraunhofer ISE CalLab (Freiburg), Konarka’s Power Plastic has also achieved 8.3% efficiency, certified from NREL. http://www.konarka.com/index.php/site/pressreleasedetail/konarkas_power_plastic_achieves_world_record_83_efficiency_certification_fr.[2] Cheng, Y.-J.; Yang, S.-H.; Hsu, C.-S. Chem. Rev. 2009, 109, 5868-5923.[3] Ren, G.; Wu, P.-T.; Jenekhe, S. A. Chem. Mater. 2010, 22, 2020-2026.

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63

USING THE CHEMICAL INFORMATION IN DNA TO CONTROL STRUCTURE

Nadrian C. Seeman

Chemistry Department, New York University, New York, NY 10003, USA

DNA is well-known as the genetic material of living organisms. We build branched DNA species that can be connected to one another using sticky ends. Such sticky-ended cohesion is used to produce N-connected objects and lattices. We have used ligation to construct DNA stick-polyhedra and topological targets, such as Borromean rings and woven patterns. Branched junctions with up to 12 arms have been produced. We have also built DNA nanotubes with lateral interactions.

Nanorobotics is a key area of application. PX DNA has been used to produce a robust 2-state sequence-dependent device that changes states by varied hybridization topology. Bipedal walkers, both clocked and autonomous have been built. We have constructed a molecular assembly line by combining a DNA origami layer with three PX-based devices, so that there are eight different states represented by the arrangements of these devices; we have programmed a novel DNA walking device to pass these three stations. As a consequence of proximity, the devices add a cargo molecule to the walker. We have demonstrated that all eight products (including the null product) can be built from this system.

A central goal of DNA nanotechnology is the self-assembly of periodic matter. We have constructed 2-dimensional DNA arrays with designed patterns from many different motifs. Recently, we have used DNA scaffolding to organize active DNA components, as well as other materials. Active DNA components include DNAzymes and DNA nanomechanical devices; both are active when incorporated in 2D DNA lattices. We have used pairs of PX-based devices to capture a variety of different targets. Multi-tile DNA arrays have also been used to organize gold nanoparticles in specific arrangements.

Recently, we have self-assembled a 3D crystalline array and have solved its crystal structure to 4 Å resolution, using traditional unbiased crystallographic methods. Nine other crystals have been designed following the same principles of sticky-ended cohesion. We can use crystals with two molecules in the crystallographic repeat to control the color of the crystals. Thus, structural DNA nanotechnology has fulfilled its initial goal of controlling the structure of matter in three dimensions. A new era in nanoscale control is beginning.

This research has been supported by the NIGMS, NSF, ARO, ONR and the W.M. Keck Foundation.

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FUNCTIONAL SELF-ASSEMBLED ARCHITECTURESFROM POLYMERS AND PROTEINS

Roeland J.M. Nolte

Institute for Molecules and Materials, Radboud University Nijmegen,

Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands

E-mail: R.Nolte@science.ru.nl

In this lecture I will present studies of bio-inspired research situated at the interface of macromolecular chemistry and supramolecular chemistry including some of the following topics: (i) the design and synthesis of self-assembled nanostructures from amphiphilic block copolymers containing a hydrophobic and a hydrophilic segment, the latter being a special type of biomacromolecules, i.e. helical isocyanopeptides. The formed architectures can incorporate different types of enzymes and act as nanoreactors that can be taken up by cells and function as artificial organelles. (ii) The synthesis of polymersome nanostructures that can undergo shape transformations to give synthetic stomatocytes, which are small nano-sized containers with an opening of controllable size. In the cavity of these containers a cargo can be entrapped, e.g. enzymes or catalytically active platinum particles. Using the latter cargo a nanomotor system was developed and the movement of this motor was followed by nanoparticle tracking analysis. (iii) The synthesis of polymer-protein hybrids, which on dispersal in water form different types of nano-sized assemblies, e.g. toroids, Y-shaped architectures, and cell-like objects in which cascade reactions can take place. (iv) The synthesis of biohybrid architectures from viruses, including the Cowpea Chlorotic Mottle Virus (CCMV) and the Potato Virus X. The genetic material of the CCMV particles has been removed and replaced by enzyme molecules to create a nanoreactor and by polymers and inorganic components to generate functional biohybrid architectures. These virus-like particles (VLP’s) have been combined with photocleavable dendritic polymers to give photoswitchable colloidal systems. The potential of these functional VLP’s will be discussed.

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DNA-PROGRAMMED ASSEMBLY AND COUPLINGOF MOLECULAR WIRES

Christian B. Rosen, Jens B. Ravnsbæk, Mikkel F. Jacobsen, Niels V. Voigt, Kurt V. Gothelf

Center for DNA Nanotechnology, Department of Chemistry and iNANO, Aarhus University, Aarhus C, Denmark

Email: crosen@chem.au.dk

A large variety of small organic molecules with potentially useful conducting properties are currently available through classical synthetic approaches. However, one major obstacle for taking advantage of their unique properties as individual molecular units is our lacking ability to couple and position individual components to form large monodisperse structures.

DNA has proven to be a powerful tool for the self-assembly of complex nanostructures. The inherent nature of DNA to selectively form a double helix by hybridization of complimentary strands has been exploited to organize molecules and materials in a programmable fashion. Furthermore, DNA-directed chemistry offers the opportunity to control synthetic chemical reactions between individual molecules and the formation of covalent linkages between molecular building blocks.

In earlier work we have reported on the DNA-programmed assembly and coupling of oligo(phenylene ethynylene) units by the formation of metal-salen complexes. [1]Here we have explored the formation of C-C bonds between the conjugated modules (Figure 1A). For this purpose we have demonstrated that DNA-directed Glaser-Eglinton reactions [2], can be applied for the formation of monodisperse conjugated wires (Figure 1B). This methodology enables the preparation of molecular rods of predefined lengths ranging from 4 to 8 nm, which are potential conducting nanowires. [3]

References

[1] Gothelf, K. V.; Thomsen, A.; Nielsen, M.; Cló, E.; Brown, R. S. J. Am. Chem. Soc. 2004, 126, 1044-1046.[2] a) Glaser, C. Ber. Dtsch. Chem. Ges. 1869, 2, 422-424; b) Glaser, C. Justus Liebigs Ann. Chem. 1870, 154, 137-171; c) Eglinton. G.; Galbraith, A. R. Chem. Ind. 1956, 737-738.[3] Ravnsbæk, J. B.; Jacobsen, M. F.; Rosen, C. B.; Voigt, N. V.; Gothelf, K. V. Angew. Chem. Int. Ed. 2011, 50, 10851-50, 10851-10854.

Macromolecular Engineering with Biomolecules

Figur 1. A) Schematic representation of the incorporated organic module.

B) DNA-directed oligomerization of dialkyne monomers by multiple

Glaser-Eglinton reactions.

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SUPRAMOLECULAR CHEMISTRY WITH DNA: TOWARDS BIOLOGICAL AND MATERIALS APPLICATIONS

Hanadi F. Sleiman

Department of Chemistry, McGill University, Montreal, Canada

E-mail: hanadi.sleiman@mcgill.ca

A central challenge in supramolecular chemistry is the organization of functional components into deliberately designed patterns, and the ability to modify these patterns at will. Because of its molecular recognition specificity and structural features, DNA presents a unique opportunity to address this problem. A number of strategies for DNA construction have been developed, such as weaving together DNA strands into ‘tiles’, or stapling a viral DNA strand into ‘origami’ structures. These approaches use DNA as the only information source to guide the assembly, resulting in DNA-dense structures that are large and rigid.

Our group has been examining a new approach to build DNA nanostructures, in which synthetic molecules are used to control and modify DNA self-assembly. This results in combining the diverse structural features and functionalities of inorganic and organic molecules, with the programmable nature of DNA, and obviates the need for interweaving DNA strands for structure definition. Thus, ‘DNA-economic’ structures with smaller sizes, increased dynamic character and intrinsic functionalities are formed. Specifically, we will describe (a) the synthesis of 3D-DNA structures, such as DNA cages and nanotubes, with deliberate variation of geometry, size, single- and double-stranded forms, permeability and persistence lengths, (b) the encapsulation of guest materials within these 3D-hosts and their selective release with externally added molecules, (c) the site-specific incorporation of transition metals and synthetic polymers in these structures, with significant stability enhancement, redox, photophysical and magnetic properties, (d) the use of small molecules to effect profound changes in both DNA nanostructure preparation and the fundamental self-assembly properties of DNA itself. Finally, we will describe the selective delivery of these responsive DNA cages and nanotubes into mammalian cells.

Selected References: Science 2008, 321, 1795; Curr. Opin. Chem. Biol. 2010, 14, 597; Angew. Chem. 2011, 50, 4620; Chem. Comm., 2011, 47, 8925; Nature Chem. 2010, 2, 320; J. Am. Chem. Soc. 2010, 132, 10212; J. Am. Chem. Soc. 2009, 131, 679; Angew Chem. 2009, 48, 9919; Nature Chem. 2009, 1, 390; Nature Nanotech., 2009, 4, 349; Angew Chem. 2008, 47, 2443; J. Am. Chem. Soc. 2007, 129, 13376; J. Am. Chem. Soc. 2007, 129, 10070; J. Am. Chem. Soc. 2007, 129, 4130.

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FUNCTIONAL SUPRAMOLECULAR POLYMERS AND THEIR HYBRIDS WITH COVALENT POLYMERS

Samuel I. Stupp

Departments of Chemistry, Materials Science and Engineering, and Medicine, Northwestern University, Evanston, IL 60208

E-mail: s-stupp@northwestern.edu

Supramolecular polymers formed through self-assembly of monomers create ordered aggregates that emulate filamentous structures in biological systems and have great potential for biomedical, energy, and environmental functions. One of the common targets explored so far by us and others has been the design of monomers that self-assemble into conducting and light harvesting nanowires of interest in electronic and photovoltaic applications. Efforts in our laboratory have also focused on fibrils that present groups with known biological functionality in highly favorable orientation and density, resulting in unprecedented efficiency in cell signaling for use in regenerative medicine. The future of the field needs to include programming of molecules for self-assembly that create more complex structures with order on scales that exceed the dimensions of the supramolecular polymers they form. Another important goal is the design of hybrid structures that integrate supramolecular and covalent polymers as well as supramolecular and inorganic structures. This lecture will discuss various forms of ordered supramolecular polymers with biological and electronic functions as well as hybrid systems of interest in solar energy functions. The lecture will also discuss self-assembly pathways that produce cell-like objects or virus-like structures containing both supramolecular and covalent polymers and their potential for biomedical functions.

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DNA BLOCK COPOLYMERS: FROM DRUG DELIVERY TO NANOELECTRONICS

Andreas Herrmann

Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9757 AG Groningen, The Netherlands

E-mail: a.herrmann@rug.nl

Within the presentation hybrid materials of DNA and different synthetic macromolecules will be highlighted.[1] Various synthetic strategies for the generation of linear, single stranded (ss) and double stranded (ds) DNA block copolymers have been elaborated some of them relying on fully automated processes using a DNA synthesizer, [2] on hybridization or on molecular biology techniques like the polymerase chain reaction.[3] The formation of nanoscopic objects which are adopted by amphiphilic DNA block copolymers in solution will be discussed. Their structural properties can be manipulated by hybridization.[4] Moreover, their incorporation into phospholipid vesicle containers and nanoelectronic devices will be demonstrated.[5]

In the context of applications, the uptake of DNA block copolymer aggregates with different shapes into various cell lines was studied. On the basis of these results their use as combinatorial platform for drug delivery was successfully demonstrated.[6]

[1] M. Kwak, A. Herrmann, Angew. Chem. Int. Ed. 2010, 49, 8574.[2] F. E. Alemdaroglu, K. Ding, R. Berger, A. Herrmann, Angew. Chem. Int. Ed. 2006, 45, 4206.[3] a)F. E. Alemdaroglu, W. Zhuang, L. Zophel, J. Wang, R. Berger, J. P. Rabe, A. Herrmann, Nano Lett. 2009, 9, 3658; b)M. Safak, F. E. Alemdaroglu, Y. Li, E. Ergen, A. Herrmann, Adv. Mater. 2007, 19 1499; c)F. E. Alemdaroglu, J. Wang, M. Börsch, R. Berger, A. Herrmann, Angew. Chem. Int. Ed. 2008, 47, 974.[4] K. Ding, F. E. Alemdaroglu, M. Boersch, R. Berger, A. Herrmann, Angew. Chem. Int. Ed. 2007, 46, 1172.[5] M. Kwak, J. Gao, D. K. Prusty, A. J. Musser, V. A. Markov, N. Tombros, M. C. A. Stuart, W. R. Browne, E. J. Boekema, G. ten Brinke, H. T. Jonkman, B. J. van Wees, M. A. Loi, A. Herrmann, Angew. Chem. Int. Ed. 2011, 50, 3206.[6] a)F. E. Alemdaroglu, C. N. Alemdaroglu, P. Langguth, A. Herrmann, Adv. Mat. 2008, 20, 899; b)M. Kwak, I. J. Minten, D. M. Anaya, A. J. Musser, M. Brasch, R. J. M. Nolte, K. Mullen, J. Cornelissen, A. Herrmann, J. Am. Chem. Soc. 2010, 132, 7834.

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ENZYME RESPONSIVE MICELLAR NANOPARTICLES FROM NOVEL PEPTIDE- AND OLIGONUCLEOTIDE-

POLYMER AMPHIPHILESMichael E. Hahn,1,2 Miao-Ping Chien,1 Ti-Hsuan Ku, Matthew P. Thomspon,1 Lyndsay M. Randolph,1

and Nathan C. Gianneschi1

1Department of Chemistry and Biochemistry, University of California, San Diego, CA 920932Department of Radiology, University of California, San Diego, CA 92103

E-mail: mehahn@ucsd.edu

Seminal studies have demonstrated the controlled destruction of soft organic nanomaterials in response to biologically relevant stimuli with burgeoning applications in drug delivery [1]. Typical triggers include pH, temperature, light, ionic strength, small molecules, and enzymatic transformation. In comparison, significantly less work exists on soft organic nanomaterials that undergo a discrete morphology change in response to biologically relevant stimuli, particularly enzymes [2]. In this lecture, we will describe our efforts toward taking advantage of enzyme driven morphology change for the control of soft organic nanomaterial behavior in vivo.

Utilizing ring opening metathesis polymerization of norbornene based monomers with Grubbs’ catalysts, we have developed smart amphiphilic polynorbornene polymers decorated with oligonucleotides and peptides [3,4]. Both direct polymerization of norbornene-biomolecule conjugates as well as post polymerization modification have generated well defined polynorbornenes of low polydispersity bearing peptides and oligonucleotides that form micellar nanoparticles. The biomolecules are displayed on the shell of the particles and their sequences are carefully chosen to enable these micellar nanoparticles to respond to particular enzymatic inputs of interest by changing their aggregate morphology. In addition, we are also exploring the assembly of micellar aggregates from molecularly dispersed unimers in response to disease-associated enzymes for potential in vivo applications [5].

Recent work has shown that nanoparticle shape has a dramatic effect on the pharmacokinetics and pharmacodynamics of nanoparticles in vivo [6-8]. Therefore, we expect that the ability to control the morphology of soft materials on the nanoscale in response to enzymes will result in the ability to fine tune the in vivo efficacy of soft organic nanoscale drug carriers and diagnostic devices.

[1] Rijcken, C. J. F.; et al. J. Controlled Release 2007, 120, 131–148.[2] Hahn, M.E.; Gianneschi, N.C. Chem. Commun. 2011, 47, 11814-11821.[3] Chien, M.-P.; et al. Angew. Chem., Int. Ed., 2010, 49, 5076–5080.[4] Ku, T.-H.; et al. J. Am. Chem. Soc., 2011, 133, 8392–8395.[5] Amir, R.J.; et al. J. Am. Chem. Soc., 2009, 131, 13949–13951.[6] Geng, Y.; et al. Nat. Nanotechnol., 2007, 2, 249-255.[7] Yoo, J.-W.; Mitragotri, S. Proc. Natl. Acad. Sci. U. S. A., 2010, 107, 11205–11210.[8] Chauhan, V.P.; et al. Angew. Chem. Int. Ed., 2011, 50, 11417-11420.

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DNA-DENDRON HYBRID: A NEW BUILDING BLOCK FOR FUNCTIONAL SYSTEMS

Zhongqiang Yang,1 Liying Wang,2 Ping Chen,2 Yawei Sun,2 Dongsheng Liu1

1Department of Chemistry, Tsinghua University, Beijing, 100084, China.

2Institute of Chemistry, the Chinese Academy of Sciences, Beijing, 100190, China

E-mail: zyang@tsinghua.edu.cn

DNA block copolymers (DBC) as a perfect combination of nucleic acid and synthetic polymer has received increasing attention due to its excellent programmability and structural diversity inherited from DNA [1]. Dendrimer/dendron with well-defined highly branched nanostructures and almost monodispersed molecular weights has been widely used in supramolecular chemistry and functional materials [2]. Covalently conjugation of DNA and dendrimer certainly provides a new class of promising supramolecular building block with the potential to fabricate smart materials systems [3].

Herein, we will introduce several successfully DNA-dendron systems. It was demonstrated that the association/dissociation of the two attached dendritic macromolecules can be actively controlled by DNA motor (e.g., i-motif) [4]. The system was further extended to the streptavidin-biotin complex and fabricated a pH responsive dendron-DNA-protein hybrid molecular system. We found the size of this molecular system could be switched by the conformation change of the i-motif DNA [5]. As a breakthrough of current DNA-dendron system, we further conjugated the hydrophobic dendrons with DNA and constructed a new kind of amphiphilic DNA-dendron hybrid, and studied their assembly and functional behaviors [6]. In short, DNA-dendron hybrid as a new kind of DBC, has showed many interesting properties, and other related work is on progress. We believe this kind of hybrid will be used as promising building blocks for constructing functional systems and open up a wide range of applications in drug delivery, supramolecular templates, biosensors and so on.

[1] Kwak, M.; Herrmann, A. Angew. Chem. Int. Ed. 2010, 49, 2–16.[2] Fréchet, J. M. J. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4782-4787.[3] Caminade, A.-M.; Turrin, C.-O.; Majoral, J.-P. Chem.–Eur. J. 2008, 14, 7422–7432.[4] Sun, Y.; Liu, H.; Xu, L.; Wang, L.; Fan, Q.-H.; Liu, D. Langmuir 2010, 26, 12496–12499.[5] Chen, P.; Sun, Y.; Liu, H.; Xu, L.; Fan, Q.; Liu, D. Soft Matter 2010, 6, 2143–2145.[6] Wang, L.; Feng, Y.; Sun, Y.; Li, Z.; Yang, Z.; He, Y.-M.; Fan, Q.-H.; Liu, D. Soft Matter 2011, 7, 7187–7190.

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SELF-ASSEMBLY AND OPTICALLY TRIGGERED DISASSEMBLY OF DENDRON-VIRUS COMPLEXES

Mauri Kostiainen1,2, Oksana Kasyutich3, Jeroen Cornelissen2, Roeland Nolte2

1Molecular Materials, Department of Applied Physics, Aalto University, 02150 Espoo, Finland.

E-mail: mauri.kostiainen@aalto.fi

2Institute for Molecules and Materials, Radboud University Nijmegen, 6525 AJ Nijmegen, the Netherlands

1H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL, UK

Nature offers a vast array of biological building blocks that can be combined with synthetic materials to generate a variety of hierarchical architectures. Viruses are particularly interesting in this respect because of their well-defined structure and their possibility to function as scaffolds for the preparation of new biohybrid materials. We have shown that Cowpea Chlorotic Mottle Virus (CCMV) particles can be assembled into well-defined micron-sized objects and be reversed back into individual viruses by a short optical stimulus. Assembly is achieved by employing photo-sensitive dendrons that bind on the virus surface through multivalent electrostatic interactions and ultimately act as molecular glue between the virus particles. Individual virus particles can adopt hexagonal close packing within the complex. Optical triggering induces the controlled decomposition and charge-switching of dendrons, which results in loss of the multivalent interactions and the release of the virus particles [1-3]. Furthermore, the method is not limited to the virus particles alone, but can also be applied to other functional protein cages, such as magnetoferritin [4].

Figure. Strategy and transmission electron microscopy images for the assembly and optically-triggered disassembly of a hierarchical CCMV-dendron complex. Upon addition of a cationic dendron the individual viral particles are “glued” together by multiple electrostatic interactions, which results in a large hierarchical assembly. Optical irradiation destroys the multivalent binding interaction and leads to the release of the virus particles.

[1] Kostiainen, M. A.; Kasyutich, O.; Cornelissen, J. J. L. M.; Nolte, R. J. M. Nature Chemistry, 2010, 2, 394-399.[2] Doni, G.; Kostiainen, M. A.; Danani, A.; Pavan, G. M. Nano Letters, 2011, 11, 723-728.[3] Kostiainen, M. A.; Hiekkataipale, P.; de la Torre, J. A.; Nolte, R. J. M.; Cornelissen, J. J. L. M. J. Mater. Chem. 2011, 21, 2112-2117.[4] Kostiainen, M. A.; Ceci, P.; Fornara, M.; Hiekkataipale, P.; Kasyutich, O.; Nolte, R. J. M.; Cornelissen, J. J. L. M.; Desautels, R. D.; van Lierop, J. ACS Nano, 2011, 5, 6394-6402.

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73

CELLULOSE NANOMATERIALS – MOLECULAR DESIGN OF BIOLOGICAL NANOFIBERS FOR THE PURPOSE

OF LARGE-SCALE INDUSTRIAL APPLICATIONSLars A Berglund1,2, Qi Zhou1,2,3,

1Dept of Fiber and Polymer Technology, 2Wallenberg Wood Science Center, 3Dept of Glycoscience, Royal Inst of Technology, Stockholm, Sweden

E-mail: blund@kth.se

Nanotechnology receives strong scientific interest, but the commercial impact is still limited. Cellulose nanofibers in the form of nanofibrillated cellulose (NFC) have the potential to change all this [1]. In principle, NFC can be obtained from all plants. Cellulose in the form of nanofibers provides mechanical reinforcement to the hydrated biopolymer mixtures in plant cell walls (ie lignin and a wide variety of heterogeneous polysaccharides). It has been demonstrated that NFC can be obtained efficiently and potentially also at low cost by mechanical disintegration of pretreated wood pulp [1]. NFC nanofibers can have a diameter of around 5-20 nm and a length exceeding 1 micrometer. NFC is flexible in bending but strong in tension, and can be processed as a hydrocolloid [2].

Low cost NFC can be used as a reinforcement mat in order to prepare traditional thermoset composites. NFC nanopaper is formed by filtration of a hydrocolloid, and this “nanopaper” mat can be impregnated by a resin and cross-linked to form a thermoset biocomposite of high modulus [1] but also somewhat brittle.

In a wider sense, NFC offers many possibilities for new materials. Polymer foams based on starch and NFC have been produced with strongly improved properties [3]. The reason for this is that the cell wall is reinforced by NFC, so that the limitations of starch in moist state can be overcome. The performance of the resulting cellular plastic composite is even competitive with expanded polystyrene (EPS) and the material is 100% from renewable resources.

Even lower density materials with mechanical robustness have also been prepared by freeze-drying the hydrocolloid into an aerogel material [4]. The porosity can be as high as 99.5% [5] and the materials are interesting for thermal insulation and as templates for modification by, for instance, conducting polymers [4].

Inorganic-organic hybrid materials can also be prepared with NFC as a template or as a nanofibrous matrix surrounding inorganic nanoparticles. Clay nanopaper is one example where fire retardancy and gas barrier properties in combination with toughness are important advantages [6]. Recently, magnetic materials were prepared with an in-situ precipitation procedure where the nanoparticles were formed on the cellulose nanofiber template [7].

[1] Berglund LA, Peijs T, MRS Bulletin, 35, 201-207 (2010)[2] Sehaqui H, Liu AD, Zhou Q, Berglund LA, Biomacromol, 11, 2195-2198 (2010)[3] Svagan, AJ, Samir, MASA, Berglund, LA, Adv Mat, 20, 1263, (2008)[4] M Pääkkö, J Vapaavuori, R Silvennoinen, H Kosonen, M Ankerfors, T Lindström, L A Berglund and O Ikkala, Soft Matter, 4, 2492 (2008)[5] H Sehaqui, M Salajkova, Q Zhou, and L A. Berglund, Soft Matter, 6, 1824-1832, (2010)[6] Liu A, A Walther, O Ikkala, L Belova, and LA. Berglund, Biomacromol, 12, 633–641 (2011)[7] Olsson RT, M. A. S. Azizi Samir, G. Salazar-Alvarez, L. Belova, V. Ström, L. A. Berglund, O. Ikkala, J. Nogues and U. W. Gedde, Nature Nanotech, 5, 584-588 (2010)

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PLANT OILS: THE PERFECT RENEWABLE RESOURCE FOR POLYMER SCIENCE ?!

Michael A. R. Meier

Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry,Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany

E-mail: m.a.r.meier@kit.edu

In ages of depleting fossil reserves and an increasing emission of greenhouse gases it is obvious that the utilization of renewable feedstocks is one necessary step towards a sustainable development of our future. Especially plant oils bear a large potential for the substitution of currently used petrochemicals, since a variety of value added chemical intermediates can be derived from these resources in a straightforward fashion taking full advantage of nature’s synthetic potential. Here, new approaches for the synthesis of monomers as well as polymers from plant oils as renewable resources will be discussed.[1]

For instance, we could show that different chain length α,ω-diester monomers can be obtained from fatty acid esters via olefin cross-metathesis (CM) with methyl acrylate taking advantage of natures “synthetic pool” of fatty acids with different chain lengths and positions of the double bonds.[2] Similarly, we could show that the cross-metathesis with allyl chloride and other functional olefins allows for the synthesis of α,ω-difunctional compounds. Moreover, thiol-ene click chemistry offers a complementary approach for the introduction of different functional groups to fatty acids in a straightforward and efficient manner, as demonstrated for the functionalization of the castor oil derived methyl 10-undecenoate with a variety of thiols.[3] The thus obtained renewable platform chemicals are valuable starting materials for a variety of polyesters and polyamides.

Moreover, olefin metathesis as well as thiol-ene click chemistry were used to prepare renewable polymers. For instance, we could demonstrate the synthesis of telechelics as well as ABA triblock copolymers via ADMET in a one-step procedure.[4] During these ADMET polymerizations we observed more or less pronounced olefin isomerization side reactions. Therefore, we developed a strategy to monitor and quantify these side reactions during ADMET polymerizations and were able to correlate their amount to the applied catalyst as well as reaction conditions.[5] In a subsequent study, we could also demonstrate how to efficiently supress these unwanted side reactions.[6] Very recently, we could show that ADMET, a typical step-growth polymerization, can be used to prepare block- and star-shaped polymers by taking advantage of the CM selectivity between terminal olefins and acrylates.[7] Moreover, thiol-ene chemistry is also perfectly suited for the polymerization of fatty acid derived monomers, as will be shown with the synthesis of biopolymers with tuneable degradation behaviour.[8] Last but not least, we recently reported a strategy to highly functionalized renewable monomers and polymers based on multi-component reactions that offers manifold synthetic opportunities for polymer chemistry.[9]

In summary, we will thus demonstrate the versatility of plant-oil derived platform chemicals for the synthesis of a large variety of monomers and polymers. Plant oils are therefore a perfectly suited renewable resource for the polymer industry.

[1] L. Montero de Espinosa, M. A. R. Meier, Eur. Polym. J. 2011, 47, 837.[2] A. Rybak, M. A .R. Meier, Green Chem. 2007, 9, 1356.[3] O. Türünç, M. A. R. Meier, Macromol. Rapid Commun. 2010, 31, 1822.[4] A. Rybak, M. A. R. Meier, ChemSusChem 2008, 1, 542.[5] P. A. Fokou, M. A. R. Meier, J. Am. Chem. Soc. 2009, 131, 1664.[6] P. A. Fokou, M. A. R. Meier, Macromol. Rapid Commun. 2010, 31, 368.[7] L. Montero de Espinosa, M. A. R. Meier, Chem. Commun. 2011, 47, 1908.[8] O. Türünç, M. A. R. Meier, Green Chem. 2011, 13, 314.[9] O. Kreye, T. Tóth, M. A. R. Meier, J. Am. Chem. Soc. 2011, 133, 1790.

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NATURAL TRITERPENOIDS AS RENEWABLE NANOS: FORMATION OF HELICAL NANO-FIBERS, NANO-

VESICLES, NANO-SPHERES & DYNAMIC SOFT-MATERIALS Braja G. Bag,* Rakhi Majumdar, Shaishab K. Dinda, Shib S. Dash,

Koushik Paul and Avishek Dey

Department of Chemistry and Chemical Technology Vidyasagar University, Midnapore 721 102,West Bengal, India

Email: braja@mail.vidyasagar.ac.in

Plant metabolites are the most significant source of renewable chemical feedstocks for a sustainable future. Among various plant secondary metabolites, triterpenoids are a large and structurally diverse C30 subset of the major component terpenoids. Computations carried out by us on sixty representative naturally occurring triterpenoids have established that all the triterpenoids are nanometer long having varied rigid and flexible lengths [9].

We have been successful in isolating several triterpenoids from different plants and initiated a long term project to utilize such renewable nanos in the design of nano-architectures and functional nano-materials. Detailed self-assembly studies revealed that these nano-sized triterpenoids and their derivatives self-assembled in different liquids at low concentrations affording self-assembled nano-arthitechtures such as helical nano-fibers, nano-vesicles, nano-spheres, etc. [10,11,12].

The alkyl chained esters of the nano-sized chiral arjunolic acid 1 could immobilize various organic solvents at low concentrations [13]. The molecules self-assembled in organic media to form nano-sized vesicles and helical nano-fibers with concomitant hardening of the media (Figure 1). The melting of a soft-solid material (obtained from a 1:1 mixture of 2 and 3 in an organic liquid) could be observed visually by concomitant color change [14]. Recent results from our laboratory will be presented in the perspective of Green, Renewable and Nanos.

References

[9] Bag, B.G.; Garai, C.; Majumdar, R.; Laguerre, M. Structural Chemistry, 2011, (DOI: 10.1007/s11224-011-9881-1). [10] Bag, B.G.; Dinda, S.K. Pure & Appl. Chem., 2007, 79 (11), 2031 - 2038. [11] Bag, B.G.; Dey, P.P.; Dinda, S.K.; Sheldrick, W.S.; Oppel, I.M. Beil. J. Org. Chem, 2008, 4(24), 1-5. [12] Bag, B.G.; Dash, S.S. Nanoscale, 2011, (DOI: 10.1039/c1nr10886g). [13] Bag, B.G.; Dinda, S.K.; Dey, P.P.; Mallia, A.V.; Weiss, R.G. Langmuir, 2009, 25, 8663-8671. [14] Bag, B.G.; Maity, G.C.; Dinda, S.K. Org. Lett., 2006, 8, 5457 - 5460.

Polymers from Renewable Resources

Figure 1: Arjunolic acid derived gels, helical nano-fibers and nano-vesicles

76

NOVEL GREEN MATERIALS FROM BIOBASED RESIN SYSTEMS AND LIGNIN HYBRID: PROCESSING AND

APPLICATIONS Manju Misra1, Harekrishna Deka1, Saswata Sahoo1 Xiogang Luo1 and Amar K. Mohanty1.2

1School of Engineering, Thornbrough Building, University of Guelph,

2Bioproducts Discovery & Development Centre, Dept. of Plant Agriculture, Crop Science Building, University of Guelph, 50 Stone Road E, Guelph, ON, N1G 2W1, Canada

*E mail: mmisra@uoguelph.ca

Lignin, the second most abundant natural biopolymer in the world, serves as a matrix component for cellulose and hemicelluloses in plant cell walls and provides mechanical strength to biofibres. Currently, about 70 million tons of lignin is generated annually as a co-product in the paper pulp industry [1]. Furthermore, in order to fulfill the demand for lignoncellulosic bioethanol in the United States in the near future, about 225 million tons of lignin generation is expected from the cellulosic bioethanol industry [1]. Only about 2% of the generated lignin is being used for value added applications while the rest is used as burning fuel in the same generating industry. Sustainability of these industries greatly depends upon the value added applications of this co-product. Lignin is an amorphous substance that has potential for material applications. It is a complex polyfunctional macromolecule which is composed of a large number of polar functional groups [2].

Utilizing the functionality of lignin, a series of novel lignin based bioblends/biocomposites have been developed in our laboratory and show tremendous promise for applications in automotives and housing. In this work; three different lignin hybrids are developed from either poly(furfuryl alcohol) or hybrid-biobased epoxy, or -bio-based polyurethane (PUR) matrices, and various natural fibers and nano fibres as reinforcements are incorporated. All of the processed bioblends/bionanocomposites showed higher static and dynamic mechanical properties as compared to the neat matrix containing the same amount of bioresins. This presentation highlights innovative value added non-food industrial applications for underutilized vegetable/plant derived resins and biomass derived biofibers and lignin.

This research is financially supported by the Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA)-University of Guelph-OMAFRA (Bioeconomy for Industrial Uses Program 2009 & 2010); OMAFRA -New Directions Research Programs 2009, the Ontario Ministry of Research and Innovation BioCar Initiative project, Natural Sciences and Engineering Research Council of Canada (NSERC)-CRD program; Grain Farmers of Ontario (GFO) fund; and Manitoba Pulse Growers Association (MPGA) fund.

[1] Satheesh Kumar MN, Mohanty AK, Erickson L, Misra M. Lignin and its applications with polymers. J Biobas Mat Bioen 2009; 3: 1–24.[2] Glasser WG, Barnett CA, Muller PC, Sarkanen KV. The chemistry of several novel bioconversion lignins. J Agric Food Chem 1983; 31(5): 921-930.

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DESIGN AND DEVELOPMENT OF HYDROLYTICALLY-DEGRADABLE POLY(QUINIC ACID CARBONATE)S FOR

ORTHOPEDIC APPLICATIONSJennifer M. Streff, Céline J. Besset, Samantha L. Kristufek, Karen L. Wooley

Departments of Chemistry and Chemical Engineering, Texas A&M University, College Station, TX 77842-3012

E-mail: jennifer.streff@chem.tamu.edu and wooley@chem.tamu.edu

This presentation will describe the synthesis and study of a new class of hydrolytically-degradable poly(quinic acid carbonate)s, which are designed to originate from renewable resources, exhibit mechanical strength, and degrade into biologically- and environmentally-resorbable products, for use in orthopedic and/or engineering applications [1]. Using the commercially-available polyhydroxy natural product quinic acid as a starting material, lactonization and selective silylation of hydroxyl groups yielded two regioisomeric monomers. Condensation co-polymerization of each monomer with a carbonylation agent afforded two polycarbonates with differing regiochemistries and interesting thermal properties. Removal of the tert-butyldimethylsilyl protecting groups altered the physical properties of the polymers and allowed for non-covalent hydrogen-bonding interactions. Hydrolytic degradation studies are underway, which are expected to lead to environmentally-benign compounds: carbon dioxide and the starting material quinic acid. The thermal and mechanical properties of films produced from both the protected and deprotected polymers, as well as the results of degradation studies, will be highlighted in the presentation.

[1] Besset, C. J.; Lonnecker, A. T.; Streff, J. M.; Wooley, K. L. Biomacromolecules, 2011, 7,

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BIOPLASTICS AND GREEN MATERIALS FROM RENEWABLE RESOURCES: WHAT IS NEW!

Amar K. Mohanty

Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture and School of Engineering, Crop Science Building, University of Guelph, 50 Stone Road E, Guelph, ON,

N1G 2W1 CANADA,

*E mail: mohanty@uoguelph.ca

The use of bio- or renewable carbon unlike petro-carbon for manufacturing bioplastics and biobased materials is moving forward for a low carbon economy. The goal of green and clean technology is to use biobased materials with maximum possible amount of renewable biomass-based derivatives and still in maintain a cost-performance attributes. This is one of the pathways to have a sustainable future. The incorporation of bio-resources, e.g. crop-derived green plastics and plant derived biofibres (natural fibres) into composite materials are gaining prime importance in designing and engineering green composites. Biocomposites derived from natural fibers and traditional polymers like polypropylene, polyethylene, epoxy and polyesters have been developed for automotive parts and building structures. Renewable resource based bioplastics like polylactic acid (PLA), polyhydroxyalkanoates (PHAs), biobased polytrimethylene terephthalate (PTT), bio-polyolefins, bio-polyamides, cellulosic plastics, soy protein based bioplastics and vegetable oils derived bioresins need value-added and diverse applications to compete with the fossil fuel derived plastics and materials. Through reactive blends, composites and nanocomposites new biobased materials are under constant development. Hybrid technology both from plastic resin prospective as well as from reinforcing fibres angle through integration of both bio- and petro- resources has been a new direction in designing sustainable industrial biomaterials. This presentation will highlight the current status, opportunities and challenges of bioplastics and biobased materials for uses in car parts, consumer goods and sustainable packaging.

Acknowledgements: Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA)-New Directions Research Programs; University of Guelph-OMAFRA (Bioeconomy for Industrial Uses); Natural Sciences and Engineering Research Council of Canada (NSERC)-Discovery Grant; and Auto21.

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EMBRACING THE ERA OF RENEWABLY SOURCED MATERIALS: A FAMILY OF HIGH PERFORMANCE

POLYMERS AND FIBERS FROM DUPONTJoseph V. Kurian, E.I. DuPont de Nemours and Company Inc.,

Experimental Station, Wilmington, Delaware 19880, USA

E-mail: joseph.v.kurian@usa.dupont.com

There is a growing need to develop environmentally friendly, sustainable polymeric materials that provide performance and functionality better than today’s fossil based materials. DuPont is committed to research and development that will increase the use of renewable feedstocks in its innovative offerings. There are many diverse applications for Renewably Sourced products ranging from fabrics to carpets, inks and coatings, to construction materials and engineering resins. DuPont has commercialized an innovative family of polymers, Sorona®, based on the key ingredient 1,3-propanediol (PDO), derived from annually renewable agricultural feedstocks. Sorona® is a unique thermoplastic polymer that can be easily shaped into a variety of articles, including fibers, to offer a unique combination of properties, such as softness, comfort-stretch and recovery, easy care, dyeability and stain resistance. Innovative Sorona® polymer and fiber technologies enable manufacturers of apparel, carpet, automotive, upholstery, specialty resins and packaging to use their existing assets to make new, higher-value products to meet customer needs. Sorona® polymer is commercially available for the textiles, carpets, engineering thermoplastics and cosmetic packaging markets. This presentation will provide an overview of DuPont’s efforts in renewably sourced materials (www.renewable.dupont.com), with special emphasis on the scale-up, development, and commercialization of Sorona® polymer (http://www.sorona.dupont.com). Carpets made with DuPont™ Sorona® polymer offers a combination of permanent built-in stain protection, superior durability, amazing comfort, and environmental benefits. Sorona® is one of the most revolutionary materials to hit the carpet industry in a long time. Mills and brand houses around the world are creating hundreds of fabrics using fibers manufactured with DuPont™ Sorona® polymer. I will highlight how we overcame multiple challenges in commercializing this polymer. Additional examples of recent DuPont polymer innovations in sustainable products will be presented to illustrate the shift away from traditional processes to the use of more renewable feedstocks. The use of life cycle assessment as a tool for designing next generation sustainable products and processes will be covered as well.

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AN OVERVIEW OF ENVIRONMENTAL BENEFITSFOR POLYMERS MADE FROM RENEWABLE RESOURCES

Martin K. Patel

Department of Science, Technology and Society (STS) / Copernicus Institute, Utrecht University, Budapestlaan 6, NL-3584 CD Utrecht, Netherlands

Across the globe, novel bio-based chemicals and bio-based plastics are receiving increased attention. This is the case also for Europe, where large-scale programmes on basic and applied R&D are in place, next to commercialization processes moved forward by companies. This talk provides insight into key projects the presenter is involved in, into the EU policy context and the importance that is being paid to environmental assessments by means of Life Cycle Assessment (LCA). While there are still important gaps to be closed in LCA methodology, remarkable progress is being made in this area to quantify environmental benefits. Moreover, there is increased interest in broad sustainability assessments, covering also the economic and social dimension.

In this talk concrete examples of results from recent LCA studies on renewably sourced polymers are presented and the progress made in reducing the environmental footprint is discussed. This includes examples from the “BREW project” (Full Title: Medium and Long-term Opportunities and Risks of the Biotechnological Production of Bulk Chemicals from Renewable Resources) and other recent studies. Results are also presented on the environmental performance at the level of end-use applications, which is an area requiring significant attention.

To summarize, the presentation shows that substantial technical progress is being made in parallel with progress in demonstrating the value of these new materials for society.

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SYNTHESIS AND POSSIBLE MEDICAL APPLICATION OF INJECTABLE MACROMERS DERIVED FROM FATTY ACIDS

Jedrzej Skrobot1, Miroslawa El Fray1, Labib Zair2

1Division of Biomaterials and Microbiological Technologies, West Pomeranian University of Technology in Szczecin, Poland

2Clinic of General and Transplantation Surgery, Pomeranian Medical University, Szczecin, PolandE-mail: jskrobot@zut.edu.pl

The fatty acids can be materials of choice for producing polymers for biomedical applications, since they contribute with many advantageous physicochemical properties and render the biomaterials degradable into naturally occurring compounds [1].

In this work, we present new telechelic macromers derived from commercially available dimer fatty acids produced from renewable resources [2,3]. Macromers with different backbone chemistry (ester, urethane, anhydride) and molecular masses (from 700 to 5500 Da, as calculated from the iodine value) were synthesized. They are viscous materials that undergo rapid liquid-to-solid transition upon benign 365 nm light irradiation. These materials were tested towards their application as injectable in situ polymerizable implants. In vitro biocompatibility studies were performed on L929 fibroblasts, while in vivo tissue response was evaluated from implantation test on rabbits. Cell response from the direct and un-direct contact with material was examined and revealed low or no toxic effect after the contact with all tested materials.

The feasibility study toward injectable and photocurable materials concept was performed on rabbits. Artificially fabricated hernia on abdominal wall was treated with injectable liquid material which was further UV cross-linked in vivo in situ. The control group of animals was treated with commonly used polypropylene hernia mesh. The observation period last for 28 days. Animals were sacrificed and regenerated tissue was collected for histological examination. The artificially fabricated defect was healed and the implants were covered by healthy tissue without being rejected (Fig. 1). The number of inflammatory cells found in sub-cutaneous tissue was comparable to these found after the contact with polypropylene mesh. No inflammatory cells were detected in connective tissues and no sign of necrosis has been observed.

The presented study proves fatty acids to be very useful starting materials for producing advanced implants with high biofunctionality and biocompatibility.

AcknowledgementsThe work was financially supported from the research project N507 434734 from Polish Ministry for Science and Higher Education and by the European Union within the ESF “Investment in knowledge as a driving force for development of innovation in the region – II edition”.[1] Jain, J.P.; Sokolsky, M.; Kumar, N., Domb, A.J. Polymer Reviews 2008, 48, 154-191.[2] El Fray, M.; Skrobot, J.; Telechelic macromer, method for manufacturing thereof and formulations containing telechelic macromer, Polish Patent Pending PL395338, 2011[3] El Fray, M.; Skrobot, J.; Kohn, J.; Synthesis and characterization of telechelic macromers containing fatty acid derivatives, submitted to Reactive and Functional Polymers

Polymers from Renewable Resources

Fig. 1. Healed abdominal wall after treatment with the injectable material.

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POLYMER MECHANOCHEMISTRY:USING FORCE TO DIRECT MOLECULAR REACTIVITY

Christopher W. Bielawski, Kelly M. Wiggins, Johnathan N. Brantley

Department of Chemistry and Biochemistry, University of Texas, Austin, TX 78712E-mail: bielawski@cm.utexas.edu

Mechanochemistry, whereby chemical transformations are facilitated using mechanical force, often induces reactivity that is otherwise inaccessible. In this presentation, we will describe how exogenous forces have been used to surmount thermally-inaccessible isomerization barriers [1], facilitate retrocycloadditions [2], and activate latent coupling or polymerization catalysts [3,4]. In general, these transformations were facilitated through the site-specific activation of mechanophores – or chemical moieties designed to respond to mechanical force in a predictable manner – embedded within high molecular weight polymer chains. Included in the discussion will be a series of extensive spectroscopic analyses and control experiments that demonstrated the aforementioned activation processes originated from forces generated under ultrasound. Finally, some perspectives on the use of mechanical force to enable novel reactivity will be discussed.

[1] Wiggins, K. M.; Hudnall, T. W.; Shen, Q.; Kryger, M. J.; Moore, J. S.; Bielawski, C. W. J. Am. Chem. Soc. 2010, 132, 3256–3257.[2] Wiggins, K. M.; Syrett, J. A.; Haddleton, D. M.; Bielawski, C. W. J. Am. Chem. Soc. 2011, 133, 7180–7189.[3] Tennyson, A. G.; Wiggins, K. M.; Bielawski, C. W. J. Am. Chem. Soc. 2010, 132, 16631–16636.[4] Wiggins, K. M.; Hudnall, T. W.; Tennyson, A. G.; Bielawski, C. W. J. Mater. Chem. 2011, 21, 8355–8359.

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POLYMER ARCHITECTURES AND NANOSTRUCTURES GENERATED VIA LIVING RADICAL POLYMERIZATION

Michael J. Monteiro

1 Australian Institute of Bioengineering and Nanotechnology, The University of Queensland, Brisbane 4072, Australia

Polymers with designer architectures prepared by ‘living’ radical polymerization (LRP) have recently invoked the interest of academia and industry. The various architectures that can be prepared in bulk or solution are now left up to the imagination, and moreover the applications for such architectures are slowly being realized over a wide area of industries. ‘Living‘radical polymerization offers the possibility for the preparation of well-defined polymer architectures with novel microstructures. Importantly, these architectures can be made through self-aggregation or direct preparation in a water environment, which opens up a new class of polymer materials for use as specialty polymers in the biomedical area.

The seminar will present work on the synthesis of complex polymer architectures using LRP and ‘click’ coupling reactions and their self-aggregation in water. Examples will be given for the use of such nanostructures in biological applications. We will also report a new approach to control the formation of a variety of 3D structures at high weight fractions of polymer in water from a single diblock.

[1] Kessel, S.; Urbani, C. N.; Monteiro, M. J. Angew. Chemie Int. Ed. 2011, 50, 8082-8085.

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RATIONAL DESIGN & SYNTHESIS OF “INTELLIGENT” STAR POLYMERS FOR CYTOPLASMIC DELIVERY OF

THERAPEUTIC NUCLEIC ACIDSYasemin Yuksel Durmaz1, Yen-Ling Lin1, and Mohamed E. H. El-Sayed1, 2

University of Michigan, 1Department of Biomedical Engineering, 2Macromolecular Science and Engineering Program, Ann Arbor, MI 48109

E-mail: melsayed@umich.edu; Web: www.bme.umich.edu/centlab.php

Plasmid DNA, antisense oligodeoxynucleotides, and silencing RNA molecules have displayed therapeutic activity against cancer, viral infection, cardiovascular diseases, and neurodegenerative disorders in preclinical models. However, development of these nucleic acids into clinically-viable treatments has been hampered by the lack of an efficient carrier that can deliver this DNA/RNA cargo selectively into the cytoplasm of the diseased cell without exhibiting non-specific toxicity to healthy tissues. We report the design and synthesis of a new family of star-shaped pH-sensitive polymers that proved effective in condensing a large dose of silencing RNA (siRNA) molecules into “intelligent” particles that efficiently shuttle their cargo into the cytoplasm of epithelial cancer cells. Specifically, we grafted copolymers of hydrophobic hexyl methacrylate (HMA) and pH-sensitive dimethyl aminoethyl methacrylate (DMAEMA) monomers from the secondary face of the cone-shaped β-cyclodextrin (β-CD) oligomer via acid-labile hydrazone linkages [1] using atom transfer radical polymerization (ATRP) techniques to prepare star-shaped pH-sensitive polymers (Figure 1). We hypothesized that star-shaped polymers will condense anionic siRNA molecules into “intelligent” nanoparticles via electrostatic interaction. Intelligent particles will enter the cell via endocytosis where the pH-sensitive polymeric carrier will “sense” the drop in environment pH in the endosome, which will trigger hydrolysis of the acid-labile hydrazone linkages and release of the cationic/hydrophobic P(HMA-co-DMAEMA) grafts to rupture the endosomal membrane and release the loaded siRNA molecules into the cytoplasm (Figure 1). We varied the molecular weight of P(HMA- co-DMAEMA) grafts, molar ratio of HMA/DMAEMA monomers, and percentage of DMAEMA quaternized into the cationic trimethyl aminoethyl methacrylate (TMAEMA) monomers to investigate the relationship between the structure of star-shaped polymers, physicochemical properties of “intelligent” particles, and the associated transfection efficiency in epithelial cancer cells.

Fig. 1: Schematic of star-shaped pH-sensitive polymers and their complexation with siRNA molecules forming “intelligent” particles that enter the cell by endocytosis. The endosomal acidity triggers the

hydrolysis of acid-labile hydrazone linkages, release of P(HMA-co-

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Results show that star-shaped pH-sensitive polymers condense siRNA molecules into “intelligent” nanoparticles at low +/- ratio of 1.5/1. Particles were internalized by > 90% of epithelial cancer cells despite their modest cationic surface charge. Star-shaped polymer with an average molecular weight of 25 KDa/graft, 50/50 molar ratio of HMA/DMAEMA monomers, and 50% quaternized DMAEMA monomers complexed with anti-GAPDH siRNA molecules achieved 70% knockdown in GAPDH expression at the mRNA and protein levels in epithelial cancer cells compared to identical particles loaded with scrambled siRNA molecules. Further, these “intelligent” particles exhibited no cytotoxicity despite their high delivery efficiency. Results indicate that star-shaped pH-sensitive polymers with an optimum combination of cationic and hydrophobic properties efficiently deliver their therapeutic cargo into the cytoplasm by a combination of hydrophobic disruption and osmotic swelling of the endosomes.

This research is funded by the US Department of Defense-Breast Cancer Research Program and Susan G. Komen for the Cure.

[1] Lin Y-L.; Jiang G.; Birrell L.; and El-Sayed M.E.H.; Biomaterials, 2010, 31, 7150-7166.

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SYNTHESIS OF WELL-DEFINED PHOTO-CROSSLINKED POLYMERIC NANOCAPSULES BY SURFACE-INITIATED

RAFT POLYMERIZATIONXin Huang, Dietmar Appelhans, Brigitte Voit*

Leibniz Institute of Polymer Research Dresden, Hohe Straβe 6, 01069, Dresden, Germany.E-mail: voit@ipfdd.de

Hollow nanocapsules with an empty core domain and a polymer shell are very interesting structures due to their unique properties including encapsulation capability, controllable surface permeability and surface functionality. Recently, some methods have been reported to synthesize these structures, including, emulsion polymerization, cross-linking of micelles, directed self-assembly, layer- by- layer templating method and surface-initiated ATRP polymerization.[1,2] Here, in this work, we use for the first time surface-initiated RAFT polymerization to synthesize narrowly distributed hollow nanocapsules (PtBMA-co-PDMIPM-b-PHPMA) employing silica nanoparticles as sacrificial templates and 2,3-dimethyl maleic imidopropyl methacrylate as a photo cross-linker. The procedure is briefly presented in Scheme 1. After anchoring CTA onto the silica nanoparticles, a core-shell structure was realized by RAFT polymerization. Upon UV cross-linking of the polymer shell and dissolving the silica core in NH4F/HF buffer solution, hollow nanocapsules were obtained. This approach, which employs RAFT as a very versatile controlled radical polymerization technique, demonstrates various advantages: (1) due to the availability of monodispersed silica nanoparticles, it is possible to synthesize nearly monodisperse hollow spheres with controlled size; (2) the composition of the capsules can be governed by choosing the desired functional monomers and CTA, e.g., RAFT polymerization has been used previously to synthesize well-defined biocompatible PEG acrylate, HPMA, and temperature responsive NIPAAm polymers; (3) the thickness of the shell can be modulated by simply controlling the molecular weight of the grafted copolymer; (4) the postmodification of well defined and photo-crosslinkable block copolymer shells can be easily performed due to the presence of the RAFT agent on the surface, using thiol-ene or Micheal addition reactions. Presently, the application of the constructed structures in controlled drug delivery is studied in our group.

Scheme 1. (A) general procedure for the synthesis of the nanocapsule, (B) normal and (C) magnified TEM images of the block copolymer grafted silica nanoparticle, and (D) TEM image of the hollow nanocapsule.

ACKNOWLEDGEMENTS:X. Huang is grateful for the Alexander von Humboldt Foundation.

[1] Wang, Y.; Angelatos, A. S.; Caruso, F. Chemistry of Materials 2007, 20, 848-858.[2] Gaitzsch, J.; Appelhans, D.; Gräfe, D.; Schwille, P.; Voit, B. Chem. Commun. 2011,

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PRECISE HIERARCHICAL SELF-ASSEMBLY OF MULTICOMPARTMENT MICELLES

André H. Gröschel, Sandrine Tea, Joachim Schmelz, Felix H. Schacher, Holger Schmalz, Andreas Walther, Axel H. E. Müller

Macromolecular Chemistry II, University of Bayreuth, D-95440 Bayreuth, GermanyE-mail: andre.groeschel@uni-bayreuth.de

The desire to mimic complex structures found in nature inspires research groups since decades. Self-assembly of block copolymers is one of the most promising approaches towards compartmentalized nanostructures and their hierarchical meso-scale superstructures. This energy efficient bottom-up assembly allows the directed aggregation of terpolymers into kinetically trapped but stable constructs with complex architecture, rich repertoire of core geometries and versatile functionality.

Figure 1: Multicompartment micelles obtained via a simple solvent driven step-by-step assembly.

Here we present a flexible route for the directed self-assembly of ABC triblock terpolymers into multicompartment micelles (MCMs) simply by choosing the right solvent conditions and solvent sequences. The presented concept is applicable to almost any terpolymer (Figure 1) and circumvents up-to-date problems in MCMs preparation such as the necessity of complex polymer architectures, aid of additives or specialized monomers and/or monomer sequences. Not only can we direct and control the assembly process, but also describe parameters that determine the hierarchical step-growth polymerization of patchy micelles into worm-like superstructures. As an application we demonstrate the novel solution based synthesis of Janus micelles using the unique architecture of spherical MCMs as templates.

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SUPRAMOLECULAR APPROACHES TO STIMULI-RESPONSIVE POLYMERS

Stuart J. Rowan

1Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland. OH 44106-7202

E-mail: stuart.rowan@case.edu

Utilizing non-covalent interactions to access controlled molecular assemblies as well as to influence communication between different components is a critical concept in most biological processes and natural biomaterials. Transferring this approach to designed synthetic polymer systems potentially opens the door to materials that exhibit unusual structural, mechanical and functional properties. The reversible nature of the non-covalent bond allows, when molecules are designed correctly, to access thermodynamically stable, complex self-assembled architectures, as well as opening the door to a new generation of adaptive, stimuli-responsive materials.[1] As such the designed utilization of supramolecular chemistry in the field of polymer science has seen a dramatic growth in the last decade or so. [2,3] We have been interested in the potential of such systems to access new material platforms and have developed a range of new mechanically stable, supramolecular polymer films that change their properties in response to a given stimulus, such as temperature, light or specific chemicals. Such supramolecular materials have been targeted toward applications that range from new implantable adaptive nanocomposites [4] and healable plastics [5] to sensors for chemical warfare agents [6,7] and thermally responsive hydrogels [8]. Our latest result in this area will be discussed.

[1] Wojtecki, R.J.; Meador, M.A.; Rowan S.J. Nature Materials 2011, 10, 14-27.[2] Fox, J.D.; Rowan, S.J. Macromolecules 2009, 42, 6823-6835.[3] Brunsveld, B. J. B.; Folmer, E. W.; Meijer, E. W.; Sijbesma, R. P. Chem. Rev. 2001, 101, 4071-4097.[4] Capadona, J.R.; Shanmuganathan, K.; Tyler D.J.; Rowan S.J.; Weder, C. Science 2008, 319, 1370-1374.[5] Burnworth, M.; Tang, L.; Kumpfer, J.R., Duncan, A. J., Beyer, F.L.; Rowan S.J.; Weder, C. Nature 2011, 472, 334-337.[6] Knapton, D.; Burnworth, M.; Rowan, S.J.; Weder C. Angew. Chem. Int Ed. 2006, 45, 5825-5829.[7] Kumpfer, J.; Jin, J.; Rowan, S.J. J. Mater. Chem. 2010, 20, 145-151.[8] Buerkle, L.E., Li, Z., Jamieson, A.M.; Rowan, S.J. Langmuir 2009, 25, 8833-8840.

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MULTIFUNCTIONAL POLYMERIC CATALYSTSAND REAGENTS

Patrick H. Toy

Department of Chemistry, University of Hong Kong, Pokfulam, Hong Kong, P. R. of China

E-mail: phtoy@hku.hk

Historically the polymer-supported catalysts used in organic synthesis have generally possessed only a single catalytic functional group. However, small molecule catalysts bearing multiple different functional groups can interact with substrates in more than one way, and often such interactions can be cooperative, and enhance reactivity and/or selectivity. While the concept of multifunctionality has been explored to a limited degree using rigid, heterogeneous silica materials as the catalyst support, the application of soluble and flexible organic polymers in this context is virtually unknown [1].

Recently we have revisited this topic, and have reported a non-cross-linked polystyrene organocatalyst functionalized with both triarylphosphine and phenol groups for the catalysis of Morita-Baylis-Hillman reactions [2]. This polymer has also been used to catalyse the isomerization of alkynoates to the corresponding E,E-dieneoates [3]. Another bifunctional polymeric catalyst we have developed incorporates both piperidine and DMAP groups, and this was found to be useful in highly stereoselective decarboxylative Doebner-Knoevenagel reactions between arylaldehydes and mono-ethyl malonate that afford the corresponding cinnamates in high yields [4]. In all of these examples, the bifunctional polymers were more efficient catalysts than polymers functionalized with only a single catalytic group.

In addition to the above mentioned polymeric catalysts, we have also extended the concept of multifunctionality to polymer-supported reagents, and have described a heterogeneous polystyrene bearing both phosphine and amine groups for use in one-pot Wittig reactions [5]. In these reactions an aldehyde and an alkyl halide were mixed together with our polymeric reagent, and the corresponding alkene was isolated in nearly quantitative yield and in high purity after only filtration and solvent removal. More recently this concept has been extended to one-pot Wittig reaction cascades where the polymer-supported phosphine oxide by-product of the Wittig reaction is used to catalyse transformations of the alkene product.

[1] Overberger, C. G.; Salamone, J. C.; Yuroslavsky, S. J. Am. Chem. Soc. 1967, 89, 6231.[2] Kwong, C. K.-W.; Huang, R.; Zhang, M.; Shi, M.; Toy, P. H. Chem. Eur. J. 2007, 13, 2369.[3] Kwong, C. K. W.; Fu, M. Y.; Law, H. C.-H.; Toy, P. H. Synlett 2010, 2617.[4] Lu, J.; Toy, P. H. Synlett 2011, 1723.

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RESPONSIVE POLYMER SOLUBILITY AS A TOOLIN SYNTHESIS

David E. Bergbreiter1

1Chemistry Department, Texas A&M University, College Station, TX 77843

E-mail: bergbreiter@chem.tamu.edu

Responsive polymer solubility is important in many biological and materials applications and is equally important in synthetic chemistry. This presentation will focus on polymers with thermoresponsive solubility and on polymers with structurally variable phase selective solubility that are useful in catalysis and synthesis in organic chemistry.[1,2] This talk will include select examples of applications of responsively soluble polymers in both areas. For example, thermoresponsive polymers that can be used to support phosphine, salen, or N-heterocyclic carbene ligands will be discussed. Such ligands form a variety of polymer-bound transition metal catalysts or organocatalysts that phase separate from a monophasic reaction mixture after a reaction. While a variety of polymer supports can be used, the emphasis will be on polyolefin supports like polyisobutylene and polyethylene. Separation strategies where the polymer support couples a separation event with other desirable outcomes will also be reported. For example, separation of an active reusable catalyst that can be directly reused without any purification in another reaction with new substrates without product cross-contamination in ring-closing metathesis will be described. Polymers where the separation process stabilizes a catalyst against adventitious decomposition events on exposure to protic workups is another strategy that will be explained. Finally, ways in which polymer-supported catalysts self separate from products or where products self-separate from a solution of a catalyst will be discussed.

[1] Bergbreiter, D. E.; Tian, J.; Hongfa, C. Chem. Rev. D. E. Bergbreiter, J. Tian, and C. Hongfa, Chem. Rev. 2009, 109, 530.[2] Bergbreiter, D. E., “Thermomorphic Catalysts”, in Recoverable and Recyclable Catalysts, Bengalia, M., Ed. Wiley, Chichester, 2009, pp. 117-154.

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CONCEALED QUALITIES - POLYMERS WITH AN UPPER CRITICAL SOLUTION TEMPERATURE IN WATER

Jan Seuring, Seema Agarwal

Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein Straße, D-35032

E-mail: seuring@staff.uni-marburg.de

Polymers showing an upper critical solution temperature (UCST) in water are rare. In most cases the UCST is based on either ionic interactions or hydrogen bonding. The first is observed for some polybetaines or quaternized polyurethanes. However, the electrostatic interactions of polyelectrolytes (e.g. polybetaines) are disturbed by the presence of salts which makes them unsuitable for the application under physiological conditions. For this reason novel nonionic polymer systems showing a sharp UCST over a wide range of concentrations and being tolerant to electrolytes are highly desirable. Recently, the nonionic homopolymer poly(N-acyloyl glycinamide) (poly(NAGA)) has been shown to exhibit a sharp upper critical solution temperature (UCST) in pure water as well as in electrolyte solution [1] (Scheme 1).

Scheme 1. The UCST-transition of poly(N-acryloyl glycinamide) is based on thermally reversible hydrogen bonding.

Although poly(NAGA) is known for decades the UCST behavior had not been reported. In this study we show that traces of ionic groups in the polymer prevent phase separation. In the past the UCST has not been observed because ionic groups have been introduced unintentionally by either acrylate impurities in the monomer, hydrolysis of the polymer side chains and/or usage of ionic initiators or chain transfer agents. It is shown how to obtain stable aqueous solutions of nonionic poly(NAGA) so that the UCST behavior can be exploited in pure water as well as in physiological milieu. We believe that this knowledge is transferable to other systems and will greatly accelerate research in the field of macromolecules that feature thermally reversible hydrogen bonding. Further, we demonstrate how powerful methods like ultrasensitive differential scanning calorimetry and light scattering can be used to get insights into the phase separation mechanism.

[1] Seuring, J., Agarwal, S. Macromol. Chem. Phys. 2010, 211, 2109-2117.

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NEXT-GENERATION COLLOIDS FOR THERAPEUTIC DELIVERY: FROM ASSEMBLY TO IN-VIVO APPLICATION

Frank Caruso1

1Department Chemical and Biomolecular Engineering, The University of Melbourne, Melbourne, VIC 3010

E-mail: fcaruso@unimelb.edu.au

Responsive polymers play an important role in the development of particle carriers for biomedical applications and biochemical reactions. This presentation will focus on nanoengineered polymer-based particle delivery systems assembled through the sequential deposition of polymers, and their utilization for the encapsulation, protection and release of oligonucleotides and peptides. The delivery of capsules to antigen presenting cells to stimulate an immune response and the specific binding of antibody-functionalized capsules to cancer cells will be highlighted. The preparation of synthetic hydrogel capsules that possess size and charge exclusion properties to allow for selective permeability of reaction components and facile control over capsule architecture, affording the continuous modification of nucleic acids and the assembly of liposome/polymer composites with a subcompartmentalized structure reminiscent of cells, will also be presented.

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POLYMER THERAPEUTICS FOR CELIAC DISEASE

Jean-Christophe Leroux,1,2 Gregor Fuhrmann,1 Maud Pinier2 and Elena F. Verdu3

1Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich, Switzerland2Faculty of Pharmacy, University of Montreal, Montreal, Canada

3Farncombe Family Digestive Health Research Institute, McMaster University, Hamilton, CanadaE-mail: jleroux@ethz.ch

Celiac disease (CD) is an inflammatory disease of the intestine triggered in genetically predisposed individuals by the ingestion of gluten and gluten-like proteins of wheat, rye, and barley. There is increased morbidity and mortality associated with CD. This disease is induced by immunogenic sequences of gluten proteins which are highly resistant to human digestive proteases [1]. The current and only treatment is life-long elimination of gluten from the diet. This dietary restriction is a difficult experience for many patients and is often associated with a decreased quality of life. Poor compliance, whether inadvertent or voluntary, to a strict gluten-free diet is frequent and predisposes patients to CD complications (e.g., nutritional deficiencies, osteoporosis, secondary autoimmune disorders, malignancies). Hence, there is an urgent need for complementary non-dietary therapies to help treat this common disorder (~1% of the population). One of the most interesting therapeutic options consists in administering to CD patients exogenous enzymes (“glutenases”) that cleave and detoxify the gluten peptides [2]. While promising, this approach is in part limited by the relative instability of the enzymes in the harsh conditions encountered in the GI tract [3].

Another intraluminal strategy, which is currently investigated in our laboratory, aims at sequestering the gluten in the gastrointestinal (GI) tract using polymer binders. We have shown that poly(hydroxyethyl methacrylate-co-styrene sulfonate), P(HEMA-co-SS), complexed α-gliadin (an important toxic fraction of gluten) with fair selectivity and abolished its deleterious effect both in vitro and in vivo in gliadin-sensitive HLA-HCD4/DQ8 mice [3]. The polymer was also efficient at counteracting the immunogenic response to whole gluten in the presence of other food components. P(HEMA-co-SS) restored the permeability of the intestinal mucosa of gluten-sensitive mice to normal values. It decreased the secretion of inflammatory cytokines, reduced the intraepithelial lymphocyte and macrophage cell counts, and decreased the stimulation of sensitized splenocytes and the production of anti-gliadin IgAs. The polymer was found to be innocuous and was mainly excreted in the feces following oral administration. It is thought that the polymer mainly acts by forming non-absorbable supramolecular assemblies with gliadin, and by decreasing the production of immunotoxic peptides by the GI enzymes [3]. Both HEMA and SS units were required to ensure effective sequestration at acidic and neutral pHs. In conclusion, P(HEMA-co-SS) has a potential adjuvant therapeutic benefit in the treatment of patients with gluten-induced disorders.

Financial support from the FQRNT, CAG/CIHR, NSERC, Canadian Celiac Association and “IG Zöliakie der Deutschen Schweiz” is acknowledged.

[1] Pinier, M.; Fuhrmann, G.; Verdu, E.F.; Leroux, J.C. Am. J. Gastroenterol. 2010, 105, 2551-2561.[2] Shan, L.; Molberg, O.; Parrot, I.; Hausch, F.; Filiz, F.; Gray, G.M.; Sollid, L.M.; Khosla, C.Science 2002, 297, 2275 – 2279.[3] Fuhrmann, G.; Leroux, J.C. Proc. Natl. Acad. Sci. USA 2011, DOI: 10.1073/pnas.1100285108.[4] Pinier, M.; Verdu, E.F.; Nasser-Eddine, M,; David, C.S.; Vézina, A.; Rivard, N.; Leroux, J.C. Gastroenterology 2009, 136, 288-298.

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THE ART OF FALLING APART:EXPLOITING NANOMATERIAL DISASSEMBLY

FOR MEDICINE AND PHARMACY Adah Almutairi1

1 Skaggs School of Pharmacy and Pharmaceutical Sciences, Department of NanoEngineering and the Materials Science and Engineering Program, UCSD

Research in nanotechnology over the last two decades has enabled scientists and engineers to build constructs of shapes, sizes and properties previously unattainable. These efforts have been rewarded with numerous Nobel Prizes. Now is the time to also focus on controlled disassembly of nanomaterial constructs to access properties and enable technologies useful in overcoming medical and pharmaceutical challenges. This presentation will cover two new classes of materials developed. Their usefulness to a number of medical challenges such as gene delivery and inflammatory diseases will be highlighted

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MONOMERS BASED ON METHACRYLIC ACID BISPHOSPHONATES FOR POLYMER DRUG DELIVERY

Souad Kachbi, Evelyne Migianu- Griffoni, Marc Lecouvey

Equipe Chimie Bioorganique et Structurale (CBS)Laboratoire CSPBAT. UMR 7244 CNRS. Université Paris 13

74 Rue Marcel Cachin F-93017 Bobigny FranceSouad.kachbi@gmail.com

Nowadays, millions of cancer patients have directly benefited from drug delivery systems, and polymers have been at the frontline of these technological advances1.

Polymerdrug conjugates improve bioavailability2, protect of unstable drugs from deterioration, offer long-lasting circulation in the bloodstream, decrease nonspecific toxicity of the conjugated drug and enhance accumulation of the drug at the tumor site by targeting, permeability and retention (EPR) effect.

Our laboratory is specialized not only in design and synthesis of new antitumor hydroxymethylene bisphosphonates (HMBPs)3,4 but also in drug targeting and vectorization5. Despite excellent therapeutic properties of bisphosphonates, only a few works have explored the incorporation of bisphosphonates onto the reactive side chains of polymers6. It is worthwhile developing a versatile bisphosphonate-based monomer which polymerizes or copolymerizes easily with ATRP method.

Therefore, we have designed and synthesized new and several categories of HMBP monomers : (1) methacrylic monomers bearing pamidronate, alendronate, neridronate (Fig.1); (2) HMBP methacrylic monomers containing ethylene glycol moiety (Fig.2) or carbamate function (Fig.3). These monomers were characterized by FTIR, 1H-NMR, 13C-NMR and 31P-NMR spectroscopies.

References

[1] Satchi-Fainaro, R.; Dunca, R.; Barnes, C. M. Adv Polym Sci. 2006, 193, 1–65.[2] Huaizhong P; Jindrich, K. Fundamental Biomedical Technologies. 2008, 4, 81-142.[3]E. Migianu, I. Mallard, N. Bouchemal, M. Lecouvey, Tet. Lett. 2004, 45, 4511- 4513.[4] Monteil, M. ; Guenin, E. ; Migianu, E. ; Lutomski, D. ; Lecouvey, M. Tet. 2005,61, 7528-7537.[5] Chebbi, I.; Migianu, E.; Sainte-Catherine, O.; Lecouvey, M.; Seksek, O. Inter .J. Pharm.. 2010, 383, 116-122.[6] Wang, L.; Zhang, A.M.; Yanga, A. Z.; Xu , B. Chem. Commun. 2006, 26, 2795-2797.

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SYNTHESIS AND EVALUATION OF BIODEGRADABLE HYDROGELS BASED ON HYPERBRANCHED

POLYESTER FOR ALVEOLAR BONE TREATMENTFiras Rasoul1,2, David Wang1, David Hill1,2, Andrew Whittaker1,2,

Srinivas Varanasi3 and Anne Symons3

1Australian Institute for Bioengineering and Nanotechnology,2Centre for Advanced Imaging and 3School of Dentistry

The University of Queensland, Brisbane, Queensland, 4072 Australiaf.rasoul@uq.edu.au

Alveolar bone is the supporting bone structure of the maxilla (top jaw) and the mandible

(bottom jaw) which are the teeth-bearing bones in humans. Periodontitis or inflammatory gum disease is the primary cause of alveolar bone loss, due to convergence of bacteria that adheres to and grows on the tooth surface below the gum line. Periodontitis is very common and has a prevalence of 40-50% of the population above 30 years old and if left untreated will cause progressive and irreversible loss of the alveolar bone around the teeth and eventually leads to the loosening and subsequent loss of teeth. The principal goal for this research is to develop an effective method for the treatment of periodontitis and perimplantitis (failing dental implants) through controlled delivery of bone-healing bioactives from biodegradable hydrogels.

Hydrogels based on acrylated poly(lactic acid)-b-poly-(ethylene glycol)-b-poly(lactic acid) (PLA-b-PEG-b-PLA) macromers were designed to maintain all of the advantages of PEG-based material while also permitting tuneable degradability[1] which become extremely useful in the biomedical field to modulate the delivery rate of drugs or growth factors. However, PLA-b-PEG-b-PLA based hydrogels are falling short in some aspects for this particular application; such as high swelling ratio which can compromise the integrity of the dental implant and the treatment process, also high swelling will results in high rates of degradation and therefore faster drug release.

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Figure 2 CryoSEM of the hydrogels at1 & 8 weeks of immersion in water

In the current study we report the synthesis of new hydrogel copolymer systems based on hyperbranched polyester (BoltornTM) macromer and acrylated PLA-b-PEG-b-PLA tri-block copolymer. The hyperbranched polyester BoltornTM) macromer was decorated with multi-PEG-arms using Cu(I) catalyzed azide-alkyne “clickchemistry” and then acrylated to produce “Acrylated-Boltorn” macromer (BH20-PEGA) (see Fig 1). The effect of the BH20-PEGA contents on the PLA-PEG-PLA hydrogels morphology, swelling ratios and degradation rates will be presented [2]. According to the developed degradation models of hydrogels based on polylactide and lactide copolymers, the hydrolytic degradation in aqueous media is known to be affected by two main parameters, namely the kinetics of hydrolysis of the ester bonds and the physical structure of the gel. Both parameters control the process of network degradation which makes the gel degradation process very complex. In this study, we report the degradation behaviour of the new hydrogels including the effect of the molecular weight of the PEG segment (structural effect), the number of the lactide unites (kinetic effect) and level of the BH20-PEGA (morphological effect). Furthermore, for thefirst time since the discovery of the Cu(I)-catalyzed click reaction, we have been able to show the presence of complexed Cu(II) residues in polymerized gels and that Cu(II) can play an important role in the hydrolytic degradation of polyester-based gelsas elucidated by the cryoSEM and EPR spectroscopic studies (Fig 2). Further to that, this work provides a new insight into the utility of Cu(I)-catalyzed click reaction in the preparation of hydrolyzable biomaterials [3].

[1] Shah, Pool and Metters, Biomacromolecules 2006, 7, 3171; [2] Wang, D. et al, Polymer, 2011, accepted; Wang, D. PhD thesis Aug. 2011; [3] Bhattacharya and Kumari, Coord. Chem. Rev., 2009, 253, 2133.Acknowledgements: The authors would like to thank The Queensland State Government-NIRAP for financial support.

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MULTIFUNCTIONAL POLYMERIS FOR THERANOSTICS AND TISSUE ENGINEERING

Marcus Weck*, Cátia Ornelas, José A. Castillo, Dorothee E. Borchmann, Thomas Patrick Carberry

Molecular Design Institute and Department of Chemistry, New York University, New York, 10003, USA

E-mail: marcus.weck@nyu.edu

A fundamental limitation of current diagnostics and therapeutics is the lack of a single delivery system that has the potential to not only deliver therapeutics to the disease site of interest with high fidelity, i.e. target delivery, but also allows for diagnostics. We are engineering novel dendritic or dendrimer-polymer scaffolds with controlled architectures that utilize a targeting group, and present a drug and group(s) for imaging. We view that precise control of dendrimer design through the integration of orthogonal functionalization strategies will lead to a unique delivery platform for a wide variety of disease. Our platform is based on polyamide based dendrimers because they are based solely on a peptide like amide backbone and have demonstrated low toxicities and non-immunogenicities. We have developed a synthetic scheme that combines up to three orthogonal functionalization strategies allowing for the formation of highly controlled multifunctional materials.

The same limitations described above for theranostics, lack of functional group diversity and limited control over polymer architectures hamper also the field of tissue engineering. For example, existing scaffolds for bone tissue engineering have inadequate mechanical properties, lack of functional group diversity and uncontrolled architectures. We are developing new concepts to overcome these limitations by combining tunable and highly functionalized block copolymers with the incorporation of biomimetic ligands to support osteoblast adhesion and function. In particular, we are combining living polymerization techniques and thermally induced phase separation to address the issues of inadequate mechanical properties and the lack of control of scaffold architectures. Our strategy is based on poly(lactic acid)/poly(norbornene) (PLA/PNB) block copolymers that have been synthesized through a combination of ring-opening polymerization of lactides with ROMP.cell adhesion and differentiation compared to polymers currently used in tissue engineering.

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MANAGING SERUM POTASSIUM WITH RLY5016.AN INSIGHT INTO POLYMER DRUG DEVELOPMENT

AT RELYPSAJerry Buysse, Wilhelm Stahl, Angela Lee, John Mills, Inez Lees,

Xinnan Zhang, Faleh Salaymeh, and Eric Connor

1Relypsa, Inc.5301 Patrick Henry Drive

Santa Clara, CA 95054, USAE-mail: econnor@relypsa.com

This presentation will describe how Relypsa, builds on the characteristics of macromolecules to make pharmaceuticals. Specifically, Relypsa focuses on the characteristic where the polymer, itself is the drug. To Relypsa, this is distinctly different from the application where polymers are used to change the bioavalability of a small molecule drug i.e. drug delivery applications.

Relypsa currently has a product, RLY5016 that has completed several clinical trials. RLY5016 is a polymeric drug that allows physicians to manage serum Potassium. RLY5016 does this by sequestering Potassium ions in the gastrointestinal tract. RLY5016 is a crosslinked polymer in a bead form having an average diameter of ~100um. The current formulation is designed to be taken orally, and then functions solely in the intestines of a patient and is not absorbed into the blood stream. This talk will describe the method that Relypsa uses to discover and optimize new drugs, such as RLY5016.

As most pharmaceutical compounds are small molecules, Relypsa has to be particularly innovative in this area in order for it to continue to succeed with its insoluble crosslinked polymer drug candidate. Highlights associated with polymer drug development will be touched upon in this presentation.

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NANOSCOPIC POLYMER OBJECTS OF UNIQUE SHAPES AND MORPHOLOGIES AND WELL-DEFINED STRUCTURES AND DIMENSIONS AS CONTROLLED

DRUG DELIVERY DEVICESGyu Seong Heo, Nam. S. Lee, Ang Li, Lily Y. Lin, Sandani Samarajeewa,

Ritu Shrestha, Shiyi Zhang, and Karen L. Wooley

1Department of Chemistry, and Department of Chemical Engineering,Texas A&M University, College Station, TX 77842

E-mail: wooley@chem.tamu.edu

This presentation will detail significant differences in drug loading capacities and drug release kinetics that can be realized by slight modifications in the compositions, structures, morphologies and dimensions of complex, well-defined polymer nanostructures. The evolution of nanostructured materials that originate from the supramolecular assembly of macromolecular building blocks, from relatively simple overall shapes and internal morphologies to those of increasing complexity, is driving the development of synthetic methodologies that allow for the preparation of increasingly complex macromolecular structures and allowing for their utility in many diverse applications, including as carriers for diagnostics and therapeutics. Moreover, the inclusion of functional units within selective compartments/domains is of great importance to create (multi)functional materials, which are capable of sensing their environment and giving tunable responses.

We have a special interest in the study of nanoscopic macromolecules, with well-defined composition, structure and topology, as components that are programmed for the formation of sophisticated nanoscopic objects in aqueous solution. Combinations of controlled radical and ring opening polymerizations, chemical transformations, and supramolecular assembly are employed to construct such materials as functional entities. We employ a variety of multi-functional monomers, together with selective polymerization chemistries, to afford regiochemically-functionalized polymers, and then further conduct supramolecular assembly processes and chemical transformations upon those precursor materials. By these iterative procedures, we are able to incorporate into single nanoscopic structures hydrophobic core domains for drug packaging, crosslinked shell layers to mediate drug release, optical and radiochemical labels to detect the local environment and track the nanoparticles, stealth coronal chemistries to tune the blood circulation half-lives, and surface-accessible targeting ligands to redirect the biodistributions. This presentation will describe our work over several years to tune the assembly and chemical transformations of di- and tri-block graft copolymers into unique bio-functional nanostructures, with emphasis on our most recent efforts that have revealed the exquisite levels of control over drug packaging and release that originate from precisely-defined compositions, structures, dimensions and morphologies. Applications for these nanoscopic materials in the treatment of lung infectious diseases, acute lung injury and cancer will be highlighted.

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SYNTHESIS OF FUNCTIONAL MATERIALSTHROUGH COMBINATION OF CONTROLLED

POLYMERIZATION TECHNIQUES AND EFFICIENT POLYMER ANALOGOUS REACTIONS

Brigitte Voit, Maria Heuken, Maria Riedel, Jan Stadermann,

Leibniz-Institut of Polymer Research Dresden, Hohe Strasse 6, Dresden, GermanyE-mail: voit@ipfdd.de

Applications of a polymeric material in micro- and nanotechnology as well organicelectronics are determined by functionality as well as molecular architecture. Today,controlled polymer synthesis methods like controlled radical polymerization (CRP) but also the chain-growth Kumada catalyst transfer polycondensation [1] enable control overstructure, molar mass and end functionality and further combination with highly efficientpolymer analogous reactions provides access to so far unknown well-defined functionalpolymeric materials.

In the first example we will show that by the combination of surface patterning via selfassembly of block copolymers with a supplemental photo-structuring, the fabrication of a more complex functional surface patterns can be realized with potential application in highly integrated micro-systems. Here, multifunctional block copolymers suitable for hybrid patterning have been realized by controlled radical polymerization (RAFT) combined with click reactions. Introduction of photolabile (NVOC) protected amino functions into one block combined with an unpolar styrene-based block resulted in the desired nanophase-separated thin polymer films. UV irradiation allows site-specific release of the free amino functions.[2]

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The second material class we would like to present are donor-acceptor block copolymers for polymer-based photovoltaic application. With a bifunctional initiator, block copolymers of P3HT and functional styrene blocks could be prepared successfully without any intermediate modifications. To further employ these materials, model copolymers were prepared to optimize reaction conditions for the functionalization with fullerenes, as this is still a difficult step towards donor-acceptor materials. Two basically different methods could be established.The reaction of fullerene C60 with a modified polymer under Bingel conditions was successful but materials of high purity but with rather low fullerene content resulted whereas the reaction of hydroxyl group containing polymers with bromo derivatives of fullerene with cesium carbonate as a base allowed the introduction of higher C60 content. The methods presented here will be applied in the synthesis of the C60 based block copolymers.

[1] Kaul, E.; Senkovskyy, V.; Tkachov, R.; Bocharova, V.; Komber, H.; Stamm, M.; Kiriy, A. Macromolecules 2010, 43, 77.[2] Stadermann, J.; Erber, M.; Komber, H.; Brandt, J.; Eichhorn, K.-J.; Bönsch, M.; Mertig, M.; Voit B. Macromolecules 2010, 43, 313

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NON-COVALENT SYNTHESIS OF FUNCTIONAL SUPRAMOLECULAR SYSTEMS

E.W. Meijer

Institute for Complex Molecular Systems, Eindhoven University of Technology. The Netherlands

E-mail: e.w.meijer@tue.nl

The intriguing prospects of molecular electronics, nanotechnology, biomaterials, and the aim to close the gap between synthetic and biological molecular systems are important ingredients to study the cooperative action of molecules in the self-assembly towards functional supramolecular systems. The design and synthesis of well-defined supramolecular architectures requires a balanced choice between covalent synthesis and the self-assembly of the fragments prepared. The current self-assembly processes are primarily controlled by solvent, temperature or concentration. For synthetic chemists, the non-covalent synthesis of these supramolecular architectures is regarded as one of the most challenging objectives in science: How far can we push chemical self-assembly and can we get control over the kinetic instabilities of the non-covalent architectures made? How can we go from self-assembly to self-organization? In the lecture, a few outlines of these challenges will be given using a number of examples out of our own laboratories, with the aim to come to new strategies for multi-step non-covalent synthesis of functional supramolecular systems.

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POLYSTYRENE COMPOSITES OF SINGLE-WALLED CARBON NANOTUBES

Abhijit Paul, 1 Brian P. Grady,2 Warren T. Ford1,3

1Department of Chemistry, Oklahoma State University, Stillwater, OK 74078, USA2Carbon Nanotube Technology Center (CaNTeC) and School of Chemical, Biological, and Materials

Engineering, University of Oklahoma, Norman, OK 73019, USA3Current address: Department of Chemistry, Portland State University, Portland, OR 97207, USA

Email warren.ford@okstate.edu

Single-walled carbon nanotubes (SWCNT) dispersed in N-methylpyrrolidinone (NMP) were functionalized by addition of polystyryl radicals from TEMPO-ended polystyrene. The amount of polystyrene grafted to the nanotubes was in the range of 20-25 wt.% irrespective of polystyrene number average molecular weight ranging from 2270 to 49500. In Raman spectra the intensity ratios of D to G bands were similar for all of the polystyrene-grafted samples and for the starting SWCNT. Numerous near-infrared electronic transitions of the SWCNT were retained after polymer grafting. The Raman and electronic spectra indicate that functionalization by polystyrene had little effect on the electronic properties of the SWCNT. TEM images showed bundles of SWCNT-g-PS of varied diameters with some of the polystyrene clumped on the bundle surfaces. Composites of SWCNT-g-PS in a commercial grade polystyrene were prepared by precipitation of mixtures of the components from NMP into water, e.g. the coagulation method of preparation. Electrical conductivities of the composites were about 10-15 S cm-1 and showed no percolation threshold with increasing SWCNT content. The glass transition temperature (Tg) of the composites increases at low filler loadings and remains constant with further nanotube addition irrespective of the length and number of grafted PS chains. The change of heat capacity (ΔCp) at Tg decreases with increasing amount of SWCNT-g-PS of 2850 molecular weight, but ΔCp changes very little with the amount of SWCNT-g-PS of higher molecular weight. The expected monotonic decrease in ΔCp coupled with the plateau behavior of Tg suggests there is a limit in the amount Tg of the matrix polymer can increase with increasing amount of filler.

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NOVEL POLYESTERS BASED ON CYCLOBUTANEDIOL: ENERGY EFFICIENT SYNTHESIS OF BISPHENOL A-FREE

MATERIALSDaniel J Burke,1,2 Martin Wolffs,2 Frank A. Liebfarth,1,2 Craig J. Hawker1,2,3

1Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA, 931062Materials Research Laboratory, University of California, Santa Barbara, CA, 93106

3Materials Department, University of California, Santa Barbara, CA 93106

E-mail: dburke@chem.ucsb.edu

The incorporation of bisphenol A (BPA) in polymeric materials such as the ubiquitous polycarbonate (PC) is of major concern because BPA is a known carcinogen and a suspected endocrine disruptor [1]. As such, there is demand for replacement materials which replicate the desireable properties of PC without the need for the use of BPA. These properties include optical clarity, high glass transition temperature, good impact resistence and tensile strength. One recent material which has been praised as a replacement for PC is Eastman Chemical’s Tritan™, which is a copolyester of tetramethylcyclobutanediol [2].

Recent work has shown that Meldrum’s acid can be a robust and versitile ketene precursor which can be incorporated into polymers as a crosslinker or as a handle for post-polymerization functionalization [3]. Here we demonstrate two new synthetic routes to a library of novel, functionalized cyclobutanediol monomers. These monomers are used in the synthesis of polyesters and copolyesters, and these resulting materials prove to be excellent candidates for replacing PC in a wide range of applications.

[1] Krishnan, A. V.; Stathis, P.; Permuth, S. F.; Tokes, L.; Feldman, D. Endocrinology 1993, 132, 2279-2286..[2] Morris, J.C.; Bradley, J.R. United States Patent 5, 955, 565, 1998[3] Leibfarth, F. A.; Kang, M.; Ham, M.; Kim, J.; Campos, L. M.; Gupta, N.; Moon, B.; Hawker, C. J. A Nature Chemistry 2010, 2, 207-212

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OLEFIN METATHESIS POLYMERIZATIONFROM ALKYNES

Tae-Lim Choi,

Department of Chemistry, Seoul National University, Seoul, Korea

E-mail: tlc@snu.ac.kr

Olefin metathesis reaction is a powerful tool to prepare various small to large molecules very efficiently. Ru-based Grubbs catalysts have popularized the reaction because the catalysts are not just highly active but also very easy to handle with good functional group tolerance. So far especially in polymerization, olefins are the main functional group for the monomer. Here, we will describe alkyne polymerization by olefin metathesis using Grubbs catalysts. Also, our strategy to achieve controlled cyclopolymerization to prepare polymers with desired molecular weights and narrow polydispersity indices will be discussed.(Fig. 1)[1] Detailed study on new monomers that produces polymers containing not five-membered ring, but six-membered ring further expands the utility of the alkyne polymerization and our investigation on their structure-activity relationship reveals that Thorpe-Ingold effect plays a crucial role for the synthesis of poly(ene)s that contains six-membered ring. [2]

Furthermore, application to synthesize various dendronized, star, diblock and graft copolymers will be disclosed.[3] Finally, images of their single molecule and nano structured supramolecules will be presented. If time allows, a new way of polymerization via tandem metathesis reactions will be discussed where relay of ring-opening-ring-closing reaction produces polymers with a conjugated back-bone. These polymers undergo efficient post-modification to build up the complexity in the polymerstructure.[3]

Fig. 1 Cyclopoymerization by metathesis mechanism

[1] Kang, E.-H., Lee, I. S., Choi, T.-L. J. Am. Chem. Soc. 2011, 133, 11904[2] Lee, I. S. ,Kang, E.-H., Choi, T.-L submitted.[2] Choi, T.-L Unpublished results.

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DESIGN AND SYNTHESIS OF CONJUGATED POLYMERS AND HYBRID MATERIALS

Suresh Valiyaveettil

Department of Chemistry, National University of Singapore3 Science Drive 3, Singapore 117543.

Tel. (65)68744327, Fax. (65)67791691, E-mail. chmsv@nus.edu.sg

Self-assembly is an important process in which defect free functional molecular architectures can be generated from simple building blocks. There are many examples in both biotic and abiotic systems. Our research interest is focused on the design and synthesis of novel conjugated polymers and use of weak interactions such as electrostatic and van der Waal’s forces to fine-tune the structure-property relationship. A series of amphphilic PPPs were synthesized in our lab showed an organized polymer lattice in the sold phase and can be organized into multilayers or honey combs on various substrates. In addition, self-assembly process also accommodates a series of additives such as fullerens, carbon nanotubes and metal nanoparticles without changing the lattice structure. The optical properties of such polymers are tunable using various additives such as acid, base or metal ions. The talk will include 1D, 2D conjugated systems, fused ring systems and donor-accepter units incorporated polymers which can be sued in various devices. The emphasis will be given to the design strategy, synthesis, and characterization of the novel molecules and materials.

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PRECISION SYNTHESIS IN CHAIN-GROWTH CONDENSATION POLYMERIZATION

Tsutomu Yokozawa, Akihiro Yokoyama

Department of Material and Life Chemistry, Kanagawa University,Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan

E-mail: yokozt01@kanagawa-u.ac.jp

Condensation polymerization is an important method of polymerization that yields not only engineering plastics such as polyamides, polyesters, polyimides but also π-conjugated polymers, which have recently received considerable attention with the development of the information technology industry. The molecular weight of those polymers is generally difficult to control and polydispersity index theoretically approaches 2 at high conversion, which is unlike the behavior of living polymerization. An uncontrolled molecular weight and broad molecular weight distribution stem inherently from a polymerization mechanism for step-growth polymerization. Accordingly, if the mechanism of condensation polymerization could be converted from step-growth to chain-growth, living condensation polymerization would be possible.

Nature already uses a chain-growth condensation polymerization process to synthesize perfectly monodisperse biopolymers such as polypeptides, DNA, and RNA. Even in artificial condensation polymerization of AB monomers, chain-growth mechanism could be involved in the following two cases. (1) The change of the substituent effect induced by bond formation of the monomer drives the reactivity of the polymer end group to become higher than that of the monomer. (2) In condensation polymerization based on coupling reaction with a transition metal catalyst, the catalyst is intramolecularly transferred to and activates the elongated polymer end group after the coupling reaction of the monomer with the polymer.

In the first case, we have attained chain-growth condensation polymerization for the synthesis of well-defined poly(p-benzamide)s, poly(m-benzamide)s, aromatic polyethers, poly(ether sulfone), and aromatic polyesters. Taking advantage of the living polymerization nature, we synthesized a variety of condensation polymer-containing architectures such as block copolymers, star polymers, and hyperbranched polymers [1].

The second case of chain-growth condensation polymerization with a metal catalyst has been independently found by us and McCullough et al. in the synthesis of poly(hexylthiophene). We have developed this polymerization to the precision synthesis of poly(p-phenylene), polyfluorene, and poly(N-alkylpyrrole). Block copolymers of different π-conjugated polymers were also synthesized by successive catalyst-transfer condensation polymerization in one pot [2].

In this paper, we report recent progress of chain-growth condensation polymerization: polymerization of AB2 monomers for well-defined hyperbranched polyamides as a category (1) and catalyst-transfer Suzuki-Miyaura coupling polymerization for a variety of well-defined π-conjugated polymers as a category (2).

[1] (a) Yokozawa, T.; Yokoyama, A. Chem. Rev. 2009, 109, 5595–5619. (b) Yokozawa, T.; Ajioka, N.; Yokoyama, A. Adv. Polym. Sci. 2008, 217, 1–77. (c) Yokoyama, A.; Yokozawa, T. Macromolecules 2007, 40, 4093–4101.[2] Miyakoshi, R.; Yokoyama, A.; Yokozawa, T. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 753–765.

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DEVELOPMENT OF NOVEL POLYMER-SUPPORTED MACMILLAN CATALYSTS WITH IONIC BOND FOR

ASYMMETRIC REACTIONNaoki Haraguchi, Yu Takemura, Masahiro Kaneko, Hitomi Kiyono, Shinichi Itsuno

Department of Environmental and Life Sciences, Graduate School of Engineering,Toyohashi University of Technology, Toyohashi 441-8580 Japan

E-mail: haraguchi@ens.tut.ac.jp

Chiral imidazolidin-4-one derivative developed by D. W. C. MacMillan is one of the mostefficient designed organocatalysts. The immobilization onto polymer has several advantages such as the facile isolation of product and the reuse of catalyst for practical use. Some research groups reported the design and synthesis of polymer-suppported MacMillan catalyst in which the catalyst was immobilized onto support polymer by covalent bond [1].

We have recently developed a novel immobilization method of chiral organocatalyst withquaternary ammonium salt onto suppot polymer [2]. Ion exchange reaction of MacMillan catalyst with sulfonated polymer proceeded smoothly to afford polymer-supported MacMillan catalyst P-1 [3]. The polymeric organicatalyst could be obtained by polymerization of monomer compraising MacMillan catalyst moiety with comonomer and crosslinker. In addition, main-chain chiral polymer with ionic bond P-2 have successfully synthesized by the reaction of dimer of MacMillan catalyst with disulfonic acid. Non-covalent immobilization has certain advantages since commercially available organocatalysts are directly used for immobilization and the reaction between sulfonatedpolymer and quaternary ammonium salt.

These catalytic activities were tested by the asymmetric Diels-Alder reaction of cyclopentadiene and trans-cinnamaldehyde. We found that the conversion and the enantioselectivity of adduct were influenced on the sulfonate, comonomer, crosslinker and synthetic method. Interestingly, the hydrophilic-hydrophobic balance of polymer structure is important for the catalyst performance. Some polymeric MacMillan catalysts showed high catalytic activity under optimizedcoditions and could be reused several times.

[1] Polymeric Chiral Catalyst Design and Chiral Polymer Synthesis; S. Itsuno, Ed., Wiley, 2011, Chapter 2, 35-42.[2] Itsuno, S.; Parvez, M. M.; Haraguchi, N. Polym. Chem. 2011, 2, 1942-1949.[3] Haraguchi, N.; Takemura, Y.; Itsuno, S. Tetrahedron Lett. 2010, 51, 1205-1208.

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SYNTHESIS OF FUNCTIONAL SMART POLYMERSD. Kuckling, A. Britze, S. Schmücker

Deparment of Chemistry, University of Paderborn, Warburger Str. 100,D-33098 Paderborn, Germany

e-mail: dirk.kuckling@uni-paderborn.de

Block copolymers exhibit unique properties like the formation of structures in the range from a few nanometers up to several micrometers by self-organization. Special interest is attracted by rod-coil block copolymers. Due to their rigid block smaller structures in dimensions of a few nanometers can be obtained. The introduction of different functionalities like electrochemical or photophysical properties is also possible by using rod segments. A variation of the polymer composition allows controlling the formed structures. Therefore controlled polymerization methods like atom transfer radical polymerization (ATRP) or nitroxide-mediated radical polymerization (NMRP) are necessary in order to prepare defined blocks. [1,2]

The aim of this work is the preparation of coil-rod-coil block copolymers composed of a middle poly(para-phenylene) (PPP) segment surrounded by stimuli-sensitive blocks. First, a PPP macroinitiator was synthesized via SUZUKI polycondensation (SPC) in the presence of a N- alkoxyamine termination reagent using microwave irradiation. By employing a microwave system instead of conventional heating by oil-bath reduced reaction times as well as increased yields could be observed. In order to prepare block copolymers nitroxide-mediated radical polymerization (NMRP) was used to introduce defined stimuli-sensitive segments. For the characterization of the polymers size exclusion chromatography (SEC), NMR spectroscopy and MALDI-TOF mass spectrometry was used.

In consequence of short range attractive forces (covalent bonds) and long range repulsive forces such as hydrophilic and hydrophobic interactions self-assembly of stimuli responsive block copolymers occurred.

[1] A. Britze, K. Moosmann, E. Jähne, H.-J. Adler, D. Kuckling, Macrom. Rapid Commun. 2006, 27, 1906-1912.[2] A. Britze, J. Jacob, V. Choudhary, V. Möllmann, G. Grundmeier, H. Luftmann, D. Kuckling, Polymer 2010, 51, 5294-5303.

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Poster Presentation Abstracts

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INFLUENCE OF SYNTHETIC CONDITIONS ON MORPHOLOGY AND ELECTRICALl conductivity

of POLYANILINE PREPARED BY INTERFACIAL POLYMERIZATION

Mona H. Abdel Rehim1, Heba Elsayed1, Ahmed M.Youssef2, Gamal Turky3

1Packing and Packaging Materials Department, Center of Excellence for advanced Science, Renewable Energy Group, National Research Center

2Packing and Packaging Materials Department, National Research Center3Microwave Physics and Dielectrics Department, National Research Center,

Cairo, Egypt

Abstract

Polyaniline is a polymer of wide applications but its lack of mechanical properties and low solubility are the main drawbacks of the polymer. In this study, we present polyaniline (PANI) samples prepared by interfacial polymerization using isopropanol, 1,3-butandiol, xylene and toluene in different organic/aqueous phase ratios and ammonium persulphate as initiator. The study also considered reaction time (4 hours or 24 hours). The formed PANI was characterized using FTIR, UV, TGA, XRD and the morphology was studied by SEM and TEM. The prepared PANI showed good solubility in many organic solvents such as ethanol and chloroform among others which facilitate the use of the polymer in many applications. The results showed also that the degree of crystallinity and morphology of the prepared polyaniline samples are affected by both type of organic solvent and ratio of organic/aqueous phases. Moreover, electrical conductivity is changed according to the type of organic solvent which reaches 5.2 S/cm for PANI prepared in xylene/water mixture.

Keywords: conductive polymer, polyaniline, interfacial polymerization, electrical conductivity.

The work was supported by through Science and Technology Development Fund (STDF), project number 1345.

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NEW SORBENTS BASED ON POLYMER COMPOSITIONS

Aiymgul M. Akimbaeva

National Nanotechnology Laboratory al-Faraby Kazakh State Natonal University,al-Faraby Street, 71, Almaty, the Republic of Kazakhstan, 050040

e-mail: amaim@yandex.ru

In the practice of water purification expensive and defficiency activated and oxidized coals have found a wide application. However, they have low abrasion resistance, losses upon thermal regeneration, high cost. For the recent time studies of sorption properties of shungite ores are being carried out, which are of interest as complex sorbents, possessing both the properties of carbon and silicate materials [1-3]. They differe advantageously from the other carbon materials by mechanic strength, thermal and chemical resistance and availability. With this purpose we have obtained shungites, modified by polyamines and epoxy compounds, and studied the conditions of sorption concentration of ions of Cu2+,Co2+,Ni2+ (CMe2+=0,25 g/l) with their individual and joint presence from the diluted solutions (ΣCMe2=0,075 g/l), modeling scrubbing and waste waters of galvanic industries of different degree of mineralization, and determined a possibility for the purification of phenol- containing solutions.

A comparison of the obtained physical-chemical characteristics of the studied sorbents (porosity, chemical and thermal stability) allows one one to predict their efficient in the processes of sorption.

Accounting for a possibility to sorb on different types of ionites we have checked a comparative study of the initial and industrial sorbents, selective to ions of non-ferrous metals. The results of the tests of sorption properties of the samples in the process of extraction of metal ions from one-component and mixed solutions testify to the efficiency of the modified shungite in comparison with natural and industrial sorbents. Saturation of shungite sorbents takes place for 30-45 min and 45-60 min on the anionite AB-17. It has been established that the modified shungite by its sorption activity in the solutions, containing simultaneously all ions of the indicated metals, is not inferior to AB-17, and in some cases purpasses it. The best characteristics by the value of exchange capacity have been attained on aminated shungite.

The obtained results of the studies demonstrate also efficiency of engrafting of amino-groups on the surface of shungite with the formation of new sorption centers and alternation of the volume properties of the materials for the extraction of phenol from water solution. Sorption practically does not depend on the contant of carbon in shungites. Extraction proceeds significantly betteron aminated shungite. Incidentally, with other equal conditions the latter efficiently purifies phenol-containing solutions in the presence of admixtures of organic substances.

The studied conditions of sorption of ions of non-ferrous metals and phenol by the modified shungite testify to a possibility of its application for the effective purification of natural and waste waters [4].

[1] Akimbaeva, A.M.; Ergozhin, E.E.; Anion exchangers based on modified schungites. 2007. T.80. №7.Вып.8.C.1269-1275. Англ. версия журнала: Russian J. of Applied Chemistry. 2007, 80(8), pp.1309-1316.[2] Ergozhin, E.E.; Akimbaeva, A.M.; Sadvokasova, A.B. New sorbents on the basis of shungite ores of Kazakhstan for the extraction of gold ions. 40th IUPAC congress. 14-19 August 2005, Beijing, China, P.89.[3] Akimbaeva, A.M. Sorption of chlorocomplexes of palladium (II) by nitrogen-containing modified shungites. Russian J. of Applied Chemistry. 2006, 79(4), pp. 312-316.[4] Akimbaeva, A.M. Sorption of phenol by modified shungites. Petroleum Chemistry. 2007.47(3), pp. 205-208.

118

SYNTHESIS & CHARACTRIZATION OF SELENIUM NANOFIBRES DOPED POLYANILINE

NANOCOMPOSITESShumaila,1,2 Masood Alam2, M. Husain1

1Department of Physics, Faculty of Natural Sciences, Jamia Millia Islamia, New Delhi-110025, India2Department of Applied Sciences and Humanities, Faculty of Engineering and Technology, Jamia

Millia Islamia, New Delhi-110025, India

E-mail: mush_reslab@rediffmail.com

Nanocomposites are special class of materials having unique physical properties and wide application potential in diverse areas1. Synthesis of polyaniline based nanocomposites has led to a number of potential applications in electronic and optical devices, catalysis, analytical sensors etc. Nanoparticles can be introduced into a matrix of polymer by different methods, the most common used strategies being the chemical2 and electrochemical routes.

In present research article we report the synthesis and electrical, morphological, thermal, structural and optical characterization of polyaniline doped with Selenium nanofibres. Polyaniline is synthesized by chemical oxidation using ammonium peroxodisulphate as an oxidizing agent and Selenium naofibres are synthesized using biomolecules (fig.1). Synthesized polyaniline was doped with different concentrations of Selenium nanofibres by chemical route. DC conductivity measurements on the doped and undoped polymer have been carried out in the temperature range 300-450 K. The results show an excellent increase in the conductivity after doping. Scanning Electron microscopy (SEM) has also been carried out for surface morphology studies. Thermal and structural properties are also studied by DSC and FTIR spectroscopy. DSC gives information about Tg and Tc. While the UV-Vis spectroscopy is used to study the optical properties. UV-Vis studies reveal that the band gap decreases on increasing the concentration of dopant which can be correlated to the increase in DC conductivity.

Fig.1: SEM image of Se nanofibres synthesized by using biomolecules.

[1] O’Mullane, A.P.; Dale, S.E.; Macpherson, J.V.; Unwin, P.R.; Chem. Commun. 2004, 10, 1606-1607.[2] Kim, B.H.; Jung, J.H.; Hong, S.H.; Curr. Appl. Phys., 2001, 1, 112-115.

119

PREPARATION, CHARACTERIZATION, IN VITRO MUCOADHESIVE AND RELEASE STUDY OF THIOLATED

CARBOXYMETHYL CHITOSAN-β-CYCLODEXTRIN NANOPARTICLES FOR CONTROLLED DELIVERY

OF HYDROPHOBIC DRUGSGhazaleh Alamdarnejad1,3, Alireza Sharif2,*, Mohsen Janmaleki3, Shahrouz Taranejoo3, Mohsen Dadgar1

1Department of Polymer Engineering, Islamic Azad University, South Tehran Branch, Abozar Blvd., Ahang 1777613651 Tehran, Iran

2Department of Polymer Science and Technology, Research Institute of Petroleum Industry (RIPI), 4th Km Karaj Highway, 1693913154 Tehran, Iran

3Nanomedicine and Tissue Engineering Research Center, ShahidBeheshti University (M.C.), Taleghani Hospital, Parvaneh St., Velenjak, 1985717443 Tehran, Iran

*Corresponding Author E-mail address: sharif.a1355@gmail.comPresenter E-mail address: gh.alamdarnejad@gmail.com

Biocompatible polymeric nanoparticulate systems, represent a very promising drug delivery platform for the oral delivery of therapeutic macromolecules with poor absorption characteristics. These polymeric nanoparticles as successful drug delivery vehicles, should have the ability to deliver drugs to desirable sites of body, protect them from degradation, facilitate drug contact with the absorption sites, promote their absorption through mucosal layer and release them in their bioactive form. In particular, much attention has been paid to the polysaccharide-based nanoparticles because of their high stability, safety, non-toxicity and biodegradability. In addition, they have low cost in their processing. Among these natural polysaccharides, chitosan is more attractive because of its biomedical [1] and pharmaceutical applications.

Although chitosan has numerous applications in pharmaceutical fields, the most important limiting factors are its poor solubility in aqueous media at neutral and alkaline conditions, poor interaction with hydrophobic drug molecules and low mucoadhesion properties. But it has numerous amino and hydroxyl groups that allow its functionalization to improve mentioned properties and possess the capacity to act as a matrix for the release of entrapped drugs in drug delivery systems.

Therefore the main objective of this study was to prepare and characterize nanoparticles of thiolated carboxymethyl chitosan (TCMCs) grafted with α-cyclodextrin (CD). First, α-cyclodextrin was grafted onto carboxymethyl chitosan (CMC) by cross-linking with 1,6-hexamethylene diisocyanate (HMDI) [2]. Next, the resultant product was grafted with thioglycolic acid (TGA) with water-soluble 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDAC) [3]. The structure of TCMC-CD was confirmed by FT-IR and XRD. Nanoparticles were developed by ionic gelation method using sodium tripolyphosphate (TPP) as a cross-linking agent [4] and were characterized by dynamic light scattering (DLS), scanning electron microscope (SEM) and atomic force microscope (AFM) and results showed that nanoparticles were quasi-spherical with average size of 80nm. In vitro mucoadhesive and release study of a hydrophobic model drug was also examined and it was indicated that the TCMC-CD nanoparticles could become an effective hydrophobic drug delivery system with controlled drug release capability.

[1] Mao, S.; Sun, W.; Kissel, T. Adv. Drug Delivery Rev. 2010, 62, 12–27.[2] Chen, L.; Tian, Z.; Du, Y. Biomaterials, 2004, 25, 3725–3732.[3] Saboktakin, M. R.; Tabatabaie, R. M.; Maharramov, A.; Ramazanov, M. A. Int. J. Biol. Macromol. 2011, 48, 403-407.[4] Anitha, A.; Deepa, N.; Chennazhi, K. P.; Nair, S. V.; Tamura, H.; Jayakumar, R. Carbohydr. Polym.2011, 83, 66–73.

120

ENGINEERING THE SELF-ASSEMBLY OF POLYCONDENSED AROMATIC HYDROCARBONS:

VERSATILE MATERIALS FOR OPTOELECTRONIC APPLICATIONS

Bassam Alameddine1 and Titus A. Jenny2

1Department of Mathematics & Natural Sciences, Gulf University for Science & Technology, Kuwait.2Chemistry Department, University of Fribourg, 1700 Fribourg, Switzerland.

E-mail: alameddine.b@gust.edu.kw2Chemistry Department, University of Fribourg, 1700 Fribourg, Switzerland

Polycondensed aromatic hydrocarbons (PAHs) have drawn much attention in the past two decades because of their remarkable stability and unsurpassed self-assembly through the noncovalent π-π stacking bonding, which bestows them with remarkable physicochemical and optoelectronic properties[1]. The disc-shaped hexa-peri-hexabenzocoronenes 1 decorated with lateral side chains self-organize in solution into highly ordered columnar molecular stacks. We found that those supramolecular structures are very sensitive to any variation of the medium as well as the nature of the lateral substituents. The cryo-SEM investigations that we carried out, among other techniques, revealed the formation of highly ordered nanowires (Figure 1). We also synthesized several derivatives of the half-lunar tribenzopentaphene 2 whose restricted symmetry allows for the decoration of various substituents at its periphery paving the way towards multifunctionalapplications.

Figure 1

References[1] Sergeyev, S.; Pisula, W.; Geerts, Y. V. Chem. Soc. Rev. 2007, 36, 1902-1929.

121

POLYMERIC NANOPARTICLES IN ENHANCINGDRUG SOLUBILITY

Aleksandra Pelczarska,1,2 Sophie Martel,2 Pierre-Alain Carrupt,2 Urszula Domanska1

1Physical Chemistry Division, Chemical Department, Warsaw University of Technology, Warsaw, Poland

2School of Pharmaceutical Sciences, University of Geneva, University of Lausanne, Geneva, Switzerland

E-mail: aleksandra.pelczarska@gmail.com

Polymeric nanoparticles present some important advantages over other colloidal carriers for drug applications, such as high storage stability and controlled release of the encapsulated drug [1, 2]. Polymeric nanoparticles can increase drug intracellular penetration by reducing the multi-drug resistance by avoiding the mechanisms of its efflux from cells [3].

The main aim of this research was to validate the usefulness of HTS-UV method (High throughput screening UV) for the estimation of thermodynamic drug solubility for drug-polymer nanoparticle-solvent systems. In recent years it appears extremely important to improve drug delivery systems due to more and more lipophilic drug structures, produced by drug design approaches. Stronger lipophilic character of drug lowers its solubility in water and also lower bioavailability in human body. Addition of nanoparticles can improve solubility of many sparingly soluble drugs. Thermodynamic solubility of drugs in liquid solvents plays a pivotal role in the design of drug compounds, as well as in the development and optimization of drug producing processes.

Solubility of sparingly soluble drugs containing aromatic ring in structure has been improved by addition of polymer nanoparticles. Maximum drug absorption and desorption on nanoparticles was measured at different drug concentrations, temperatures and pHs. The stability constants were determined by the measurements of the concentration of the drug in the sample as a function of the nanoparticles concentration.

This work is continuation of our previous research on enhancing drug solubility [4].

[1] De Campos, A. M.; Sanchez, A.; Alonso, M. J. A. Int. J. Pharm. 2001, 224, 159–168.[2] Kreuter, J. J. Microencapsulation 1988, 5, 115– 127.[3] Barratt, G.M. Pharm. Sci. Technol. Today 2000, 3, 163–171.*4+ Domaoska, U.; Pelczarska, A.; Pobudkowska, A. Int. J. Mol. Sci. 2011, 12, 2383-2394.

122

DENDRITIC GLYCOPOLYMERS IN BIOMEDICAL APPLICATIONS

Dietmar Appelhans,1 Josep Cladera,2 Mark Rogers,3 Brigitte Voit1

1 Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany2 Biophysics Unit and Center of Studies in Biophysics, Department of Biochemistry and Molecular

Biology, Universitat Autònoma de Barcelona, Bellaterra, Catalonia, Spain.3 UCD School of Biology and Environmental Science, University College Dublin, Belfield, Dublin 4,

Ireland

E-mail: applhans@ipfdd.de

The use of linear and dendritic glycopolymer is steadily growing up in the field of life sciences and nanotechnology. Especially, the multifunctional features of the sugar moieties such as non-covalent interactions, molecular recognition, tailoring of biological processes, enhancing biocompatibility and many others are of importance for the development of polymeric therapeutics and diagnostics. Our main research interest is the fundamental understanding of complexation and stabilization properties of dendritic glycopolymers towards metal ions,[1] drugs[2] and (inorganic) particles,[3] cellular uptake of dendritic glycopolymers and their drug@glycopolymer associates,[4] the bio-interaction with different biological materials and systems[5] for finally being able to tailoring the biohybrid materials for in-vitro[6,7] and in-vivo[7,8] experiments in the field of (bio-)medical applications.

Here, we present recent examples which concern the potential use of dendritic glycopolymers as polymeric therapeutics (e.g. non-toxic antiamyloidogenic agents in Alzheimer’s disease) and diagnostics (e.g. prion strains typing). A further example is directed to the establishment of an Au NP@dendritic glycopolymer hybrid material which is involved in the apoptosis of cancer cells. In this case antibody-conjugated hybrid materials induce the lysis of mitochondria in the cell where in separated biological experiments the dendritic glycopolymers showed no negative influence on the functions of the mitochondria organelle. Finally, the results give us a better view on the importance of oligosaccharide units attached on different dendritic scaffolds on gaining promising results from different biological experiments.

[1] D. Appelhans et al. Proc. R. Soc. A 2010, 466, 1489.[2] a) S. Boye et al. J. Chromatogr. A 2010, 1217, 4818.; b) A. Richter et al. New J. Chem. 2010, 34, 2105.[3] a) A. Köth et al. Colloid Polym. Sci. 2008, 286, 1317; b) A. Fahmi et al. New J. Chem. 2009, 33, 703; c) M. Kubeil et al. Chem. Asian J. 2010, 5, 2507.[4] D. Appelhans et al. Biomacromolecules 2009, 10, 1114.[5] a) B. Klajnert et al. Chem. Eur. J. 2008, 14, 7030; b) M. Fischer et al. Biomacromolecules 2010, 11, 1314; c) O. Klementieva et al. Biomacromolecules 2011, accepted; d) A. Janaszewska et al. New J. Chem. 2011, accepted; e) A. Köth et al. Soft Matter 2011, DOI: 10.1039/c1sm06439h.[6] M. Mkandawire et al. J. Biophoton. 2009, 2, 596.[7] S. Höbel et al. J. Control. Release 2011, 149, 146.[8] a) B. Ziemba et al. J. Biomed. Mater. Res. 2011, DOI:10.1002/jbm.a.33196; b) A. Janaszewska et al. New J. Chem. 2011, DOI: 10.1039/C1NJ20444K.

123

INCORPORATION OF CARBON NANOTUBES INTO ORGANIC POLYMER MONOLITHIC COLUMNS FOR

CAPILLARY CHROMATOGRAPHY

Ahmad Aqel1, Kareem Yusuf2, Zeid A. ALOthman2, A. Yacine Badjah-Hadj-Ahmed2,Abdulrahman A. Al-Warthan1

1King Abdullah Institute for Nanotechnology, College of Science, King Saud University, P.O. Box 2454 Riyadh 11451 Saudi Arabia, Kingdom of Saudi Arabia

2Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Kingdom of Saudi Arabia

Email: ahmad3qel@yahoo.com, aifseisi@ksu.edu.saTelephone: +966505284007, +96614674198, Fax: +96614675992.

This work describes fabrication of polymer monolithic materials to be used as stationary phases in capillary liquid chromatography. Multi-wall carbon nanotubes (MWCNT) were incorporated into an organic polymer monolith containing benzyl methacrylate (BMA) and ethylene dimethacrylate (EDMA). The porogenic solvents were selected to maintain a uniform polymer matrix in the capillary column. Several columns have been synthesized in the confines of 320 μm i.d. and 150 mm length fused-silica capillaries by single step in-situ copolymerization reaction.

The porous and hydrodynamic properties; i.e. porosities, permeabilities and mechanical stabilities of the prepared monolithic columns were thoroughly investigated. Also, their morphology were characterized by using different techniques, such as the optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA). The columns were then chromatographically evaluated; efficiency and performance towards different sets of analytes were obtained and compared, mixtures of ketonic and phenolic compounds were successfully separated and evaluated.

KeywordsCapillary liquid chromatography; Organic polymer monolith; Benzyl methacrylate; Ethylene dimethacrylate; Carbon nanotube.

124

SIMULTANEOUS CORE DEGRADATION AND DRUG RELEASE FROM NOVEL NANOSTRUCTURES:

BRANCHED-ARM STAR POLYMERS VIA“THROUGH-ARM” POLYMERIZATION

Alan O. Burts1 and Jeremiah A. Johnson1

1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

E-mail: aburts@mit.edu

Polymer-drug conjugates,1 specifically branched polymer-drug architectures, possess attractive features for in vivo drug delivery applications.2 PEGylated dendrimers have proven effective for in vivo and in vitro treatment of cancer;3 synthetic challenges limit access to libraries of dendrimer-based delivery systems for combinatorial therapy. We have developed a novel synthetic approach termed “through-arm” polymerization that allows rapid access to multiple drug-loaded, nanoscopic polymers of easily tunable size and composition. Here we describe water-soluble polyethylene-glycol (PEG) based branched-arm star polymers, which possess photodegradable cores and an anticancer drug (doxorubicin) covalently bound near the core via a photodegradable linker. The synthesis was facilitated by ring-opening metathesis polymerization (ROMP) combined with “click” chemistry; a small library of drug-loaded polymers with sizes that ranged from 22 nm to 36 nm was prepared and evaluated in vitro for effectiveness against human breast cancer cells. Ultraviolet irradiation lead to simultaneous drug release and degradation of the star core to yield particles with Dh < 6 nm. The drug-loaded polymers were non-toxic to cells in the absence of light; 10 min of irradiation induced cell toxicity equivalent to the free drug. Due to their ease-of-synthesis and modular structures, these materials may be useful candidates for targeted delivery of cancer chemotherapeutics.

[1] Duncan, R. Nat. Rev. Cancer 2006, 6, 688-701.[2] Peer, D., Karp, M. J., Hong, S., Farokhzad, C. O., Margalit, R., Langer, R. Nat. Nanotechnol. 2007, 2, 751-760.[3] Fox, M. E., Guillaudeu, S., Frechet, M.J., Jerger, K., Macaraeg, N., Szoka, C. F. Mol. Pharmaceutics. 2009, 6, 1562-1572.

125

ORGANOSILANE-BASED SELF-ASSEMBLED MONOLAYERS AND SURFACE PROTECTION

Elisa Cappelletto,1 Rosa di Maggio1

1Department of Material Engineering and Industrial Technology of Trento, via Mesiano 77, 38123 Trento, Italy, Phone:+39-4611282453, Fax: +39-4612824145,

e-mail: elisa.cappelletto@ing.unitn.it

Sol gel process is a colloidal route used to synthesize inorganic or hybrid materials. This approach is adaptable for the production of film and fibers as well as bulk pieces with desirable properties [1-2]. This method can also be used to prepare self assembling monolayers (SAMs) on various surfaces. SAMs are two-dimensional films, one molecule thick, covalently assembled at an interface. The aim of this research work is the study of different functionalized alkoxysilanes to form self assembling layers. The solutions of active materials are prepared starting from the precursors ((R)4-nSi(OC2H5)n, R= CH3, Ph, F etc.) through acid catalysis (sol-gel process); the low pH allows to obtain chain polymers with a fast hydrolysis step. Self assemblies are formed by simply immersing a substrate into the sol (dip coating). The driving force for the assembly is the formation of polysiloxane during the condensation step (classic sol-gel process) and the reaction with the surface of the substrate [3]. SAMs of alkoxysilane require a hydroxylated surface as substrate to their formation. In this work we have studied alkoxysilanes functionalized with hydrophobic groups, these molecules are arranged with these groups on the surfaces changing its wettability. The structure of SAMs and their hydrophobic behavior are investigated through solid NMR and water contact angle measurements. An important application of these SAMs is the protection of wood. The hydroxyl groups present on its surface ensures the formation of a covalent bond with alkoxysilanes compounds, hydrophobic functional groups allow to protect the wood from fungal attacks. It is possible to modify properties of different surfaces changing functional groups of alkoxysilanes.

Reference

[1] Belleville, P. Comptes Rendus Chimie. 2010, 13, 97–105.[2] MacKenzie, J.D.; Bescher, E. Journal of Sol-gel Science Technology. 2003, 27, 7-14.[3] Ulman, A., Chem Rev. 1996, 96, 1533-1554

126

A STUDY ON THE EFFECT OF NANOPARTICLES ON THE CRYSTALLINE PLANES IN THERMALLY

CONDUCTIVE POLYPROPYLENEHassan Ebadi-Dehaghani,1 Monireh Nazempour2

1 Polymer Department, Shahreza Branch, Islamic Azad UniversityShahreza, Isfahan, Iran2 Material Department, Shahreza Branch, Islamic Azad UniversityShahreza, Isfahan, Iran

E-mail: ebadi@iaush.ac.ir(Polymer Department, Shahreza Branch, Islamic Azad University, P.O. Box 81145-311, Shahreza,

Isfahan, Iran Tel: +983213243001-5)

Thermally conductive polymer nanocomposites have attracted many research efforts because they can be used instead of metal parts [1]. In this study three nanocomposite containing 5 to 15 wt% of nanoparticles prepared by extrusion were used. The thermal conductivity (TC) of compression moulded polypropylene (PP) and PP filled nanoparticles was studied using thermal conductivity analyser (TCA). The incorporation of nanoparticles improved crystallinity and thermal conductivity simultaneously. The experimental TC values of PP nanocomposites with different level of nanoparticles concentration showed a linear increase with an increase in crystallinity. The TC improvement in PP/ZnO nanocomposite is greater than that of PP/calcium carbonate nanocomposites. This fact can be attributed to intrinsic thermal conductivity of the ZnO nanoparticles. The morphological features of polymer nanocomposite, such as crystalline form, spherulite and nanoparticle size and also the nature of nanoparticles can affect the final properties. It is well known that PP mainly has three crystalline forms: monoclinic α, hexagonal α and orthorhombic α. However α-PP is difficult to form unless specific agents are used [2-3]. A new peak at 2α=15.5° corresponding to the (300) crystal plane of α-PP was observed which is caused by the presence of CaCO3 and ZnO nanoparticles, respectively.

The K value of both PP/ CaCO3 and PP/ZnO nanocomposites had an increase with an increase in nanoparticle contents The higher K values of the nanocomposites indicate that the nanoparticles favor α-PP, inducing higher ductility and strength.

[1] Han, Z.; Fina A. Prog. in Polym. Sci. 2011, 36, Issue 7, 914-944.[2] Labour T.; Vigier G.; Seguela R. J. of Polym. Sci.: Part B Polym. Phys. 2002, 40 (1), 31–42.[3] Liu J.J.;Wei X.F.; Guo Q.P. J. of App. Polym.Sci. 1990, 41(11–12), 2829–2835.

127

COMPARING THE EFFECT OF NANO-CaCO3 AND NANO-ZnO ON RHEOLOGICAL PROPERTIES OF

POLYPROPYLENE USING SEVERAL MODELSHassan Ebadi-Dehaghani

Polymer Department, Shahreza Branch, Islamic Azad UniversityShahreza, Isfahan, IranE-mail: ebadi@iaush.ac.ir

(Polymer Department, Shahreza Branch, Islamic Azad University, P.O. Box 81145-311, Shahreza, Isfahan, Iran Tel: +983213243001-5)

Polymer nanocomposites have attracted increasing attention in recent years because of their significant improvement of physical and/or chemical properties over the matrix polymers [1-2]. Melt rheometry is vitally important for processing of polymer-based nanocomposites. Also, it is a powerful tool for inspecting the internal microstructure of polymer nanocomposites [3-4]. In order to understand how the nanofillers enhance the properties of the polymers, many studies have been performed using dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM), to find a link between the structure and the properties of the nanocomposites [4]. There are no comprehensive studies reported on the effect of nano-structured CaCO3 and ZnO on the rheological properties of PP using literature models. In the current study, we will report on these effects.

The CaCO3 and ZnO nanoparticles were dried in an oven at 60°C for 12 hours before melt extrusion. The PP pellets and nanoparticles were melt-compounded in a co-rotating twin screw extruder (Dr. Collin Company, ZK 25 Model, Ebensburg, Germany) at a temperature in the range of 155 to 190°C and a screw rotation rate of 60 rpm. The CaCO3 and ZnO nanoparticle contents were 5, 10 or 15 wt% with the addition of 1 wt% stearic acid in order to prevent coalescence of nanoparticles. The extrudates were pelletized at the die exit, dried and then compression molded into 1cm thickness sheets (30cm×30cm×1mm) at 180°C.

The morphology of nanocomposites was evaluated by SEM to observe the distribution of nanoparticles within the extruded materials. The micrographs of cryofractured surface of the nanocomposites showed moderate nanoparticle dispersion. However, partial coalescence was unavoidable especially in PP/nano- ZnO composite.

The plots of experimental and theoretical storage moduli values at 20°C for various loadings of nanoparticles by wt% Showed that the Einstein model had better agreement with experimental values while the Guth model deviated the most. Dynamic rheometry using a parallel plate rheometer showed that the rheological moduli of the nanocomposites increased with increase in nanofiller concentration; however this increase was greater in the high frequency region. There was an increase in complex viscosity of the nanocomposites with increasing the nanofiller concentration. Moreover, the rheological behavior of nanocomposites is more sensitive to nanoparticle concentration at low frequencies. All of the models used for prediction of melt viscosity underestimated the viscosity of nanocomposites, but the Einstein and Roscope equations was the nearest to experimental values for PP/CaCO3 and PP/ZnO nanocomposites respectively.

[1] Sun, T.; Chen, F.; Dong, X. and Han, C.C. Polym. 2008, 49, 2717-2727.[2] Zhang QX, Yu ZZ, Xie XL and Mai YW. Polym., 2004, 45, 5985-5994.[3] Cassagnau, Ph. Melt rheology of organoclay and fumed silica nanocomposites. Polym. 2008, 49, 2183-2196.[4] Ajayan, PM., Schadler L.S. and Braun, P.V. “Nanocomposites Science and Technology”. Wiley-VCH GmbH & Co. KGaA 2004 122-127

129

PREPARATION, CHARACTERIZATION AND PROPERTIES OF NOVEL FERROCEN-BASED ORGANOMETALLIC

POLY(ETHER SULFONE AMIDE IMIDE)S

Hassan Ebadi-Dehaghani,1 Shahram Mehdipour-Ataei2

1 Polymer Department, Shahreza Branch, Islamic Azad UniversityShahreza, Isfahan, Iran2 Iran Polymer and Petrochemical Institute, Tehran, Iran

E-mail: ebadi@iaush.ac.ir(Polymer Department, Shahreza Branch, Islamic Azad University, P.O. Box 81145-311, Shahreza,

Isfahan, Iran Tel: +983213243001-5)

Organometallic polymers have attracted many attentions in recent years due to the fact that polymers containing metals might be expected to possess properties different from those of conventional organic polymers [1-3]. Outstanding properties of ferrocene-containing polymers including air-, heat-, and photochemical stability make them suitable for a variety of applications including thermal stability lubricants and thermal stability elastomers. A new ferrocene-based diamine (ESAFDA) with built-in ether, sulfone, and amide groups was prepared via reaction of two different synthetic precursors. Firstly, 1,1’-ferrocenedicarbonyl chloride was prepared from 1,1’-ferrocenedicarboxylic acid using oxalyl chloride. In another reaction, nucleophilic substitution reaction of 3-aminophenol with bis(4-chlorophenyl sulfone) was used for synthesis of 3,3’-(4,4’-sulfonyl bis(1,4-phenylene) bis (oxy)) dianiline (SBOD). Finally, the diamine was prepared via nucleophilic reaction of SBOD with 1,1’-ferrocenedicarbonyl chloride. The precursors and diamine were characterized by conventional methods and the diamine was used for preparation of different ferrocene-based poly(ether sulfone amide imide)s through polycondensation with three different dianhydrides. The polymers were characterized by elemental analysis, FTIR and 1H-NMR spectroscopy. Various properties of the polymers including inherent viscosity, molecular weight, solubility, thermal stability and behavior, flame-retardant nature, mechanical properties, and crystallinity were studied. Presence of ferrocene structure in companion to ether, sulfone, and amide units in the backbone of polyimides led to improved solubility of the polymers in polar aprotic solvents and enhanced thermal stability and flame-retardant character of polyimides.

[1] Culbertson B.M.; Pittman C.U.; New monomers and polymers. Plenum, New York 1984.[2] P. Stepnicka, Ferrocenes: ligands, materials and biomolecules; Wiley, Chichester 2008.[3] C.E. Carraher, J.E. Sheats, C.U. Pittman, Advances in organometallic and inorganic

130

PHOTO-ASSISTED SONOLYTIC DEGRADATION OF (ACRYLIC ACID -CO- ACRYL AMIDE) HYDROGELS IN

THE PRESENCE OF TIO2 NANOPARTICLES

Rajabali Ebrahimi,1 Mahsa Narjabadi1, Hamed Khani1

1Member of Scientific Association of chemistry, Takestan branch, Islamic Azad University,Takestan IranE-mail: Ebrahimi_r@qiau.ac.ir

The degradation of one of the commercially important hydrogel based on acrylic acid and acryl amide, (acrylic acid-co-acryl amide) hydrogels, by means of ultrasound irradiation and its combination with heterogeneous (TiO2) was investigated. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. The extent of sonolytic degradation increased with increasing ultrasound power (in the range 30–80 W). TiO2 sonophotocatalysis led to complete (acrylic acid-co-acryl amide) hydrogels degradation with increasing catalyst loading, while, the presence of TiO2 in the dark generally had little effect on degradation. Therefore, emphasis was totally on the sonolytic and sonophotocatalytic degradation of hydrogels and a synergy effect was calculated for combined degradation procedures (Ultrasound and Ultraviolet) in the presence of TiO2 nanoparticles. TiO2 sonophotocatalysis was always faster than the respective individual processes due to the enhanced formation of reactive radicals as well as the possible ultrasound-induced increase of the active surface area of the catalyst. A kinetics model based on viscosity data was used for estimation of degradation rate constants at different conditions and a negative order for the dependence of the reaction rate on total molar concentration of (acrylic acid-co-acryl amide) hydrogels solution within the degradation process was suggested.

Fig. 1 Typical The relationship between ηr and sonication time in sonocatalytic process, for different loading of catalyst at constant power of ultrasound (30W) at 25˚C.

[1] Taghizadeh, M.T.; Abdollahi, R. Ultrason. Sonochem. 2011, 18, 149-157.[2] Ebrahimi, R. Iran Polym. J. 2011, in press

131

NEW TREND FOR PREPARATION FRIENDLY ENVIRONMENTAL CHEMICALS FROM WASTE

PETROLEUM PRODUCTS FOR DIFFERENT APPLICATIONS

A.Kamel El-Morsi & Noura el Mehbad2

and A.M.A. Omar*

Department Of Process Design & Development, Egyptian Petroleum Research Institute, Cairo, EgyptUniversity of Gizan , Kingdom of Saudi Arabia

Corresponding author mail : abdelazimomar@yahoo.co.uk

Abstract

One of the most advanced catalytic reactions is phase transfer catalysis ( PTC ) that avoids the use of solvent. In phase transfer catalytic reactions one of the participant reactants can be brought in to the normal phase of the other reactant in such form that high reaction rates are observed .In this paper we prepare different types of poly aromatic alcohols from waste products of petroleum industry such as aromatic extract & heavy alkylate. Aromatic extract as received from refineries contains undesirable components e.g long chain saturates and other different impurities, e.g. asphaltenes, resins, sulphur compounds and heterocyclic compounds so the aromatic extract must be purified. The used purification method is based on dewaxing of saturated components and the remaining components are treated by active clay to remove heterocyclic and resin components. The purified aromatic extract was chloromethylated in the presence of phase transfer catalysts. The chloride derivatives are directly converted into valuable alcohol by condensing the yield of purified chloromethylated compounds with sodium hydroxide in the presence of the synthesized phase transfer catalysis, (CH3CH2 ), CH3 C6H4 N

+ ( C2H4OH)3 and CH3 (CH3CH2) C6H4 N+ [ ( C2H4OH) 3 ]

Co++] CH3 COO--

(A and B). The mechanism of hydroxyl group substituted chloride ion was suggested. The reaction rate was accelerated and the results were discussed according to kinetic studies of reactions and surface properties of catalysts.

132

CHIRAL-AT-ANSA-BRIDGED GROUP 4 METALLOCENE COMPLEXES {(R1R2C)-(3,6-TBU2FLU)(3-R3-5-ME-C5H2)}MCL2: SYNTHESIS, STRUCTURE, STEREOCHEMISTRY,

AND USE IN HIGHLY ISOSELECTIVE PROPYLENE POLYMERIZATION

Manal Farah,1 Evgeny Kirillov,2,3 Nicolas Marquet,2 Manuela Bader,2 Abbas Razavi,4 Vincenzo Belia,4 Frank Hampel,3 Thierry Roisnel,2 John A. Gladysz,3,5 Jean-François Carpentier,2

1Total Petrochemicals, Total Research Center Qatar, Doha, Qatar2Organometalliques et Catalyse, U M R 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex,

France3Institut für Organische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Henkestrasse

42 91054 Erlangen, Germany4Total Petrochemicals Research Feluy, Zone Industrielle C, 7181 Feluy, Belgium

5Department of Chemistry, Texas A&M University College Station, Texas 77842-3012, United StatesE-mail: manal.farah@total.com

A family of bridged group 4 metallocene precatalysts with carbon-linked mixed fluorenyl-cyclopentadienyl ligand has been prepared in order to study the relation between various unsubstituted, monoaryl, and diaryl substituted methylene bridged precatalysts and their catalytic performances, in isotactic polypropylene production.

Different chiral, sterically crowded ansa-zirconocene and ansa-hafnocene complexes have been investigated to evaluate first the impact of modifying the bridge substituents between single or double aryl bridge substitutions, on the catalyst reactivity. The second objective is to study the effect resulting from having a chiral centre on the bridge upon the catalytic performance of each of the two diastereomeric ansa-metallocene generated.

The synthesis of various ligand structures (R1R2C)-((3,6-tBu2Flu)H)(3-R3-5-Me-C5H3) where (R1=H, R2=Ph, R3=tBu) 2a, (R1=H, R2=2,4,6-Me3C6H2(Mes), R3=CMe2Ph(cumyl) 2b, (R1=H, R2=3,5-(CF3)2C6H3, R

3=tBu) 2c, (R1=CF3, R2=Ph, R3=tBu) 2d, (R1=R2=H, R3=tBu) 2e and their correspondent

ansa-metallocene are reported. The structure and stereochemistry of these metallocene complexes are correlated to the polypropylene properties. The goal is to target structural modifications improving the performance of such catalysts and the control they afford on propylene polymerization and thus the targeted polymer properties.

[1] Kirillov, E.; Marquet, N.; Bader, M.; Razavi, A.; Belia, V.; Hampel, F.; Roisnel, T.; Gladysz, J. A.; Carpentier, J. F. Organometallics 2011, 30, 263–272.[2] Kirillov, E.; Marquet, N.; Razavi, A.; Belia, V.; Hampel, F.; Roisnel, T.; Gladysz, J. A. ; Carpentier, J.-F. Organometallics 2010, 29, 5073.

133

ENGINEERING OF PHENYLBORONIC ACID-BASED GLUCOSE-SENSITIVE POLYMER MICROGELS WITH 4-VINYLPYRIDINE FOR WORKING AT

PHYSIOLOGICAL PH AND TEMPERATURE

Zahoor H. Farooqi, 1 Mohammad Siddiq, 1, 2 Weitai Wu, 2 Shuiqin Zhou, 2

Abbas Khan1

1Department of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan2Department of Chemistry of College of Staten Island, The City University of New York, Staten Island,

New York 10314E-mail: zhfarooqi@gmail.com

Aqueous colloidal glucose-sensitive poly(N-isopropylacrylamide-4-vinylpyridine-phenylboronic acid) [p(NIPAM-4VP-PBA)] microgels have been synthesized in aqueous media by the functionalization of poly(N-isopropylacrylamide-2-vinylpyridine-acrylic acid) [p(NIPAM-4VP-AA)] microgels with 3-aminophenylboronic acid via carbodiimide coupling using different percentage of 4VP. The morphology of the microgel particles was characterized by TEM. The glucose-sensitive, pH responsive and thermosensitive behaviors of the microgels were investigated using dynamic light scattering technique. The feeding contents of the hydrophilic 4-vinylpyridine group increase the hydrodynamic radius and volume phase transition temperature of the resultant microgels. The glucose-sensitivity of the PBA-containing microgels relies on the stabilization of the charged phenylborate ions by binding with glucose, which can convert more hydrophobic PBA groups to the hydrophilic phenylborate ions. The effect of 4VP contents on hydrodynamic radius and volume phase transition was systemic studied at different pH values. The effect of VP contents on the glucose sensitivity was also investigated at physiological pH and temperature [1].

[1] Farooqi, Z.H.; Wu, W.; Zhou, S.; Siddiq. M. Macromol. Chem.Phys. 2011,212, 1510-1514.

134

QUANTITATIVE STRUCTURE PREPERTY RELATIONSHIP MODELING OF FREE RADICAL CHAIN TRANSFER

CONSTANT IN STYRENE POLYMERIZATION

Mohammad Hossein Fatemi, Fereshte Dorostkar

Laboratory of Chemometrics, Faculty of Chemistry, University of Mazandaran, Babulsar, IranE-mail: mhfatemi@umz.ac.ir

In the present work, the quantitative structure–reactivity relationship (QSRR) [ 1,2] was used to predict the chain transfer constant (log Cx) for some organic agents as chain transfer agent in free-radical polymerization of styrene. Energy of the lowest unoccupied molecular orbital (ELUMO), hydrogen-bonding dependent hydrogen donor charged area (HDCA-1), first-order Kier and Hall index (1χ), final heat of formation/ number of atoms (ΔHf/NA), count of H donors sites (CHD) and Min> (0.1) bond order of a C atom (BOC,min) are selected as the most relevant variable from the pool of calculated descriptors by stepwise multiple regression feature selection method. Then artificial neural network (ANN) and multiple linear regression (MLR) were utilized to construct the nonlinear and linear quantitative structure-reactivity relationship models, respectively. The standard errors in the prediction of log Cx by MLR model are; 0.641, 0.964, and 0.843 and for ANN model are; 0.049, 0.076 and 0.090 for training, internal and external test sets, respectively. The predictivity of ANN model was further examined by cross-validation methods which produce the statistics of Q2 = 0.85 and SPRESS= 0.484. The results of this study revealed the applicability of QSRR modeling of kinetic chain transfer constant by using artificial neural network.

References:

[1] Fatemi, M.H.; Baher, E.; Ghorbanzade, M. J. Sep. Sci. 2009, 32, 4133-4142. [2] Fatemi, M.H.; Dorostcar, F. Europ. J. Med. Chem. 2010, 45, 4856-4862.

135

CHARACTERIZATION BY TGA AND UV-VISIBLE OF NEW PIGMENT MATERIALS CONTAINING MICA, P4VP

AND D&C Red 6 Dye

Ali MANSRI 1, Fayçal DERGAL 1 et Laurent BILLON 2

1Laboratoire d’application des électrolytes et des polyélectrolytes organiques (LAEPO)Département de Chimie, Faculté des Sciences, Université de Tlemcen.

B.P.119, Tlemcen 13000, Algeria.Tel/Fax: 00 213 43286308; e-mail: alitilimsen_60@yahoo.fr ; dergalf@yahoo.fr

2Laboratoire de physique et de chimie des polymères- Institut Pluridisciplinaire de Recherche en Environnement et Matériaux, IPREM-EPCP, UMR-CNRS 5254 de l’Université de Peau et des pays de

L’Adour.2, Avenue du Président Agnot, 64053 Pau Cedex 9, France.

Tel: 00 33 559407600; Fax: 00 33 559407623; e-mail: laurent.billon@univ-pau.fr

Key words: Mica, P4VP, composite, hybrid, pigment, D&C Red6

Summary:

The pigments and dyes industry must constantly develop new products with more innovative visual effects. Various industrial sectors such as cosmetics, textile fibers, the car industry or paintings… etc, looking up new optical effects for their commercial products. The field of study of these pigments is vast and the market is in full expansion. Among the desired optical effects, manufacturers try to imitate nature by creating the appearance of increasingly sophisticated products: for example interferential compounds changing color and aspect under the effect of the light and according to angle. Such effects can achieve through the existence of well structures defined and organized within compounds to be developed. [1-3] In our work, we succeeded in formulating new pigmentary materials by adsorption of polymer on mica particles and fixation of D&C Red 6 dyes on polymer. These new pigmentary materials can either differ by their colors, or to present interferential effects.

Scheme1: concept of fixation of D&C Red6 dye on hybrid material [P4VP/Mica] The materials obtained were characterized by TGA and UV-VISIBLE. The amount of D&C Red 6 dye fixed on the

hybrid materials [P4VP/Mica] is determined by TGA. The presence and the shape of the dye fixed on hybrid materials [P4VP/Mica] are determined by UV-VISIBLE.

Référence:

[1] Colorants and auxiliairies. Vol 1. Ed Society of Dyers and Colourists. 2002.[2] Ghanam Leïla. Thèse de Doctorat. France: Université de Pau. 2006.[3] L. Ghannam, H.Garay, M.E. R. Shanahan, J. François, and Laurent Billon American Chemical Society 2005.

136

METAL-ORGANIC COMPLEX ARRAYS (MOCAs)

Alejandro M. Fracaroli,1 Pothiappan Vairaprakash,1 Hisanori Ueki,1 Kentaro Tashiro,1 Omar M. Yaghi2

1International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.

2Center for Reticular Chemistry and the Center for Global Mentoring, Department of Chemistry and Biochemistry,University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles,

California 90095, United States.E-mail: FRACAROLI.Alejandro@nims.go.jp

For many years the selective synthesis of multimetallic heteronuclear complexes has been a challenging objective in the field of inorganic chemistry. The escalating number of possible structure outcomes (e.g., for six different metals with n positions, there are 6n possibilities) turns the final goal in a complicated issue. Nevertheless the access to such materials may lead to highly selective catalysts, cascading reactions, tunable emissive materials, molecules containing sequences of metal complexes that code for specific chemical transformations and many other potential applications. Recently, several research groups have shown interests in this goal, where multimetallic dendrimers [1] and heteroheptametallic complexes [2] have been reported as the typical examples so far. Their preparation, however, requires particular properties of the ligands or multi-step synthesis and hence more simple and versatile methodologies are still demanded.

In this work we present the results in the sysntesis of heterometallic complexes arrays by using a solid phase synthesis (SPSs) technique adapted from Merrifield solid-phase peptide synthesis [3]. Trough this novel methodoly we succesfully achieve the loading of six metal centers including Ru(III), Pt(II), Rh(III), Ir(III) and Re(I), in one array controlling especifically the sequency and the distance between of them (Figure 1) [4].

Figure 1

[1] Takanashi, K.; Fujii, A.; Nakajima, R.; Chiba, H.; Higuchi, M.; Einaga,Y.; Yamamoto, K. Bull. Chem. Soc. Japan 2007, 80, 1563–1572.[2] Packheiser, R.; Ecorchard, P.; Rüffer, T.; Lang, H. Organometallics 2008, 27, 3534-3546.[3] Merrifield, R. B. J. Am. Chem. Soc. 1963, 85, 2149-2154.[4] a) Vairaprakash, P.; Ueki, H.; Tashiro, K.; Yaghi, O. M. J. Am. Chem. Soc. 2011, 133, 759-761. b) C&EN. 2011, 89, 8. c) In preparation.

137

DE NOVO BENZENE SYNTHESIS USING NOVEL 1,3-DIENIC-δ-SULTONES

Jens Gaitzsch,1,2 Victor Rogachev,1 Martin Zahel,1 Peter Metz1

1Technische Universität Dresden, Organic Chemistry I, Dresden, Germany2Leibniz Institute of Polymer Research Dresden e. V., Dresden, Germany

E-mail: gaitzsch@ipfdd.de

In the query to synthesize bioactive natural compounds and functional materials, benzene derivatives are important intermediates. In cases, when the necessary benzene core’s substitution may not be reached using substitution, other methods have to be used. For this purpose it is essential to develop novel reactions leading to substituted benzenes.

Among others, the domino Diels-Alder/retro-Diels-Alder(DA/RDA) reaction of α-2H-pyranones or 1,2-diazines are attractive processes in this respect. Their 1,3-dienic moiety reacts with acetylene derivatives as dienophils to provide substituted benzenes by elimination of either CO2 or N2, respectively. To the best of our knowledge, the corresponding transformation of δ-sultones embedding a 1,3-diene moiety, the sulfonic acid analog to α-2H-pyranones, was only reported from our group1. We synthesised a variety of phenylic substituted 1,3-dienic δ-sultones2,3, which had the potential to perform a Diels-Alder/retro-Diels-Alder reaction. Here, we show the potential of this reaction, by using sultones 2-4 with a variety functionalized arylic residues3. The de novo benzene synthesis of phtalic acid derivatives 6a-6g could be achieved with sultones 2a-2g, using a Diels-Alder/retro Diels- Alder approach with DMAD 5 as a dienophile. We showed successfully, that 1,3-dienic δ- sultones with alkynes react analogous to their CO2 and N2 analogists δ-pyranones and δ-diazines. The activation using microwave radiation proved to be the most efficient way to start the reaction, while high pressure activation is the cleanest way to perform this reaction. The similar reaction with monosubstituted alkynes, like 1a, give 1,2,4 but not 1,3,5 substituted benzenes. A substitution of the sultone 2a at the adjacent phenyl rings in sultones 2b-2g shows only little influence on the reactivity of the sultones with the DA/RDA sequence. However, an introduction of substitutes in α position to the sulfur atom totally blocks the desired reaction path. Hence, we showed the first example of a sultone used in a de-novo benzene synthesis using a Diels-Alder/retro-Diels-Alder approach.

[1] Gaitzsch, J.; Rogachev, V. O.; Metz, P.; Yusubov, M. S.; Filimonov, V. D.; Kataeva, O. J. Sulfur Chem. 2009, 30, 4-9.[2] Rogachev, V. O.; Yusubov, M. S.; Filimonov, V. D. Russ. J. Org. Chem. 1999, 35, 415-418.[3] Gaitzsch, J.; Rogachev, V.O.; Metz, P.; Filimonov, V.D.; Zahel, M.; Kataeva, O. J. Sulfur Chem. 2011, 32, 3

138

PHOTO CROSS-LINKED AND PH SENSITIVE POLYMERSOMES FOR BIOMEDICAL APPLICATIONS

Jens Gaitzsch,1 Dietmar Appelhans, Giuseppe Battaglia,2 Petra Schwille,3 Brigitte Voit1

1Leibniz Institute of Polymer Research Dresden e. V., Dresden, Germany2Department of Biomedical Science, University of Sheffield, Sheffield, United Kingdom

3 TU Dresden, Biotechnological Center, Dresden, GermanyE-mail: gaitzsch@ipfdd.de

Over the past decade, researchers have tried to develop feasibly polymer-based systems for biomedical applications, such as drug delivery systems or artificial organelles1. Polymersomes have proven to be a promising candidate for such systems. Compared to their biological counterpart, the liposomes, their membrane is considerably thicker and show increased mechanical and chemical strength2. This strength can yet be improved by introducing chemical bonds within the membrane, e.g. to cross-link it. We combined this cross-linking with a well-known pH sensitive polymer to give a highly stable polymersome with strictly controlled trans-membrane diffusion by reversible pH switches3.

Polymersomes consist of amphiphilic block-copolymers, which eventually self-assemble into hollow vesicles (Fig. 1, left). We use polyethylenglycole (PEG) as a biostable hydrophilic block, which is combined the pH sensitive polydiethylaminoethyl-methacrylate (PDEAM) and photocross-linkable poly-dimethylmaleicimidobutylmethacrylate(PDMIBM) as hydrophobic components3. The content of the PDMIBM is high enough to provide effective cross-linking after 30 s of UV irradiation, while the pH sensitivity remains. While pH sensitive polymersomes usually disassemble upon acidification, ours show a definite swelling, since the cross-linked membrane remains intact. This swelling is reversible as well as reproducible, indicating a highly stable cross-linking (Fig. 1, right).

These vesicles provide a very good basis for a synthetic bionanoreactor. While the membrane is not open for diffusion traffic in the basic state, small molecules are able to diffuse inside in an acidic state. Additionally, they are non-toxic and show good cellular uptake into different cell types. Therefore, a bioactive protein (myglobin) could be incorporated into the vesicle. Only, if the membrane is made open for diffusion, the myoglobin can react with substrate added to the solution. Therefore, an enzymatic reaction is observed at pH 6, but not at pH 8 (Fig. 2). Thus, we demonstrate that our system is capable as a bionanoreactor for applications in synthetic biology and may be the starting point in creating a synthetic organelle.

[1] A. Blanazs, S. P. Armes, A. J. Ryan, Macromol. Rapid Commun. 2009, 30, 267.[2] C. LoPresti, H. Lomas, M. Massignani, T. Smart, G. Battaglia, J.Mater.Chem. 2009, 19, 3567.[3] J. Gaitzsch.; D. Appelhans; D. Gräfe; P. Schwille; B. Voit; Chem. Commun. 2011, 47, 3466.

Figure 4: Pictures of polymersomes (left) and reversible swelling uponswitching between pH 3

and 10 (right).

Figure 3: Scheme of an pH dependent enzymatic

reaction within an polymersome.

139

AB INITIO STUDY IN 5,6 DIHYDROXYNAPHTALEN 1,4 DION AND DERIVATIVES,

NICS AND RING CURRENT EFFECTMohammadali Ghorbani1, Alireza Heidari1, Niloofar Heidari1,2 , Ahmet Yıldırım3

1Institute for Advanced Studies, Tehran 14456-63543, Iran2Department of Materials Engineering, Institute of Mechanical Engineering, University of

Tabriz, Tabriz 51666-16471, Iran3Department of Mathematics, Science Faculty, Ege University, 35100 Bornova-Izmir, Turkey

E-mail: mohammadalighorbani1983@yahoo.com

The study of ground state intramolecular proton transfer reaction has received increasingattention in the last few years aiming at the characterization of a large number of compounds in which hydrogen migration occurs rapidly. The presence of two hydrogen bonds in the former two compounds enables a double proton transfer that can take place either in two steps or in a concerted manner. This phenomen was conducted using ab initio quantum mechanical methods with the HF/6-31G* and HF/6-31+G (2d,2p) basis sets. Nucleus independed chemical shift (NICS) was determined in several structure (GS1,TS,GS2) displacement of electron-withdrawing and electron-donating groups in process of intramolecular proton transfer in different situation revealed. NICS value of rings for extraction NMR data carried out by B3LYP/6-311+G(2d,p) basis set of level of ab initio calculation, NMR shielding tensors was computed with the continues set of gauge transformations (CSGT) method. NICS value in both of rings in which the intramolecular proton transfer occurred, was calculated at zero and 1.0 ° A above the ring. These results indicated that value of electron density in the α ring increased and it decreased in β ring. In he following table is presented collection of B3LYP/6-311+G(2d,p) NICS values (in ppm) calculated at the rings center, NICS (0), 1.0 ° A above its rings, NICS (1), for the optimized HF/6-31G* ground state and transition state geometry of each species.

[1] Drasar, B. S.; Hill, M. J. Human Intestinal Flora. Academic press. New York, 1974.[2] Li, J.; Zhou, M.; Li, B.; Zhang, G. Synth. Commun. 2004, 34, 275.[3] Mo, L. P.; Ma, Z. C.; Zhang, Z. H. Synth. Commun. 2005, 35, 1997.[4] Xia, M.; Wang, S.; Yuan, W. Synth. Commun. 2004, 34, 3175.[5] Chen, D.; Yu, L.; Wang, P. G. Tetrahedron Lett. 1996, 37, 4467.

140

CONFORMATIONAL, STRUCTURAL AND AROMATIC FEATURES OF (8,8) CLOSE-ENDED

CARBON NANOTUBE 7/5/7 RING ARRANGEMENT: A THEORETICAL AB INITIO STUDY

Mohammadali Ghorbani1, Alireza Heidari1, Niloofar Heidari1,2 , Ahmet Yıldırım3

1Institute for Advanced Studies, Tehran 14456-63543, Iran2Department of Materials Engineering, Institute of Mechanical Engineering, University of Tabriz,

Tabriz 51666-16471, Iran3Department of Mathematics, Science Faculty, Ege University, 35100 Bornova-Izmir, Turkey

E-mail: mohammadalighorbani1983@yahoo.com

In the present work, (8,8) close-ended carbon nanotube with 7/5/7 ring arrangement has been studied. Conformational and geometrical parameters of included rings in this nanotube have been investigated by HF/STO-3G level of theory. We have also analyzed the aromaticity of this compound by means of nucleus independent chemical shift (NICS) criterion. We have computed the NICS values using the HF/STO-3G method by G98 program for computed this structure at the a, b, c points and included rings in this compound. The results of these calculations will be presented and discussed.

[1] Knoevenagel, E. Chem. Ber. 1894, 27, 234.[2] Jones, G. In Organic Reactions; Wiley: New York, 1967, 15, 204–599.[3] Freeman, F. Chem. Rev. 1981, 80, 329.[4] (a) Tietze, L. F.; Saling, P. Synlett. 1992, 281. (b) Borah, H. N.; Deb, M. L.; Boruah, R. C.; Bhuyan, P. J. Tetrahedron Lett. 2005, 46, 3391.[5] Tietze, L. F. Chem. Rev. 1996, 96, 115.[6] (a) Ayoubi, S. A.-E.; Texier-Boullet, F.; Hamelin, J. Synthesis. 1994, 258. (b) Binev, I. G.; Binev, Y. G.; Stamboliyska, B. A.; Juchnovski, I. N. J. Mol . Struct. 1997, 435, 235. (c) Brufola, G.; Fringuelli, F.; Piermatti, O.; Pizzo, F. Heterocycles 1997, 45, 1715.[7] Prajapati, D.; Lekhok, K. C.; Sandhu, J. S.; Ghosh, A. C. J.Chem. Soc. Perkin Trans. 1996, 959.

141

STUDYING OF THE FORMS OF AZA-CYCLO ALKADIENES WITH MIDDLE SIZE

BY AB INITIO METHOD

Mohammadali Ghorbani1, Alireza Heidari1, Niloofar Heidari1,2 , Ahmet Yıldırım3

1Institute for Advanced Studies, Tehran 14456-63543, Iran2Department of Materials Engineering, Institute of Mechanical Engineering, University of Tabriz,

Tabriz 51666-16471, Iran3Department of Mathematics, Science Faculty, Ege University, 35100 Bornova-Izmir, Turkey

E-mail: mohammadalighorbani1983@yahoo.com

In this research, we examine the amount of energy necessary for establishing the different forms of the cyclo alkadienes and aza-cyclo alkadienes combinations with medium size. The amount of energy for establishing them were computed by the two orders HF/STO-3G and B3LYP/6-31G** and a comparison was made between their stability. In these compounds, cyclo alkadienes is the most stable and cyclo octadienes is the most unstable compounds. Also, the flat forms of ten-member compounds of aza-cyclo alkadienes were obtained and the difference amount of energy for establishing between two flat and non-flat states as the above-mentioned compounds was computed and when there is no resonance between unconnected electron pair of nitrogen and triple band (C=C), this difference is greater. Finally, the different forms (boat, twist, and chair) of cyclo alkadienes and aza-cyclo alkadienes were obtained, the amount of energy necessary for them was computed and a comparison was made between their stability. It was concluded that the chair form is the most stable form and stability of the twist form is lower than boat form.

[1] Collard-Motte, J.; Janousek, Z. Top. Curr. Chem. 1986, 130, 89.[2] Ficini, J. Tetrahedron 1976, 32, 1449.[3] Viehe, H. G. In Chemistry of Acetylenes; Viehe, H. G., Ed.; Mercel Dekker: New York, 1968; Ch. 12, pp 861–912.[4] Katrizky, A. R.; Jiang, R.; Singh, S. K. Heterocycles 2004, 63, 1455.[5] Viehe, H. G. Angew. Chem., Int. Ed. En. 1967, 6, 767.[6] (a) Furber, M. In Comprehensive Organic Functional Group Transformations; Katritzky, A. R.; Metht-Cohn, O.; Rees, C. W. Eds.; Pergamon: Oxford, 1995; Vol. 1, p. 997. (b) Ficini, J. Tetrahedron 1967, 32, 1449. (c) Collard-Motte, J.; Janousek, Z. Top. Current Chem. 1986, 130, 89. (d) Zificask, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L. Tetrahedron 2001, 57, 7575. (e) Tanaka, K.; Takeishi, K. Synthesis 2007, 18, 2920.[7] Mantani, T.; Ishihara, T.; Konno, T.; Yamanaka, H. J. Flurine Chem. 2001, 108, 229.[8] (a) Yavari, I.; Sabbaghan, M.; Hossaini, Z. Synllet. 2006, 2501. (b) Yavari, I.; Djahaniani, H. Tetrahedron Lett. 2006, 47, 2953. (c) Yavari, I.; Moradi, L. Tetrahedron Lett. 2006, 47, 1627. (d) Yavari, I.; Hossaini, Z.; Sabbaghan, M. Tetrahedron Lett. 2006, 47, 6037. (e) Yavari, I.; Djahaniani, H. Tetrahedron Lett. 2005, 46, 7491.[9] Scriven, E. F.V., Org. Synth. Coll. 1955, 3, 735.

142

N,N’-BIS-(BIPYRIDYL)-N’’-ALKYL-BTA FUNCTIONALIZED POLYMERS AS SINGLE CHAIN

POLYMERIC NANOPARTICLE CHEMOSENSORSMartijn A.J. Gillissen,1,2 Anja R.A. Palmans,1,2 E.W. Meijer1,2

1Laboratory of Macromolecular and Organic Chemsitry, Eindhoven University of Technology2Institute of Complex Molecular Systems, Eindhoven University of Technology

P.O. Box 513, 5600 MB, Eindhoven, The NetherlandsE-mail: m.a.j.gillissen@tue.nl

The functional properties of natural proteins inspired us to engineer artificial polymer systems that fold via non-covalent interactions into well-ordered protein-like structures: single-chain polymeric nanoparticles (SCNPs). The folding of single polymeric chains into well-defined structures is a field of research receiving considerable attention over the last few years. Our focus lies on developing well-defined single chain polymeric nanoparticles by making use of non-covalent interactions, investigating their properties and understanding their folding behaviour [1]. Next to gaining more insight into the fundamental aspects of polymer folding we envision applications in catalysis or coating technology. Another potential application for SCNPs is making use of the susceptibility of non-covalent interactions towards changes in the environment to prepare sensor materials. The copper ion is an important trace mineral in organisms and an essential component of many enzymes and proteins; it is also identified as an environmental pollutant potentially very toxic to organisms [2]. Therefore the design of chemosensors for Cu(II) is still actively investigated [3]. A supramolecular sef-assembly unit recently developed within our group is N,N’-bis-(bipyridyl)-N’’-alkyl-BTA, the aggregation behaviour of such discotics can be influenced by Cu(II) ions. With this in mind we have prepared polymers incorporating this unit and studied their conformational and self-assembly behaviour in solution as potential candidate for a Cu(II) sensor material.

Figure 1: a) Synthesis of SCNP polymers, b) Fluorescent response upon Cu(II) titrations.

Using a combination of scattering and spectroscopic techniques we have studied the dilute solution behaviour of this polymer. In further experiments the polymer was tested for its potential as a sensor material, by addition of Cu(II) to the solution. The fluorescence of the discotic agregate could be completely quenched revealing the potential of these systems for use as Cu(II) chemosensor materials. Next to having more insight into the conformational changes in the discotic functionalized single chain nanoparticles upon decreasing the overall solvent quality, the concept of detecting pH and Cu(II) concentration changes with these nanoparticles is feasible. For further experiments we are currently working on the preparation of water soluble norbornene-based polymers for detecting pH and Cu(II) changes in water.

[1] T. Terashima et al., J. Am. Chem. Soc. 2011, 133, 4742.[2] R. Seth et al., Toxicol. in Vitro 2004, 18, 501.[3] R. Krämer, Angew. Chem. Int. Ed. 1998, 37, 772.[4] M.A.J. Gillissen et al., Isr. J. Chem. 2011, DOI: 10.1002/ijch.201100063

143

A TETRADENTATE AZA LIGAND-COBALT COMPLEX AS EFFICIENT WATER BASED REVERSIBLE MOLECULAR

OXYGEN BINDING SYSTEMBaris Gure, Ahmet Ince, Gokhan Cankaya, Niyazi Bicak

Istanbul Technical University, Department of Chemistry, Maslak 34469 Istanbul, TurkeyE-mail: gurebaris@gmail.com

Water soluble cobalt complex of non-volatile ligand (HEPTETA), obtained by reaction of triethylene tetramine (TETA) with glycidol (Scheme-1) was demonstrated to be an excellent reversible oxygen binding-storage system. Experiments showed that, the oxygen binding occurs by forming 1:1 oxygen adducts with air oxygen and completed within few minutes under atmospheric pressure as inferred from UV, oxygen sensor and volumetric gas measurements. The adduct is stable up to 95 oC and quantitative oxygen releasing takes place above this temperature as evidenced by volumetric gas measurements and TGA techniques.

Scheme 1: Synthesis of HEPTETA and its cobalt complex

The system presented seems to be superior to well-known CoSalen [1] due to its high capacity (ie.20 L per mole) and excellent reversibility. The synthesis pathways, oxygen uptake-release characteristics and possible use of the cobalt complex as oxidation catalyst will be discussed in this presentation.

Scheme 2 : HEPTETA oxygen binding mechanism

[1] E. Tsuchida, H. Nishide, M. Ohyanagi, H. Kawakami; Macromolecules 20, 1907-1912,1987.

144

SURFACE-MODIFIED POLYETHYLENE FILM ASAN INDICATOR FOR HEAVY METAL CONTAMINANTS

Chayanant Hongfa, Peerada Samunual, Sukhvinder Singh Khanuja, Wayne Nicholas Phillips

Science Division, Mahidol University International College, Salaya, Phutthamonthon,Nakhon Pathom 73170, Thailand

E-mail: icchayanant@mahidol.ac.th

Heavy metals contamination is a major problem in both developed and developing countries. Heavy metals, such as lead or mercury are often found in products such as children toys, paints, and food products. As a result, there is an urgent need for an economical heavy metal indicator. In order to address this issue, the modern approach of layer-by-layer (LbL) assembly to modify a surface of polyethylene can be used. The strip of high-density polyethylene (HDPE) was obtained from used water and milk bottles. A solution of chromium trioxide and sulfuric acid was then used to oxidize the surface of HDPE into multiple carboxylic acid groups. The polyethylene glycol was attached covalently to the surface of HDPE by the esterification process using oxalyl chloride. The newly made HDPE with hydrophilic surface was non-covalently embedded with various types of water-soluble ligands that can change their colors based on the coordination with different heavy metals.

145

DECORATION OF POLYMER MICROSPHERESWITH AMINE FUNCTIONAL DENSE POLYMER BRUSHES

VIA PHOTOINIFERTER TECNIQUEAhmet Ince, Niyazi Bicak

Istanbul Technical University, Department of Chemistry, Maslak 34469 Istanbul, TurkeyE-mail: ahmetince85@gmail.com

Decoration of solid surfaces with functional polymer brushes has been one of the interesting areas of intensive research in recent years. Various methods; “grafting from” “grafting through” and “grafting onto” have been studied for modification of solid surfaces with polymers. Among those, “grafting from” approach has been found the most fruitful process for decoration of solid surfaces with polymers. This approach has been termed as “surface initiated polymerization” (SIP). In this approach ATRP is of paramount importance due to its advantages over controlled radical polymerization techniques such as RAFT and NMP operating by chain transfer mechanism. However ATRP is almost limited to acrylic and styrenic monomers. Other monomers such as vinyl amides or vinyl esters cannot be polymerized buy means of ATRP. This limitation is important drawback to build up of surface tethered functional graft copolymers.

In recent years our research group has interested in developing synthesis method to produce solid microspheres with amine functional polymer brushes [ref]. Our interest is mainly focused on grafting of newly commercialized monomer, N-vinylformamide (NVF ). Its polymer has been most important precursor of polyvinylamine.

In this presentation we will discuss generation of dense polyvinylamine brushes on crosslinked polystyrene microspheres. The experiments showed that, NVF can be polymerized from ditiocarbamate functional surface groups successfully by photoiniferter technique. It was found that this approach enables high grafting yields up to 1200 %. The PNVF brushes so generated were hydrolyzed to give polyvinylamine (Scheme 1)

Scheme 1: Generation polyvinylamine functions on PS-DVB microspheres surface

Having a reactive amine function, the polymer brushes offer numerous modification possibilities to generate various functionalities for diverse applications. The use of such architectures as carrier for catalyst or reagent is interesting and expected to provide nearly homogenous conditions due to partial mobility of graft chains.

[1] Gazi, M.; Giancarlo Galli ,;Bicak, N., Separ. Sci. Tech. 2008,62 484–488.

146

OLIGOMERIZATION OF ACETYLENE FROM GAS ELECTROCRACKING OVER Pd/CNFs CATALYST

A. S. Ismail

Department of Chemistry, Faculty of Education for Pure Sciences, University of Al Anbar, Iraq. E-mail: chemocenter@gmail.com

The unique properties of carbon nanofibers (CNFs), a novel structured carbon material developed in the last two decades, have generated a large number of applications including selective absorption, energy storage, polymer reinforcement, and catalyst supports [1].

The results show the possibility production of olefin hydrocarbons from gas electrocracking as a first stage, and the subsequent stage investigated the regularities of the oligomerization of acetylene in the gas electrocracking on palladium catalyst, we supported palladium on CNFs and developed a highly active catalyst for hydrogenation of hydrocarbons. CNFs supported palladium catalysts (0.5%Pd) were prepared by a standard incipient impregnation method using aqueous solutions of palladium (ll) chloride PdCl2 as a palladium precursor. Carbon nanofibers (CNFs) were synthesized from a previous study [2], obtained also from acetylene in the gas electrocracking over γ-Fe2O3 catalyst, oligomerization of acetylene with a Pd/CNFs catalyst has been investigated. Catalytic experiments were performed in a fixed bed reactor at atmospheric pressure, synthesized at 140 - 270 ºC, using gas hourly space velocity (GHSV) in the range 3000-7000 h-1 of feed gas. Resulting shows that the yield of green oil or (liquid hydrocarbons) reduce when the temperature increase and increase in the yield of methane, ethene, propene and butene, as well as a more stable catalyst.

[1] Pechuro N. S., Francesov V. K., Reception of fibrous carbon from gases containing carbon monoxide, .M.: Center research institute of information and techno-economic, petrochemistry 1989, 76.[2] Ismail A. S., Nikolaev A. I., Peshnev B. V., Production of carbon nanofibers from the gas electrocracking on iron oxide catalyst, Solid Fuel Chemistry J. 2009, 1,54-57.

147

EFFICIENT PREPARATION OF DHMF AND HMFA IN IONIC LIQUIDS FROM BIOMASS-DERIVED HMF

Eun-Sil Kang, 1 Da Won Chae, 1 Baekjin Kim2 and Young Gyu Kim*1

1Fine Chemicals Laboratory, Department of Chemical & Biological Engineering, Seoul National University, Seoul, 151-744, Republic of Korea

2Green Chemistry & Manufacturing System Division, Green Process R&D Department & PolymerMaterials Research, Korea Institute of Industrial Technology (KITECH), ChoeonAn, 330-825,

Republic of KoreaE-mail: ygkim@snu.ac.kr

The growing concern about depletion of traditional energy sources is making biomassderived resources more attractive. 5-Hydroxymethylfurfural (HMF) is one of the novel biomassderived platform chemicals corresponding to those already established for fossil fuel-based platform chemicals. 2,5-Dihydroxymethylfuran (DHMF) and 5-hydroxymethylfuranoic acid (HMFA) are versatile intermediate chemicals of high industrial potential that can be obtained from HMF. For example, DHMF is a six-carbon monomer in the manufacture of novel resins, polymers and artificial fibers. It can also be used as an intermediate in the synthesis of drugs and crown ethers. HMFA not only serves as a new component in various polyesters but also as a precursor of 2,5- furandicarboxylic acid (FDCA) with high potential applications in the polymer field. Here, an efficient, mild, and operationally simple Cannizzaro reaction process for the synthesis of both DHMF and HMFA from HMF using ionic liquids as reaction solvents will be reported.

Figure 1. Cannizzaro reactions of HMF

[1] Blanksma, J. J. Rec. trav. chim. 1911, 29, 403-406.[2] Durant-Pinchard, M. FR Patent 2556344, 1985.[3] Gandini, A. ACS Symp. Ser. 1990, 433, 195-208.[4] Timko, J. M. ; Cram, D. J. J. Am. Chem. Soc. 1974, 96, 7159-7160.[5] Hirai, H. J. Macromol. Sci. Chem. 1984, A21, 1165-1179.[6] Gandini, A.; Belgacem, M. N. Prog. Polym. Sci. 1997, 22, 1203-1379.[7] Moreau, C.; Belgacem, M. N.; Gandini, A. Top. Catal. 2004, 27, 11-30.

148

PREPARATION OF A CHIROPTICAL OLIGOMER FROM3,4-ETHYLENEDIOXYTHIOPHENE AND (˜)-MYRTENAL

Hirotsugu Kawashima,1 Hiromasa Goto1

1Goto Lab., Institute of Materials Science, Graduate School of Pure and Applied Sciences,University of Tsukuba, Tsukuba, Ibaraki, 305-8573, Japan

1Tel: +81-29-853-5128, Fax: +81-29-853-4490,E-mail: gotoh@ims.tsukuba.ac.jp

Conjugated polymers which have benzenoid and quinonoid alternating structure in the main chain bridged via methine group (methine polymer) have been paid much attention because of the relatively small-bandgap [1]. Polycondensation between arylene unit and aldehyde group in the presence of sulfuric acid has been developed for conducting methine polymers.

Scheme 1. Synthesis of methine bridged oligomer from 3,4-ethylenedioxythiophene and (-)-myrtenal.

In this paper, we synthesized a methine oligomer from EDOT and (–)-myrtenal, achiral compound (Scheme 1). Chiroptical activity and doping effect for the resultant thusprepared is examined based on consideration of high sensitivity derived from low bandgap [2].

Absence of the aldehyde signal in the IR absorption spectrum of the resulting material indicates completion of the polycondensation reaction. GPC measurement evaluated that the number average molecular weight (Mn) is 900, the weight average molecular weight (Mw) is 1600, polydispersity (Mw/Mn) is 1.72. The oligomer shows a broad absorption band and circular dichroism (CD) in the long wavelengths. The chiral side chain induces helical conformation of the main chain to exhibit chiroptical activity. Iodine doping for the oligomer was examined, and the doped state was monitored with UV-vis, CD, and electron spin resonance (ESR) spectroscopy.

The UV-vis absorption and the ESR measurements confirm the formation of radical cations. CD spectra of the oligomer show blue shift of the CD signal during the doping. Figure 1 shows CD and UV-vis absorption spectra of the oligomer in CHCl3 with various iodine doping levels. This suggests that the change in electronic structure upon doping tunes its chiroptical activity.

[1] S. A. Jenekhe, Macromolecules, 1990, 23, 28482854.[2] H. Kawashima, H. Goto, Materials, 2011, 4, 10131022.

Fig. 1 CD and UV-vis absorption spectra of theoligomer in CHCl3 with various

iodine doping levels.

149

PREPARATION OF A GREEN COLORED CHIRAL POLYMER FILM: ELECTROCHEMICAL

POLYMERIZATION IN A CHOLESTERIC LIQUID CRYSTALLINE MEDIUM

Hirotsugu Kawashima,1 Yusuke Nitta,1 Hiromasa Goto1

1Goto Lab., Institute of Materials Science, Graduate School of Pure and Applied Sciences,University of Tsukuba, Tsukuba, Ibaraki, 305-8573, Japan

1Tel: +81-29-853-5128, Fax: +81-29-853-4490, E-mail: gotoh@ims.tsukuba.ac.jp

Electrochemical polymerization is a method for preparing π-conjugated polymers as films on surfaces of electrodes. Because of reversible redoxactive properties, films obtained by electrochemical polymerization are expected to be applied to display devices.

Fig. 1 Polarized optical microscopic images of a cholesteric liquid crystalline electrolytesolution (a) and the polyEBE film prepared by electrochemical polymerization in the cholesteric

liquid crystalline medium (b).

Our group previously reported an approach to control microscopic structures of conjugated polymer films by electrochemical polymerization using liquid crystalline media [1]. This method allows us to transcribe microscopic structure of the liquid crystalline media to obtained films. Figure 1a shows a polarized optical microscopic (POM) image of a characteristic fingerprint texture of a cholesteric liquid crystalline phase. Electrochemical polymerization in the cholesteric liquid crystalline phase affords transcription of the fingerprint texture of the liquid crystal to a resulting film (Figure 1b). This is because polymerization reaction of monomers which dissolve in the liquid crystalline medium undergoes on a surface of a positive electrode, along the direction of the liquid crystalline molecular orientation.

Herein, we synthesized 4,7-di(2,3-dihydrothieno[ 3,4-b][1,4]dioxin-5-yl)benzo[1,2,5]thiadiazole (EBE). It was reported that a polyEBE film obtained by electrochemical polymerization exhibits green color in the reduced state [2]. We also conducted electrochemical polymerization of EBE using a cholesteric liquid crystal as a reaction medium (Scheme 1).

[1] K. Kawabata and H. Goto, Chem. Lett., 2009, 38, 7, 706707.[2] A. Durmus, G. E. Gunbas, P. Camurlu and L. Toppare, Chem. Commun., 2007, 3246–3248.

150

PHOSPHOROUS DENDRIMERS AND THEIR USESIN SUSTAINABLECATALYSIS

Michel Keller,1,2 Armelle Ouali,1,2 Anne-Marie Caminade,1,2 Jean-Pierre Majoral 1,2

1Laboratoire de Chimie de Coordination UPR 8241 CNRS, BP 44099, 205, route deNarbonne, 31077, Toulouse Cedex 04, France

2Université de Toulouse ; UPS , INPT ; LCC ; F-31077 Toulouse France.E-mail: keller@lcc-toulouse.fr

The availability of non-renewable resources such as metals does not seem to be guaranteed over the next decades so that solutions have to be found to ensure their future supply [1]. Transition and rare earth metals being involved as catalyst in a wide range of chemical reactions, their recycling at the end of chemical processes thus appears as a fruitful strategy. In this context, the use of large sized polymeric supports for catalysts enables the recovery of metals after the reaction by simple filtration for example [2]. Among the large array of available polymers, dendrimers are appealing candidates. Indeed, because they are synthesized step by step, dendrimers are well-defined hyperbranched and monodisperse macromolecules. Moreover, in some cases, dendritic ligands were shown to greatly increase the catalytic activity of the metal (dendritic effect) [3].

In this communication, we will present the synthesis of phosphorous-based dendrimers [4] as catalytic ligands involving various functions at their periphery: diketones, iminopyridines, thiazolylphosphines and also terpyridines. The catalytic activity conferred by the latter to different metals (Cu, Pd) or rare earth (Sc, Y) will be evaluated in different reactions enabling the formation of C-O and C-N (Cu-catalyzed arylations of phenols and nitrogen heterocycles) or C-C bonds (Pdcatalyzed Suzuki reaction, Sc or Yb promoted-Mukaiyama reaction). The recycling of metals complexes has been studied in these reactions.

[1] UNEP report “Metals stock in society”, http://www.unep.org/resourcepanel/Portals/24102/PDFs / Metalstocksinsociety.pdf[2] a) McNamara C. A.; Dixon M. J.; Bradley M. Chem. Rev. 2002, 102, 3275-3300. b) Ikegami S.; Hamamoto H. Chem. Rev. 2009, 109, 583–593.[3] a) Helms B.; Fréchet J. M. J. Adv. Synth. Catal. 2006, 348, 1125-1148. b) Ouali A.; Laurent R.; Caminade A.-M.; Majoral J.- P.; Taillefer M. J. Am. Chem. Soc. 2006, 128, 15990-15991.[4] a) Majoral J.-P.; Caminade A.-M. Chem. Rev. 1999, 99, 845-880. b) Launay N.; Caminade A.-M.; Lahana R.; Majoral J.-P. Angew. Chem. Int. Ed. 1994, 33, 1589-1592.

151

LEVONORGESTREL RELEASE FROM A PLGA IN SITU FORMING DRUG DELIVERY SYSTEM

Mazyar Khakpour,1,2 Ali Akbar Entezami,3 Hamid Mirzadeh4

1Department of Novel Drug Delivery Systems, Iran Polymer and Petrochemical Institute, Tehran, Iran.E-mail: m.khakpour@gmail.com

2Department of Polymer Engineering, Islamic Azad University, Kashan Branch, Kashan, Iran.3Department of Chemistry, University of Tabriz,Tabriz, Iran.

4Department of Biomaterials, Iran Polymer and Petrochemical Institute, Tehran, Iran.

In situ forming implants have been used to deliver both hydrophilic and hydrophobic drugs. In these systems, a solution of biodegradable polymer in a biocompatible, water miscible solvent is injected into the body, the solvent diffuses away and polymer precipitates and forms a solid implant. biodegradable in situ forming drug delivery systems have received considerable attention over the past few years [1-5].

In this work, in vitro release of levonorgestrel (LNG) from an in situ forming drug delivery system based on poly(lactide-co-glycolide) 50:50 (PLGA) was investigated. Effects of such parameters as polymer molecular weight, polymer concentration and presence and amount of two release rate modifying agent was studied.

Formulations were prepared by dissolving certain amounts of PLGA (20-40% w/w) and LNG (1-5% w/w of polymer) in N-methyl pyrrolidone. In some formulations defined amounts of glycerol or ethyl heptanoate (1-5% w/w of solvent) was added as release rate modifying agents. Release experiments were done by placing 0.2 g of each formulation in 25 ml vials and then adding 20 ml 60/40% v/v ethanol/water mixture to the vials. At specified time intervals, samples were collected and drug concentration was measured by HPLC.

Results showed that Increasing polymer molecular weight, polymer concentration and the addition of glycerol and ethyl heptanoate decreases the initial burst in drug release, but ethyl heptanoate was more effective. Increasing polymer molecular weight and concentration and amount of additives reduced both initial burst release and drug release rate.

The morphological evaluation of formulations using scanning electron microscopy indicated formation of less porous structure in the matrix for formulations containing glycerol and ethyl heptanoate. Thermogravimetric analysis studies for determination of solvent removal rate from formulations, showed a good accordance with release profiles and morphological studies.

The addition of ethyl heptanoate and glycerol have significantly influenced the release behavior from the studied system by influencing its morphology [6,7]. Based on these results, a mechanism was proposed for the explanation of the effect of release modifying agent on the morphology and release behavior of in situ forming drug delivery systems.

This system shows suitable release behavior for controlled delivery of levonorgestrel.

[1] Hatefi, A.; Amsden, B. J. Controlled Release 2002, 80, 9-28.[2] Bakhshi, R.; Vasheghani-Farahani, E.; Mobedi, H.; Jamshidi, A.; Khakpour, M. Polym. Adv. Technol. 2006, 17, 354-359.[3] Eliaz, R. E.; Wallach, D.; Kost, J. Pharm. Res. 2000, 17, 1546-1550.[4] Kranz, H.; Yilmaz, E.; Brazeau, G. A.; Bodmeier, R. Pharm. Res. 2008, 25, 1347-1354.[5] Jeong, B.; Bae, Y. H.; Kim, S. W. J. Biomater. Mater. Res. 2000, 50, 171-177.[6] Smolders, C. A.; Reuvers, A. J.; Boom, R. M.; Winek, I. M. J. Membr. Sci. 1992, 73, 259-275.[7] Stropnik, C.; Germic, L.; Zerjal, B. J. Appl. Polym. Sci. 1996, 61, 1821-1830.

152

SYNTHESIS OF CONJUGATED POLYMER CONTAINING PRE-FUNCTIONAL GROUP

VIA CYCLOPOLYMERIZATION

Jeongeun Kim, Eun-Hye Kang, Tae-Lim Choi*

Department of Chemistry, Seoul National University, Seoul 151-747, Korea*E-mail: tlc@snu.ac.kr

Post-functionalization of polymers has a limitation due to the possibility of defect and intrinsic characteristics of each polymer such as solubility. Direct polymerization of monomer having pre-functional group which enables to be converted to very reactive functional group provides an alternative, even better way for post-functionalization. Meldrum’s acid is a powerful candidate, which generates ketene through thermolysis. In this study, we prepared the monomer by one step and synthesised conjugated polymers containing Meldrum’s acid by cyclopolymerization using Grubbs 3rd catalyst. Cyclopolymerization is the fast and facile method generating conjugated polymer with highly controlled molecular weight distribution. However, low solubility of the polymer disturbs its characterization, so we moved to random copolymerization and block copolymerization using cyclopolymerization and ring opening metathesis polymerization (ROMP). Ketene generation and further reaction of ketene were characterized by TGA and IR. The conjugated polymer containing very labile ketene is expected to be applicable to polymeric materials, especially in electronics.

153

SYNTHETIC STRATEGIES TOWARD MONOMERSFOR TPES FROM NATURAL RESOURCES.

Moo-hyun Koh,1 Hyun Su Kim, 1 Hyeonjeong Kim, 1 Nara Shin1 and Young Gyu Kim*1

1Department of Chemical and Biological Engineering, Seoul National University, Seoul 151-744, Republic of Korea

E-mail: ygkim@snu.ac.kr

A lot of efforts have been made to secure novel technologies for production of renewable resource- based polymers that can reduce carbon dioxide (CO2) emissions and prepare for depletion of fossil fuels. Among others, there are increasing demands for eco-friendly production of polyamide type thermoplastic elastomers (TPEs) which have a wide range of applications because of their good thermal stability, and excellent chemical and hydrolytic resistance. Compared to the conventional synthesis using petrochemicals, the synthesis of monomers for TPEs from natural resources would be a good solution for the era of green chemistry. In the present presentation, our synthetic efforts for the monomers of TPEs from natural resources such as castor oil, soybean oil and olive oil will be reported.

154

EFFECTS OF LIGNOCELLULOSE DERIVATIVE ADDITIONS ON PROPERTIES OF EPOXY RESINS Gen Komiya1, Ken-ichi Yamazaki1, Takahiro Imai1, Takeshi Fukumoto2, Akio Takahashi3

1 Power and Industrial Systems R&D Center, Toshiba Corporation, Tokyo, Japan 2Transmission & Distribution System Division, Toshiba Corporation, Tokyo, Japan

3Department of Advanced Materials Chemistry, Yokohama National University, Kanagawa, JapanE-mail: gen.komiya@toshiba.co.jp

Bio-plastics are made from renewable biomass sources, such as vegetable oil, corn starch or pea starch. Many studies have been conducted on bio-plastics. We focus on lignocellulose extracted from corncob waste, and develop epoxy resins containing lignocellulose derivatives. In this paper, we describe the effects of lignocellulose derivatives added to the properties of epoxy resin. Firstly, the lignocellulose (LC) was treated with acidic H2O/C2H5OH solution under high temperature and pressure. Secondly, this acidolysis lignin (ALG) was reacted with epichlorohydrin. Thus, the epoxidized ALG (ep-ALG) was obtained with epoxidation of the phenolic group of the ALG. The structures of LC, ALG, and ep-ALG were investigated using 13C CPMAS NMR spectroscopy. In the spectrum of LC, the cellulose (50 - 110ppm) and the lignin (10 - 65ppm, 110 - 180ppm) signals were observed, and the cellulose signals disappeared in the spectrum of ALG. These results indicate the lignin were isolated from the LC. The epoxidation of ALG was confirmed by the signals of 44, 50 and 70ppm in the spectrum of ep-ALG. The LC derivatives (the ALG and ep-ALG) have active functional groups such as the phenolic group and epoxy group. Hence, those utilizations were investigated as a hardener (ALG) and cross-linking agent (ep-ALG), in the epoxy resin system.

Fig.1 DMA curves of epoxy resin cured with ALG (solid lines) and phenol novolac (dot lines).

The DMA curves of epoxy resins cured with the ALG and cured with phenol novolac are presented in Fig.1. The specimen of ALG shows broader peaks than that of phenol novolac, because the ALG, which was made from biological materials, is polydisperse.

Table1 shows properties of the epoxy resin modified by ep-ALG. The epoxy/ hardener (acid anhydride)/ep-ALG system had higher cross-link density than the epoxy/ hardener system (conventional material). Since the ALG has polyphenol structure, the ep-ALG whose phenolic group has been epoxidized is a multi-functional epoxy resin. Therefore, the ep-ALG seems to work as a cross-linking agent. Moreover, the heat-resistance of epoxy resin adding ep-ALG was improved.

Table1 General properties of epoxy/hardener/ep-ALG system.

a) Measured by DMA, heating rate : 2ºC/min, Frequency : 1Hz.b) Measured by TMA, heating rate : 2ºC/min.c) Measured by three-point bending test at room temperature according to JIS K 6911.

155

BIODEGRADABLE POLYESTER MICROCAPSULES FROM ALIPHATIC RENEWABLE-BASED MONOMERS

Agnieszka Kozłowska

Division of Biomaterials and Microbiological Technologies, Polymer Institute,West Pomeranian University of Technology Szczecin, Poland

E-mail: agak@zut.edu.pl

Polymer microcapsules and microspheres are very interesting controlled release systems and they are used in many different applications in chemical, pharmaceutical, cosmetic and food industries [1].

Focused on this biodegradable microcapsules from poly(butylene sebacate-co-butylene dilinoleate) (PBSe/PBDL) were prepared. Novel biodegradable polyesters from aliphatic renewable-based monomers composed of dimmerized fatty acid (saturated dilinoleic acid - DLA), sebacic acid and butanediol were synthesized by polycondensation in the melt [2]. Polymers consist of different weight content of butylene esters of dimmerized fatty acid (soft segment) and polysebacate as hard segment.

In presented paper possibility of preparation of microcapsules from synthesised polyesters by emulsion-coacervation method was studied. Vitamin B3 and caffeine were used as a core. According to received results the conclusion is examined group of polymers show ability for formulation of microcapsules and they have great potential as tailor-made biodegradable drug delivery systems.

Fig. 1. Microcapsules prepared from polymer PBSe/PBDL 80/20 with vitamin B3 as a core. Magnification: A x 100 and B x 2000 (3D Laser Scanning Microscope)

Financial supports from Polish Ministry for Science and Higher Education research project N N209 216538: “Synthesis and properties of novel ester copolymers for microencapsulation technology” (2010-2013) is acknowledged.

[1] Benita S; Microencapsulation: Methods and Industrial Applications; CRC Press 2006[2] Kozlowska, A.; Gromadzki, D.: El Fray, M.; Štαpánek, P. Fib. & Text. in East. Eur. 2008, 71, 85-88

156

THEORETICAL INVESTIGATIONS OF STRUCTURAL, ELECTRONIC AND THERMAL PROPERTIES

OF VARIOUS PHASES OF CDO

S Labidi, M. Labidi and H. Meradji

Laboratoire de Physique des Rayonnements, Département de Physique, Faculté des Sciences, Université de Annaba, Algeria

We present the results of a theoretical study of the structural, electronic and optical properties of all possible phases (rocksalt, zinc blende and wurtzite) of CdO, using the full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential is treated by local density approximation (LDA) and GGA (PBE), a more accurate nonempirical density functional generalized gradient approximation (GGA), as proposed by Wu and Cohen [Phys. Rev. B 73, 235116 (2006)]. Quantities such as, equilibrium lattice constants, bulk modulus, band structures, density of states and optical properties have been calculated for all the phases and the results have been discussed and compared with the existing experimental data. Furthermore, the quasi-harmonic Debye model is applied to determine the thermal properties at room temperature.

Keywords: FP-LAPW; CdO, Electronic properties, Optical properties.

157

SYNTHESIS OF FUNCTIONAL INORGANIC-ORGANIC HYBRID POLYMERS USING ZIRCONIM OXOCLUSTERS AND POLYFUNCTIONAL SULPHUR BASED LIGANDS

Simona Maggini, Rosa Di Maggio

Materials Engineering and Industrial Technologies Department, University of Trento,Via Mesiano 77, I-38123 Trento, ItalyE-mail: simona.maggini@ing.unitn.it

Hybrid materials synthesized from organically modified transition-metal oxide clusters often retain the well defined structure and original properties of the clusters. This allows to better control the size and dispersion of the inorganic component and the use of rational design principles to obtain materials with enhanced properties.[1]

Air and moisture stable organically modified zirconium-oxoclusters [Zr6O4(OH)4(OOCCH2X)12]n (X = CH=CH2, C=CH or C(SCN)=CH2, n = 1, 2) have been used together with trimethoxy alkyl silane (CH3O)3SiR (R = vinyl, propyl mercaptan) to prepare inorganic-organic hybrid polymers with great stability and thermo-mechanical properties in the absence of remarkable mass loss, including high stiffness and glass transition temperature.[2] The polymers were tested as penetrating coatings on wood and paper samples.

The Zirconium clusters, besides conferring particular properties to the coating (such as flame-retardant) are responsible for the organization of the polymer architecture, and are grafted to the polymer matrix through covalent bonds. The siloxanes can penetrate, for example, into the wood texture and improve water repellence, resistance to photochemical degradation, combustion, and shrinkage.[3] The introduction of key functional groups (SH, SCN) on the organic component, can make the polymer capable of responding to external stimuli from weathering (oxygen, light, moisture) and biological attack, conferring to the polymer a higher strength.

[1] (a) Schubert, U. J. Sol-Gel Sci. Technol. 2004, 31, 19-24. (b) Kickelbick, G.; Schubert, U. Monatsh. Chem. 2001, 132, 13-30. (c) Schubert, U. Chem. Mater. 2001, 13, 3487-3494.[2] a) Maggini, S.; Girardi, F.; Müller, K.; Di Maggio R. J. Appl. Polym. Sci. 2011, in press. b) Di Maggio, R.; Dire,S.; Callone,E.; Girardi,F.; Kickelbick, G. Polymer 2010, 51(4), 832-841.c) Di Maggio,R.; Dire,S.; Callone,E.; Girardi,F.; Kickelbick G. J. Sol-Gel Sci. Technol. 2008,48,168-171.[3] a) DeVetter, L.;Van den Bulcke, J.; Van Acker, J. Holzforschung 2010, 64, 463–468.b) Donath, S.; Militz, H.; Mai, C. Holz Roh Werkst 2007, 65, 35–42.c) Saka, S.; Ueno, T. Wood Sci.Technol. 1997, 31, 457-466.d) Donath, S.; Militz, H.; Mai, C. Wood Sci. Technol. 2004, 38, 555-566. e) Schneider, M.H.; Brebner, K.I. Wood Sci. Technol. 1985, 19(1), 67–73.

158

SELF-ASSEMBLY OF RENEWABLE-NANO ARJUNOLIC AND GLYCYRRHETINIC ACIDS: VISUAL DETECTION OF ELECTRON DEFICIENT AROMATIC COMPOUNDS

Rakhi Majumdar and Braja Gopal Bag*

Department of Chemistry and Chemical TechnologyVidyasagar University, Midnapore 721 102, West Bangal, India

E-mail: braja@mail.vidyasagar.ac.in

Triterpenoids, the C30 plant metabolites are large and structurally diverse molecules having varied rigid and flexible lengths. We have recently shown by computations that all the triterpenoids are nanometer long [15]. We have been successful in isolating arjunolic acid 1 from the heavy wood powder of Terminalia Arjuna and glycyrrhetinic acid 2 from the root extract of Glycyrrhiza Glabara[16,17].

Detailed selfassembly studies carried out in our laboratory revealed that the triterpenics acids selfassemble in different liquids affording noncovalent polymeric networks and spherical objects of nano- to micorometer diameters [3,18]. The alkyl chained esters of the nano-sized arjunolic acid 1 could immobilize various organic solvents at low concentrations [19].

The anthrylidene derivative of methyl arjunolate formed colored gels (Figure 1) in the presence of stoichiometric amount of electron deficient aromatic compounds [20]. Optical microscopy revealed fibrillar network with optical birefringence (Figure 2). The melting of the deep red soft material could be observed visually by concomitant color change [6] and all these soft solids were thermoreversible. The coloration with electron deficient aromatic compounds led the development of simple visual detection techniques for such compounds (unpublished results). Glycyrrhetinic acid 2 self-assembled in different liquids forming mostly spherical objects along with fibrillar netoworks in some liquids. Recent results from our laboratory will be presented in the poster.

References[15] Bag, B.G.; Garai, C.; Majumdar, R.; Laguerre, M. Structural Chemistry, 2011, (DOI: 10.1007/s11224-011-9881-1).[16] Bag, B.G.; Dey, P.P.; Dinda, S.K.; Sheldrick, W.S.; Oppel, I.M. Beil. J. Org. Chem, 2008, 4(24), 1-5.[17] Bag, B.G.; Majumdar, R. First Self-assembly Study of Glycyrrhetinic Acid, to be communicated.[18] Bag, B.G.; Dash, S.S. Nanoscale, 2011, (DOI: 10.1039/c1nr10886g).[19] Bag, B.G.; Dinda, S.K.; Dey, P.P.; Mallia, A.V.; Weiss, R.G. Langmuir, 2009, 25, 8663-8671.[20] Bag, B.G.; Maity, G.C.; Dinda, S.K. Org. Lett., 2006, 8, 5457 - 5460.

Figure 1: Visual detection of electron

deficient aromatic

Figure 2: OpticalMicroscopy image of a gel of arjunolic acidderivative and TNF.

159

ORIGINAL SYNTHESIS OF SUBSTITUTED CYCLOPENTADIENE DERIVATIVES

Hind Mamlouk,1 Etienne Vilain2, Vincenzo Biondo3 , Olivier Miserque3

1Total Petrochemicals, Total Research Center – Qatar, Doha, Qatar2Haute Ecole Provinciale de Hainaut – Condorcet, 6000 Charlerois, Belgium

3Total Petrochemicals Research Feluy, Zone Industrielle C, 7181 Feluy, BelgiumE-mail: hind.mamlouk@total.com

Since their discovery in the 1950’s, cyclopentadiene-based metallocene complexes have attracted considerable attention in biochemistry as well as in catalytic processes in the chemical and pharmaceutical industries and more recently in the field of medicine as a potential treatment for cancer. Amongst them, complexes containing saturated cycles as substituents on the cyclopentadienyl ring itself (Figure 1) are particularly interesting as precursors to α-olefins polymerization catalysts. Their interest might lie in the greater stability or increased activity or differentiated selectivity of the resulting catalyst and in the better control of the catalyst residues. The unsaturated ligands and most specifically the ρ5-indenyl types might be directly available, while the classical way to obtain the saturated ones is via the catalytic hydrogenation of the parent molecules. However, catalytic hydrogenation reactions usually require severe conditions that are not always compatible with the stability of the target molecules.

We are interested in developing versatile, flexible and efficient routes to ligands containing saturated ring systems attached to the cyclopentadienyl ring. This type of ligands, characterized by new structures, allows the synthesis of differentiated metallocene complexes, having outstanding performance in catalytic processes for the polymerization of α-olefins.

We report here the synthetic protocols for saturated ligands precluding the hydrogenation step, starting from cycloalkanones. Elegant synthetic routes have been studied. However, the overall yields were often low or the method used was of limited applicability.

Figure 1: Substituted cyclopentadiene with at least one saturated cycle

160

ELECTROCHEMICAL SYNTHESISAND CHARACTERIZATION OF CONDUCTING

COPOLYMERS: POLY(DIPHENYLAMINE) CO ORTHO-, METHA-, AND PARA- PHENYLENEDIAMINE)

Mohammad Hossein Mashhadizadeh, Mahmoud Amouzadeh Tabrizi

Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iranmashhadizadeh@tmu.ac.ir, Tel: +98-21-88848949; Fax: +98-21-88820993

Conducting polymers, also sometimes called conjugated conducting polymers or organic polymeric conductors, are materials consisting of polymeric molecules, which have high electrical conductivity. Although conducting polymers can also be prepared chemically, the most convenient and most widely used method for synthesis of conducting polyheterocycles is the electrochemical anodic oxidation [1, 2]. In this work copolymerization of diphenylamine (DPA) with ortho-, meta- and, para-phenylenediamine were achieved electrochemically in aqueous solution containing HClO4 as supporting electrolyte. Cyclic voltammetry was used for electrochemical synthesis and characterization of the copolymers deposited on gold electrode. The influence of polymerization conditions such as electrode potential, monomer concentration, type of supporting electrolyte on the electrochemical properties of final polymers have been studied. The results showed that the conductivity of DPA-para-phenylenediamine copolymer was higher than that of poly-DPA. However, DPA- meta-phenylenediamine and DPA-ortho-phenylenediamine copolymers have lower conductivity than poly-DPA. In addition, DPA- ortho-phenylenediamine copolymer has a good electrochemical activity even at pH 9.5.

1. Roncali, J. Chem. Rev. 1992, 92, 711-7382. Ballarin, B.; Seeber, R.; Tonelli, D.; Andreani, F.; Bizzarri, P.C.; Casa, C.D.; Salatelli, E.; Synthetic Metals, 1997, 88, 7-13.

162

THREE DIMENSIONAL ‘DNA-MINIMAL’ SCAFFOLDS: ASSEMBLY, ORGANIZATION OF BLOCK COPOLYMERS

AND CELLULAR UPTAKE STUDIES

Christopher K. McLaughlin1, Graham D. Hamblin1, Kevin Haenni1, Manoj K. Nayak2, Johans Fakhoury, Hassan S. Bazzi2 and Hanadi F. Sleiman1

1Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, Canada 2Chemistry Department, Texas A&M University at Qatar, Doha, Qatar

E-mail: christopher.mclaughlin@mail.mcgill.ca

Three-dimensional (3D) DNA structures hold promise for numerous applications, from biological probes and drug delivery tools to organizational scaffolds. Unlike most nanomaterials, they provide fine control over geometry, precise and monodisperse sizes, symmetric or asymmetric positioning of molecules, and molecule-responsive switching of structure [1]. Conventional methods to make 3D-DNA structures, such as DNA origami [2] or tile-based assembly [1], result in double-stranded, DNA-dense structures, making them potentially more difficult to functionalize and selectively integrate with biological systems.

We first present an approach to 3D-DNA assembly that strives to be ‘DNA-economical’ as a means to create geometrically well-defined 3D-scaffolds. These contain a large number of single-stranded arms and are accessed from a minimum number of DNA strands. A variety of structures are generated in a facile manner and excellent yield using a minimum number of DNA strands.Each 3D DNA scaffold can act as a core structure that guides the site-specific organization of other materials as its shell. As an example, a cubic DNA structure, containing 8 single-stranded arms, is used to test organizational capacity through selective arrangement of a polymer-DNA conjugate (Figure 1). The biohybrid conjugate is generated by covalently attaching a synthetic polymer [3], prepared using ring-opening metathesis polymerization (ROMP) [4], to a short DNA strand that is complementary to single-stranded regions of the DNA cube (Figure 1). The resulting conjugate efficiently hybridizes to the individual arms of the DNA scaffolds (Figure 1) to produce block-copolymer DNA cages that are more nuclease-resistant than the unfunctionalized DNA cages

163

We next outline in vitro studies designed to probe the cellular internalization of a variety of the above outlined DNA nanostructures. Cultured HeLa cells are treated with fluorescently labelled DNA structures and examined using fluorescence-activated cell sorting (FACS) and confocal fluorescence microscopy (CFM). For each of the 3D DNA nanostructures, substantial cellular uptake is observed without the requirement of a transfection reagent. The in vitro data, along with the simple 3D DNA construction strategy and ability to functionalize with synthetic polymers, support the potential application of these self-assembled structures for bio-imaging and targeted drug delivery applications.

[1] F. A. Aldaye; A. L. Palmer; H. F. Sleiman, Science, 2008, 321, 1795-1799.[2] T. Torring; N. V. Voigt; J. Nangreave; H. Yan; K. V. Gothelf. Chem .Soc. Rev., 2011, DOI: 10.1039/C1CS15057J.[3] M. Kwak; A. Herrmann, Chem. Soc. Rev., 2011, DOI: 10.1039/C1CS15138J.[4] N. B. Sankaran et al, Macromolecules, 2010, 43, 5530–5537.

164

EXPERIMENTAL INVESTIGATION OF HIGH MOLAR MASS IMPURITIES IN STEADY ELONGATIONAL

VISCOSITY SAMPLESOlga Mednova,1 Qian Huang,2 Ole Hassager,2 Kristoffer Almdal1

1Department of Micro- and Nanotechnology, Technical University of Denmark, Kgs.Lyngby, Denmark2Department of Chemical and Biochemical Engineering, Technical University of Denmark, Kgs.

Lyngby, Denmark

E-mail: omed@nanotech.dtu.dk

Luap et al. [1] discusses whether chain stretching in extensional flow in polymer melts will give rise to an upturn in the steady elongational viscosity when the strain rate exceed the reciprocal Rouse time. Laup et al. collected availably steady elongational viscosity data from the literature. Apart from a single point (due to Li et al. [2]) the data are in agreement with no upturn in the steady elongational viscosity. However, theoretical predictions following current molecular theories predict an upturn in the steady elongational viscosity. Furthermore the outlying point by Li et al. is in agreement with the theoretical predictions. We hypothesize that the reason for the outlying data point is a sample with a bimodal molar mass distribution where the nominal narrow molar mass distribution sample contains a small amount of molecules with twice the molar mass of the main component. We have observed the formation of such high molar mass impurities in polystyrene sample synthesized by anionic polymerization even in the case careful exclusion on oxygen in the termination process. In this study we investigate the influence of such bimodal molar mass distribution on the steady state elongational viscosity.

Samples were prepared by anionic polymerization and standard procedures of purification and reagents preparation have been used. Styrene (>99%, Merck) was purified by passing through basic Al2O3 with further distillation from finely ground calcium hydride followed by distillation from dibutyl magnesium. Cyclohexane as a polymerization solvent was refluxed with a mixture of n-butyl lithium and styrene under argon to generate living polystyryl anions. The initiator sec-butyl lithium was titrated by Gilman double method immediately prior to use. A small amount of degassed methanol was added to terminate the polymerization after three hours. All chemical reagents used for the synthesis have been purchased from Sigma Aldrich.

The final molar mass is determined by the reaction stoichiometry. The reaction condition was adjusted inspired by [3]. Optimally, the synthesis was conducted for three hours at 30ºC and overall two polystyrenes with molar masses of 248kg/mol and 484kg/mol have been synthesized. The proposed kinetic scheme of alkyl lithium initiated polymerization includes the participation of lithium compounds forming aggregates with non-zero reactivity. That assumption easily explains development of molecular weight averages during polymerization as well as the acceleration period of initiation reaction [3]. Size exclusion chromatography has been applied (SIL-10AD Shimadzu) to examine molecular weight and its distribution.

Acknowledgment: Support for this work was provided by VKR-foundation financed centre NAMEC and the Marie Curie Action DYNACOP

[1] Luap C.; Muller C.; Schweizer T.; Venerus D.C. J. Rheol. Acta. 2005, 45(1), 83-91.[2] Li L.; Masuda T.; Takahashi M.; Ohno H.; J Soc Rheol Jpn. 1988, 16, 117–124[3] Rivero P.; Herrera R. J. Polym. Res. 2011, 18(4), 519-526.

165

WOOD PLASTIC COMPOSITE FROM HDPE/PET BLEND REINFORCED WITH WOOD FLOUR AND RICE

HUSK HYBRIDUTAI MEEKUM

School of Polymer Engineering, Suranaree University of Technology, Nakorn Ratchasima, 3000, THAILAND

E-mail:umsut@g.sut.ac.th

Wood Plastic Composite manufactured from the HDPE blended with PET waste as matrix and wood flour as reinforcement in the DCP/silane crosslink system was studied. The 2k factorial design of experiment(DOE) was employed to statistically quantify the optimal amount PET(A), DCP(B) and silane(C) contents for best properties of the WPC. The WPC sample was mixed through the closely intermeshing co-rotating twin screw extruder and then injection molded at 190ºC. Two set of samples, with and without sauna treatment, were prepared. The standard testing by mean of MFI, impacts, flexural, HDT and flammability were conducted. It was found that the most excellent formula of the WPC was consisted of 20 phr of PET, 0.3 phr of DCP, 2.0 phr of silane, 40 phr of reinforcement and 2.0 phr of processing stabilizer.

Wood/rice husk hybrid at 0:40, 10:30, 20:20, 30:10 and 40:0 were also studied. It was found that the impact strengths were decreased when increasing the rice husk ratios. However, HDT and flexural properties were elevated with increasing the rice husk loading. The flammability of the WPC was almost unchanged with the rice husk. It was obvious that silane/water crosslinking through the sauna treatment had improved the measured properties.

UHMWPE as toughener was added, from 5 to 25 phr, into the WPC reinforced with 40 phr rice husk. It was witness that the not only MFI of WPC was dramatically decreased with increasing the UHMWPE content but also the HDT was slowly deduced. The toughness and stiffness of the composite by mean of impact and flexural properties were slightly increased with increasing the UHMWPE loading.

The SEM investigation was evidenced that the crosslink bridge between the fiber and the polymer blend matrix, via the DCP initiated silane/water condensation, was occurred after sauna treatment. Consequently, the interfacial adhesion was enhanced and then the fracture toughness of the WPC.

166

HELICAL CHIRAL POLYACETYLENES AS HIGHLY ENATIODIFFERENTING ORIENTING MEDIA

FOR ORGANIC COMPOUNDS

Nils-Christopher Meyer,1 Alexis Krupp,1 Volker Schmidts,1 Christina M. Thiele,1* Michael Reggelin1*

1Clemens-Schoepf Institute for Organic Chemistry, Technical University DarmstadtPetersenstr. 22, 64287 Darmstadt Germany.

E-mail: nmeyer@thielelab.deProf. Dr. Michael Reggelin, Prof. Dr. Christina M. Thiele, Technical University Darmstadt, Petersenstr.

22, 64287 Darmstadt, Germany

The determination of conformations and relative configurations by nuclear magnetic resonance usually involves distances from the NOE and dihedral angles from 3J couplings. It is, however, often complicated by either absence of NOE data and/or 3J coupling data, remoteness of the stereocenters or conformational equilibria.The recently reintroduced residual dipolar couplings (RDCs)[1] provide complementary information to these conventional NMR restraints.

RDCs belong to the class of anisotropic NMR parameters and therefore the compound in question needs to be oriented with respect to the magnetic field in order to be able to observe them. The only known class of chiral orienting media for organic solvents are the lyotropic liquid crystalline (LC) phases of rigid polymers like homopolypeptides[2] and as first non peptidic polymer, helical chiral polyguanidines[3].

Here we want to present the first enantiodifferenting alignment media based on helically chiral polyacetylenes. The polyacetylenes based lyotropic liquid crystalline phase showed some beneficial properties, like weak alignment, small polymer residue signal in the spectra, simple phase preparation and the highest degree of enantiodifferenting known today for any alignment media in organic solvents. This new system has been validated for several chiral analytes like isopinocampheol (IPC) and strychnine.

[1] Reviews: Gschwind, R.M. Angew. Chem. 2005, 117, 4744-4746; Angew. Chem. Int. Ed. Engl. 2005, 44, 4666-4668; Yan, J., Zartler, E.R. Magn. Res. Chem. 2005, 43, 53-64; Thiele, C. M., Conc. Magn. Res. 2007, 30A, 65-80; Thiele, C. M., Eur. J. Org. Chem. 2008, 14, 5465-5481.[2] Marx, A., Thiele, C. M. Chemistry - A European Journal 2009, 15, 254-260.[3] Arnold, L., Reggelin M. Chemistry - A European Journal 2010, 16, 10342-10346.

167

CONTROL OF SOLUTION ACIDITY WITH THERMORESPONSIVE POLYMERS

Alexander J. Mijalis,1 David E. Bergbreiter,1 Yanfei Yang1

1Chemistry Department, Texas A&M University, College Station, TX 77843E-mail: mijalis@gmail.com

Pendant groups on polymers that have temperature dependent responsive solubilities (i.e. an LCST) experience a hydrophilic water-like environment below the LCST where the polymer is soluble. Above the LCST, the precipitated polymer hydrogel has fewer waters of hydration and the environment for functional pendant groups changes. When these pendent groups are amphoteric, e.g., ammonium salts or carboxylate salts, the change in solvation that accompanies the polymer precipitation event at the LCST significantly changes these groups’ acidity or basicity, respectively. When the pH is near the pKa of the functional group, these changes in acidity or basicity can lead to ammonium salts reverting to the neutral amine or carboxylate salts forming carboxylic acid groups. This involves either the release of protons to the bulk solvent or the capture of protons from the bulk solvent. We have found that polymers like PNIPAM that contain sufficient loadings of comonomers with ammonium salt or carboxylate salt groups can undergo such solubility changes, and that these solubility changes alter bulk solution acidity by ca. 100-fold. Moreover, such changes are fully reversible by cooling, are consistent through multiple heat/cool cycles, and occur when the LCST event is brought about by the addition of a kosmotropic salt. These effects can be visually followed using common indicators.

168

PREPARATION AND ANTIBACTERIAL PROPERTIES OF ORGANIC/INORGANIC HYBRID FIBERS

BY PHOTOCATALYTIC DEPOSITION OF SILVER NANOPARTICLES

Byung Gil Min, Jing Zhou, Seong Min Cho

Department of Materials Design Engineering, Kumoh National Institute of Technology,Gumi, Korea

E-mail: bgmin@kumoh.ac.kr

Much attention has been focused on the incorporation of silver nanoparticles into polymers because of possible applications in medical fields, sensors, and so on.[1] Meanwhile, some researches have reported upon the Ag/TiO2 nanocomposite system using titania as stabilizers of silver nanoparticles using photocatalytic properties of TiO2, which can immobilize Ag nanoparticles in polymer systems through a chemical reduction process of silver ion. [1-3]

Hybrids of poly(ethylene terephthalate) (PET) and nano-TiO2 were prepared by melt compounding using a twin-screw extruder. The hybrids were hot-pressed to thin sheets or melt-spun to fibers. For silver photodeposition, PET/TiO2 hybrids were immersed in aqueous AgNO3 solution followed by irradiation of UV-light (254 nm) for 30-60 seconds. The antibacterial properties of the PET/TiO2 hybrids against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria were evaluated using Shaking flask method and paper disc method. The PET/TiO2 hybrids showed excellent antibacterial properties.

[1] Lim, S. K.; Lee, S-K.; Hwang, S-H.; Kim, H. Macromol. Mater. Eng. 2006, 291, 1265–1270.[2] Cozzoli, P. D.; Comparelli, R.; Fanizza, E.; Curri, M. L.; Agostiano, A.; Laub, D. J. Am. Chem. Soc. 2004, 126, 3868.[3] Sakai, H.; Kanda, T.; Shibata, H.; Ohkubo, T.; Abe, M. J. Am. Chem. Soc. 2006, 128, 4944.

169

CRYSTAL STRUCTURE AND ISOMERIZATION BEHAVIOR OF AROYLATED NAPHTHALENES

Ryosuke Mitsui, Atsushi Nagasawa, Akiko Okamoto, Noriyuki Yonezawa

Department of Organic and Polymer Materials Chemistry,Tokyo University of Agriculture and Technology,

2-24-16 Naka-machi, Koganei, Tokyo 184-8588, Japan.E-mail: 50009832204@st.tuat.ac.jp

The author’s group has investigated acidpromotedhighly react ive and consecut ive electrophilic aromatic substitution (ArSE) aroylationand applied it to synthesis of wholly aromatic polyketones [1]. In the course of the study, unique ArSE aroylation behavior, i.e. ready and regioselective format ion of highly conges ted aroy lated naphthalenes and reversed aroylation (dearoylation), has been found recently.

The regioselective Friedel–Crafts type C – C bond formation reaction of 2 , 7 - dimethoxynaphthalene (1) with 4-chlorobenzoic acid (2a) /acid chloride (2b) in the presence of Brønsted or Lewis acid as mediator affords 1,8-diaroylated naphthalene 4 in high yields [ 2 ].

1-Monoaroylated naphthalenes 3 are also synthesized in high yields by regulation ofreaction conditions (Scheme). Single crystal X-ray studies of 1-monoand 1,8-diaroylated naphthalenes 3 and 4 have revealed that the aroyl groups are attached almost perpendicularly to naphthalene ring (Figure). And two atropisomers exist in the crystal lattice [3]. On the other hand, details of the stable position of carbonyl groups in organic solvent remain unsettled. On the basis of these results, the authors have planned to assess the spatial structure of the molecules via investigation of the reaction behavior through modification of molecules. For this purpose, preparation of diastereomeric mixture by reaction of resolving agent with aroylated naphthalenes was undertaken. Thereafter investigation of isomerization behavior of aroylated naphthalenes caused by rotation of C–C single bond between carbonyl group and naphthalene ring using variable-temperature NMR spectroscopy was undertaken to estimate the rotational barrier.

in this paper, the authors briefly report and discuss the synthesis and characteristics of aroylated naphthalenes. For instance, aroylation behavior against 2,7-dimethoxynaphthalene (1), and regioselective cleavage of ether group at 2-position of naphthalene ring to react with resolving agent. Furthermore, on the basis of X-ray crystal structures of aroylated naphthalenes existence of ntramolecular hydrogen bond between carbonyl group and hydroxy group is discussed in relation with rotation ability of carbonyl group–naphthalene ring bond.

[1] Yonezawa, N.; Okamoto, A. Polymer J. 2009, 41, 899.[2] a) Okamoto, A.; Yonezawa, N. Chem. Lett. 2009, 38, 914.b) Okamoto, A.; Mitsui, R.; Oike, H.; Yonezawa, N. Chem. Lett. 2011, 40, 1283.[3] a) Nakaema, K.; Okamoto, A.; Noguchi, K.; Yonezawa, N. Acta Cryst. 2007, E63, o4120.b) Mitsui, R.; Nakaema, K.; Noguchi, K.; Yonezawa, N. Acta Cryst. 2008, E64, o2497.

Scheme ArSE aroylation of 1 with 2 Figure ORTEP drawings of 1-mono- and 1,8-diaroylatedn aphthalenes3 (left) and 4 (right)

170

REACTION BEHAVIOR AND STRUCTURAL FEATURES OF AROYLATED NAPHTHALENES: IMINATION OF

CARBONYL GROUP IN NON-COPLANARLY ARRANGED AROMATIC-RINGS-ACCUMULATED MOLECULE OF

CONGESTED AND OBLIQUE CONFIGURATION

Atsushi Nagasawa, Ryosuke Mitsui, Akiko Okamoto, Noriyuki Yonezawa

Department of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture and Technology, 2-24-16 Naka-machi, Koganei, Tokyo 184-8588, Japan.

E-mail: 50009832204@st.tuat.ac.jp

The authors have recently reported curious behavior in acid-mediated aroylation of 2,7-dimethoxynaphthalene and unique molecular structures of the products and the relating compounds, such as regioselectivity and consecutiveness in aroylation, Brønsted acid-mediated dearoylation [1], and selective scission of ether linkage of aroylated naphthalene molecules [2]. In crystal structures of the resulting aroylated naphthalenes, 1,8-diaroylated products and 1-monoaroylated ones exhibit non-coplanar arrangements of aromatic rings of the aroyl groups at the 1- and 1,8-positions of the naphthalene cores [3, 4]. In a natural consequence, the authors have planned to investigate the structural modification of these aroylated naphthalene molecules for expansion of the accumulated aromatic rings system having three aromatic rings by the carbonyl transformation reaction such as imination with aromatic amines.

In this paper, the authors wish to introduce the highly congested characteristic structure of the resulting molecule in which three aromatic ring planes are situated almost perpendicularly to each other. Furthermore, the authors demonstrate the curious transformation reaction behavior of 1-monoaroylnaphtalene compounds 1/2 with aniline derivatives 3 and discuss the reaction governing factors from the aspect of the molecular structures of non-coplanarly accumulated aromatic-rings of the aroylated naphthalenes along with substituent effect of oxy group at 2-position (Scheme). In this reaction, half-hydrolyzed substrate 2 gives the imine compound 5 almost quantitatively, which has rather planar molecular structure contrary to the corresponding dimethoxy homologues. The reaction behavior is rationally explained on the basis of spatial structures of the substrates and the products.

References:[1] Okamoto, A.; Yonezawa, N. Chem. Lett. 2009, 38(9), 914.[2] Okamoto, A.; Mitsui, R.; Yonezawa, N. Chem. Lett. 2011, 40(11), 1283.[3] Hijikata, D.; Nakaema, K.; Watanabe, S.; Okamoto, A.; Yonezawa, N. Acta Cryst. 2010, E66, o554.[4] Watanabe, S.; Nagasawa, A.; Okamoto, A.; Noguchi, K.; Yonezawa, N. Acta Cryst. 2010, E66, o329.

171

SINGLE CHAIN CONFORMATION ANALYSIS OF BLOCK AND GRADIENT COPOLYMER

Kyung Oh Kim, Tae-Lim Choi*

Department of Chemistry, Seoul National University, Seoul 151-742, Korea*E-mail: tlc@snu.ac.kr

Polymer has been being a good candidate for the material in wide range. Among them, copolymers are one of the most interesting materials because they can make various nanostructures by assembly and used in nanotechnology. However, the single chain imaging analysis of copolymer is rarely studied compared to homopolymer which had been studied. In this study, we introduced the dendron moiety to the monomer to make the microscopically visible polymer. With this dendronized macromonomers, diblock copolymer and gradient polymer were synthesized via ring opening metathesis polymerization (ROMP) with various monomer combinations. The kinetics of polymerization was determined by 1H NMR, and the polymers were characterized by multi angle laser light scattering (MALLS) and atomic force microscopy (AFM). The molecular weights of polymers were more than 200 k with narrow PDI (1.08), and clear height image could be obtained.

Figure 1. polymer visualization by dendronization.

172

ELECTROPOLYMERIZATIONOF 4-AMINOACETANILIDE IN THE PRESENCE

OF SODIUM DODECYL SULFATE; APPLICATION FOR ELECTROCATALYTIC OXIDATION OF ETHYLENE GLYCOL

Reza Ojani1, Jahan-Bakhsh Raoof1, Vanoushe Rahemi1

1Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran

E-mail: fer -o@umz.ac.ir

Recently, much attention has been paid to using anionic surfactant, based mainly on sodium dodecyl sulfate (SDS), for electrosynthesizing conducting polymers, such as polypyrroles and polythiophenes. Adding SDS to the monomer solution leads to an increase of the polymer growth rate[1].

In this work, poly (p-aminoacetanilide) (PPAA) was prepared by oxidation of PAA in acidic aqueous solution in the presence of sodium dodecyl sulfate (SDS) at the surface of carbon paste electrode (CPE). By adding SDS to the monomer solution, the monomer oxidation potential was shifted to less positive potentials (EOx = 0.78 V) and its oxidation current increased. Also, the rate of polymerization increased considerably and their peak currents increased. This behavior may be due to specific interaction occurring between dodecyl sulfate and the radical-cations formed during the electropolymerization mechanism. Then Ni(II) ions were incorporated to the polymer by immersion of the modified electrode in a 0.1 M Ni(II) ions solution. The experimental results exhibited the stable redox behavior of the Ni(III)/Ni(II) couple immobilized at the polymeric electrode. This polymeric modified electrode has a very good activity toward the ethylene glycol (EG) electrooxidation in a 0.1 M NaOH solution. By comparison of the different responses to EG oxidation using electrodes Ni/SDS-PPAA/CPE, Ni/PPAA/CPE and Ni/CPE, we observed that Ni/SDS-PPAA/CPE is a more effective catalyst for the electrooxidation of ethylene glycol. The anodic peak current of EG increases with increasing ethylene glycol concentration up to 0.08 M. A diffusion-controlled process at low EG concentrations and a kinetic-controlled process at high EG concentrations are predominant. Finally, the catalytic rate constant (k) for the ethylene glycol oxidation reaction was calculated 1.1× 104 cm3 mol-1 s-1 by using a chronoamperometric technique.

[1] Ojani, R.; Raoof, J. B.; Norouzi, B. J. Mater. Sci. 2009, 44, 4095-4103.

173

POLYMERIZATION AND STRUCTURE-PROPERTY RELATIONSHIP OF POLYETHYLENE AND ITS α-OLEFIN

COPOLYMERS

Mabrouk Ouederni1, Abdulaziz A. Bashraheel2

1Research and Development, Qatar Petrochemical Co. (QAPCO), Doha, Qatar2Technical Customer Service, Qatar Petrochemical Co. (QAPCO), Doha, Qatar

Email: mouederni@qapco.com.qa

Polyethylene is the most widely used polymer in the world today. Its use covers a wide range of markets ranging from packaging and agricultural film, to transportation, construction and energy related applications. The properties, and hence the applications, of this polymer depend on its polymerization process and on a number of structural parameters such as molecular weight, molecular weight distribution, crystallinity and chain branching.

This paper examines the effect of structure on properties of Qatar produced Polyethylene and its α-olefin copolymers. It will be demonstrated that achieving good processability and superior mechanical properties of polyethylene is possible through careful selection of the polymerization process and manipulation of the polymer chemical structure.

Specific examples of Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene (LLDPE) will be discussed in terms of their molecular chain structure and properties developed for target applications.

174

CHARACTERIZATION OF POLYURETHANE FOAMCONTAINING MELAMINE PHOSPHATE

Kyeong-Kyu Park, Seung-Wook Shin and Sang-Ho Lee

Department of Chemical Engineering, Dong-A UniversityHadan2-dong, Saha-gu, Busan 604-714, Republic of Korea

E-mail: sangho@dau.ac.kr

Polyurethane Foams (PUFs) are widely used in human life. For instance, flexible polyurethane foams are used as cushioning material for furniture, automobiles, and packaging.[1] Rigid polyurethane foams are employed to insulate refrigerators, freezers, piping, tanks, building, and liquefied natural gas cargoes.[2] The properties of PUFs, such as thermal and dimensional stability, density, and mechanical strength, have to be modulated properly for each application. In addition, fire resistance and low toxicity are essential to all PUF products. Halogen type flame retardants, which release toxic gases and ozone-depleting substances at fire, are broadly applied to PUFs to endow fire resistance. In order to make environmentally benign PUFs, we replaced halogen type flame retardants with melamine phosphate. When exposed to fire, melamine phosphate endothermically decomposes and acts as a heat sink to cool PUFs. More significantly, the released phosphoric acid from melamine phosphate reacts with PUFs to form a char and the the relaeaed nitrogen is expected to intumesces the char to protect PUFs from the fire heat.[3]

We synthesized of PUFs containing melamine phosphate, from poly(adipate)-diol nanocomposite containing melamine phosphate, high functional polyether type-polyols, and polymeric methylene diphenyl diisocyanate. Cyclopentane and distilled water were used as a blown agent, which the both are more environmentally benign than CFC and HFC. The rising rate of the PUFs using distilled water was faster than the rising rate with cyclopentane at the same content of melamine phosphate. Whereas the rising time of the PUFs blown with distilled water increased steadily and linearly with the MP content, the rising time of the PUFs blown with cyclopentane was independent on the melamine phosphate content over 2.5 wt% melamine phosphate. While cyclopentane is physical blowing agent, the water is chemical blowing agent. Therefore it is expected that the property of the PUFs and the reaction to PUFs vary with the type of networking catalyst. With dibutyltin dilaurate and N,N-dimethylcyclohexylamine catalysts, the kinetics of the PUFs was studied at various melamine phosphate contents of the PUFs.

We measured the properties of the PUFs, such as density, thermal and mechanical properties, and flame retardancy. The PUFs blown with distilled water had lower density than that blown with cyclopentane. And the density of the both PUFs decreased with increasing the content of melamine phosphate. As the melamine phosphate content increased, the cell morphology changed from spherical to ellipse shape and the cell size decreased almost lineally. Between 1.5 and 6 wt% melamine phosphate, the glass transition temperature (Tg) of the PUFs blown with cyclopentane increased with the melamine phosphate content at the rate of 5.6K/% melamine phosphate. The Tg of the PUFs blown with distilled water increased at the rate of 4.4K/% melamine phosphate.

[1] Chao, C.Y.H.; Wang, J.H. Combustion and Flame. 2001, 127(4), 2252-2264.[2] Cao, X.; Lee, L. J; Widya, T. C. Polymer 2005, 46, 775.[3] Liu, M.; Liu, Y.; Wang, Q. Macromol. Mater. Eng. 2007, 292, 206–213.

175

HELICALLY CHIRAL POLYACETYLENES-TOWARDS POLYMERIC CATALYSTS

Vibeke Petersen, Michael Reggelin*

Clemens-Schoepf-Institut for Organic Chemistry and Biochemistry,Technical University Darmstadt, Petersenstrasse 22, D-64287 Darmstadt

E-mail: vp@punk.oc.chemie.tu-darmstadt.de

The helix is a common structural motif for bioactive polymers. It plays a central role in chiral recognition and asymmetric transformations. The ability of synthetic helically chiral polymers to carry stereoinformation and to be catalytically active has already been exemplified for a number of different polymers by us1 and others2. Our aim is to develop polyacetylenes as a new kind of macromolecular catalysts. Besides an easy synthetic access the most promising benefit is the functional-group-tolerating polymerisation leading to stereoregular polyacetylenes.3

The idea is to present catalytically active sites in an uniform environment due to the helical structure. Additionally, the chiral polymeric backbone as the source of the stereoinformation should allow stereocontrol in the asymmetric reaction (Figure 1).

Figure 1: Schematic representation of the catalytically active polyacetylene.

Based on the work of Yashima, where the helicity of the polymeric backbone was stabilized by intramolecular H-bonds,4 we intend to prepare new catalytic active polyacetylenes bearing biphenolic pendant groups with a preferred-handed helix by helix-sence-selective polymerisation. The introduced biaryl unit may populate a preferred chiral conformation under the influence of the chiral backbone which should allow asymmetric transformations known for biphenolic systems.5

[1] (a) Holbach, M.; Schultz, M.; Reggelin, M. Angew. Chem. Int. Ed. 2002, 41, 1614 1617; (b) Reggelin, M.; Dörr, S.; Klußmann, M.; Schultz, M.; Holbach, M. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 5461-5466; (c) Müller, C. A; Hoffart, T.; Holbach, M.; Reggelin, M. Macromolecules 2005, 38, 5375-5380.[2] (a) Megens, R. P.; Roelfes, G. Chem. Eur. J. 2011, 17, 8514-8523; (b) Ikeda, A.; Terada, K.; Shiotsuki, M.; Sanda, F. J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 3783-3796.[3] Lam, J. W. Y.; Tang, B. Z. Acc. Chem. Res. 2005, 38, 745-754.[4] (a) Aoki, T.; Kaneko, T.; Maruyama, N.; Sumi, A.; Takahashi, M.; Sato, T.; Teraguchi, M. J. Am. Chem. Soc. 2003, 125, 6346-6347; (b) Liu, L.; Zang, Y.; Hadano, S.; Aoki, T.; eraguchi, M.; Kaneko, T.; Namikoshi, T. Macromolecules 2010, 43,9268-9276.[5] (a) Schenker, S.; Zamfir, A.; Freund, M.; Tsogoeva, S. B. Eur. J. Org. Chem. 2011, 2209-2222; (b) Christoffers, J.; Koripelly, G.; Rosiak, A.; Roessle, M. Synthesis 2007, 9, 1279–1300.

176

ADSORPTION OF ENDOSULFAN ON BIODEGRADABLE POLYMER

Armila Rajbhandari (Nyachhyon)1, Thomas Gremm2, Fritz H. Frimmel2

1Central Department of Chemistry, Tribhuvan University, Kathmandu, Nepal2Engler Bunte Institute, Karlsruhe, Germany

Email: armila3@yahoo.com

The organochlorine pesticides are regarded as pollutants throughout the world. The indiscriminate use of this pesticide in agriculture, forestry and public health has left considerable residues and toxic metabolites in the environment. Endosulfan is a chlorinated insecticide. This and its metabolites are often detected in the environment. The endosulfan and its biological active oxidation product endosulfan sulphate are of particularly concern in water ways [1] as they are extremely toxic and the half lives endosulfan and endosulfan sulphate is 5-8 months. In this regard, the adsorption of endosulfan and endosulfan sulphate on natural (Bamboo and Sea weed) and synthetic polymer (Polycaprolacton PCL) [2] were investigated for the removal of Endosulfan and Endosulfan sulphate from water. The analysis of pesticide was carried out by gas chromatography/mass spectrometry (GC/MS). The PCL was studied in 3 different conditions (1) fresh, unused PCL, (2) biofilm covered PCL,(3) previously used and cleaned PCL. Fresh PCL showed the highest adsorption of endosulfan and endosulfan sulphate. From the results of adsorption experiments on PCL, it can be concluded that removal of endosulfan and endosulfan sulphate is caused by sorption rather than adsorption. Natural polymers showed good adsorption behavior.

[1] EEC Drinking water Guidelines, 80/779/EEC No L229/11-29, EEC, Brussels (1980).[2] Rajbhandari (Nyachhyon) A., Grem T., Frimmel F.H., Wissenschaftliche Abschlussberichte 35, Internationales Seminar 2000, 86-94.

177

SYNTHESIS OF NEW BENT-CORE LIGANDS DERIVEDFROM RESORCINOL AND [1,2,3]-TRIAZOLE

Narimane Kheddam, S. Saïdi-Besbes*, A.Derdour

Applied Organic Synthesis Laboratory – LSOA, Chemistry department, Sciences faculty, Oran Es Senia University. BP 1524 El M’naouer, Oran – Algeria

E-mail: salima_saidi@yahoo.fr

Since the first report of the Cu(I)-catalyzed 1,3-dipolar cycloaddition of azides to alkynes, also known as ‘click chemistry’ reaction, the number of applications of [1,2,3]-triazole derivatives has grown dramatically to cover a wide range of fields from synthetic chemistry to biomedicine and material science [1].

In the field of coordination materials, many reports dealing with the synthesis and the characterization of metal-[1,2,3] triazole complexes have been published [2]. The versatility of this heterocycle as ligand is determined by the number and the arrangement of the nitrogen atoms in the cycle as well as by the nature of the substituents. Transition metal complexes with this ligand have a great interest from both theoretical and practical viewpoints. Various applications in bioinorganic chemistry and materials science are well known [3-5].

In this paper we present new five-ring bent-core ligands which contain resorcinol as the central core and ester connecting groups between this aromatic ring and the [1,2,3] triazole units.

The triazolic heterocycle plays an important role since it acts as a linker between the conjugated segments of the compounds and also because it has a good electron affinity, potentially acting as an electron-transporting material.

Particular attention was focused on structure-property relationship, in which the variation of molecular structure and its subsequent effect on the coordination properties was investigated.

References[1] Rostovtsev, V.V.; Green, L.G.; Fokin, V.V.; Sharpless, K.B. Angew. Chem. Int. Ed. 2002, 41, 2596–2599.[2] Aromia, G.; Barriosa, L. A.; Roubeaub, O.; Gameza, P. Coordination Chemistry Reviews 2011, 255, 485–546[3] Beyer, B.; Ulbricht, C.; Escudero, D.; Friebe, C.; Winter, A.; Gonz Alez, L.; Schubert, U.S. Organometallics 2009, 28, 5478–5488.[4] Wang, X.L.; Qin, C.; Lan, Y.Q.; Shao, K.Z.; Su, Z.M.; Wang, E.B. Chem. Commun. 2009, 410–412.[5] Jones, L.F.; O’Dea, L.; Offermann, D.A.; Jensen, P.; Moubaraki, B.; Murray, K.S. Polyhedron 2006, 25, 360–372.

178

PREPARATION, CHARACTERIZATION AND ELECTRICAL PROPERTIES OF SOME

NANOCOMPOSITES BASED ON MULTIFUNCTIONAL POLYMERS

Sh. Said1, M. Abdel rehim2, A. Ghoneim1 and G. Turky1

1Microwave Physics and Dielectrics Dept, 2 Packing and Packaging Materials Dept, National Research Centre, Cairo, Egypt

gamalturky@yahoo.com

Abstract

Two different hyperbranched polymers, namely, poly ester amine and poly amide amine were prepared and characterized. In addition, the linear architecture of the later is also prepared by using piprazine and methyl acrylate for comparison. Thermal analysis (TGA and DSC) data, coupled with NMR and FTIR spectroscopic analysis were used to characterize synthesized polymers and distinguished between linear and hyperbranched poly amide amine. On the other hand, the treatment of kaolinite was performed to increase the basal space. X- ray diffraction (XRD) confirmed that the interlayer space of kaolinite was increased from 7.15 Ao to 11.13 by intercalation dimethyl sulfoxide (DMSO). Also the intercalation of dodecylamine enlarged the basal space to 37.8 Ao.

The dispersion of the nanocomposite systems into a polymer matrix in order to prepare polymer nanocomposite exhibiting better mechanical and electrical properties is the main goal throughout this work. Dielectric and electrical properties of the prepared samples were investigated and interpreted in some details.

[1]Mona Abd Elrehim, Shereen Said, Ahmed Ghoneim, Gamal Turky, Macromol. Symp.254, 2007, 1–8.[2]Gamal Turky, Shereen Said, Andreas Schoöenhals, J of Appl Polym Sci 113, 2009, 2477–2484.[3]G. Turky, J. R. Sangoro, M. Abdel Rehim and F. Kremer, Polym. Sci Part B: Polym Phys 48, 2010, 1651-1657.

179

DEVELOPMENT OF DEGRADABLE SHELL CROSSLINKED NANOPARTICLES FOR THE DELIVERY

OF NUCLEIC ACIDS

Sandani Samarajeewa, Ritu Shrestha, Karen L. Wooley

Departments of Chemistry and Chemical Engineering,Texas A&M University, College Station, TX 77843

E-mail: sandani.samarajeewa@chem.tamu.edu

Construction of nanoassemblies from enzymatically-degradable components is desired for packaging and controlled release of active therapeutics, and eventual biodegradability in vivo. In the first part of this study, shell crosslinked knedel-like (SCK) nanoparticles composed of biodegradable poly(lactic acid) (PLA) core were prepared by the supramolecular self-assembly of an amphiphilic diblock copolymer synthesized by a combination of ring opening polymerization (ROP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. Enzymatic degradation of the PLA cores of the nanoparticles was achieved upon the addition of an ester- and amide-degrading enzyme, proteinase K. Rigorous characterization measurements by 1H NMR spectroscopy, fluorescence spectroscopy, dynamic light scattering, atomic force microscopy, and transmission electron microscopy were employed to confirm core excavation. Kinetic analyses and comparison of the properties of the nanomaterials as a function of degradation extent are reported.

As cationic nanoparticles are a promising class of transfection agents for oligonucleotide and gene delivery, in the second part of the study, synthetic methodologies were developed for the conversion of the negatively-charged shell of the enzymatically-degradable SCKs to positively-charged cationic SCK (cSCK) nanoparticles for the complexation of nucleic acids. In addition to the exciting possibility of these degradable cSCK nanoparticles serving as vessels for efficient intracellular delivery of nucleic acids, the hydrolysis of the PLA core and crosslinkers may provide a mechanism for programmed disassembly of the cSCK nanoparticles within endosomes that would in turn promote endosomal disruption due to osmotic swelling, and release of active therapeutics from the nanoparticles.

180

SURFACE-MODIFIED POLYETHYLENE FILM ASAN INDICATOR FOR HEAVY METAL CONTAMINANTS

Chayanant Hongfa, Peerada Samunual, Sukhvinder Singh Khanuja, Wayne Nicholas Phillips

Science Division, Mahidol University International College, Salaya, Phutthamonthon,Nakhon Pathom 73170, Thailand

E-mail: icchayanant@mahidol.ac.th

Heavy metals contamination is a major problem in both developed and developing countries. Heavy metals, such as lead or mercury are often found in products such as children toys, paints, and food products. As a result, there is an urgent need for an economical heavy metal indicator. In order to address this issue, the modern approach of layer-by-layer (LbL) assembly to modify a surface of polyethylene can be used. The strip of high-density polyethylene (HDPE) was obtained from used water and milk bottles. A solution of chromium trioxide and sulfuric acid was then used to oxidize the surface of HDPE into multiple carboxylic acid groups. The polyethylene glycol was attached covalently to the surface of HDPE by the esterification process using oxalyl chloride. The newly made HDPE with hydrophilic surface was non-covalently embedded with various types of water-soluble ligands that can change their colors based on the coordination with different heavy metals.

181

THE RELATIONSHIP BETWEEN MOLECULAR GRAPH AND VIBRATIONAL NORMAL MODES, THE CRITICAL

INVESTIGATION ON C6H6 PES

Gholam Hossein Shafiee1*, Seyed Abdolreza Sadjadi1, Jamshid Njafpour2 shirin mehman navaz1

1. Molecular Modeling Lab, Department of Chemistry, Islamic Azad University of Abadeh, P.O.Box:73135-168, Abadeh, Fars, Iran.

2. Department of Textile Chemistry, Faculty of Engineering, Islamic Azad University Shahr-e-Ray Branch, P.O.Box: 18735/334, Tehran, Iran.

It seems that the general applicability of the quantum theory of atoms in molecules (QTAIM) specially the relationship between the molecular graph and potential energy surface (PES) still questionable even after passing 30 years from its formulation since the latter is used to deduce the cocept of bond. For clarifying this situation, the C6H6 isomers were chosen as the model systems and the results from molecular charge density analysis and vibrational normal modes computations were compared. It is demonstrated that the mathematical properties of molecular graph derived from charge density analysis are in good correlation with that of the vibrational normal modes derived from ab initio computations. The failure of other methods of deducing bond like Mulliken-Lowdin bond order analysis was also established rigorously.

*. Corresponding author: Shafiee@iaug.ac.ir

182

TOPOLOGICAL ANALYSIS AND QUANTUM MECHANICAL STRUCTURE OF C4 AND C5 PURE

CARBON CLUSTERS

Gholam Hossein Shafiee1*, Jamshid Najafpour2, Seyed Abdolreza Sadjadi3

1. Department of Chemistry, Islamic Azad University Abadeh, Abadeh , Fars, Iran 2. Department of Chemistry, Faculty of science, Islamic Azad University Shahr-e-Rey Branch, Tehran, Iran 3.

Department of Chemistry, Islamic Azad University of Kazeroon, Kazeroon, Fars, Iran

The Chemistry of Carbon and its compounds is one of the main domain of researches since 19th century. It is safe to say that the classical concepts of chemistry like 3D molecules, chemical bond, double bond, have been proposed from this branch. It is interesting to note that less attention has been paid to the nonclassical chemical behavior of Carbon in large amounts of pure carbon compounds known as Carbon clusters which is the main subject of research in chemistry of nanotubes. The first pioneering work on the molecular orbital calculations of carbon clusters has been reported by Pitzer and Clementi [1]. Two bonding models i.e cumullenic and acetylenic models have been proposed to account for the bonding patterns in linear carbon clusters while the bonding patterns in cyclic and 3D geometries have remained ambiguous.

This work presents the bonding patterns in various C4 and C5 pure clusters at MP2/aug-cc-pVTZ level of theory. The related wave function files for each geometry were produced at the same theoretical level. All MP2 computations were performed using PC GAMESS7.1 firefly [2]. This latter subject is studied in the light of modern bonding theory known as Quantum Theory of Atoms in Molecules, QTAIM. The electron density analysis was done using the AIM2000 software [3].

In linear clusters the ethylene like chemical bonds are reported, while in cyclic and 3D geometries the single and triple C-C bonds are found.

Keywords: Caron clusters, C4, C5, QTAIM, Chemical bond

References1. Pitzer, K.S.; Clementi, E. J. Am. Chem. Soc. 1959, 81, 4477.2. Granovsky, A.A. http://classic.chem.msu.su/gran/gamess/index.html, Schmidt, M.W.; Baldridge,K.K; Boatz, J.A.; Elbert, S.T.; Gordon, M.S.; Jensen, J.H.; Koseki, S.; Matsunaga, N.; Nguyen, K.A.; Su, S.J.; Windus, T.L.; together with Dupuis, M.; Montgomery, J.A. J. Comput. Chem., 1993, 14, 1347.3. Biegler-König, F.; Schönbohm, J.; Bayles, D. “AIM2000 - A Program to Analyze and Visualize Atoms in Molecules”, J. Comp. Chem., 2001, 22, 545.

183

SYNTHESIS OF POLYADIPATE-DIOL/CLOISITE 30B NANOCOMPOSITE BY CIRCULATION REACTOR

Seung-Wook Shin, Kyeong-Kyu Park and Sang-Ho Lee

Department of Chemical Engineering, Dong-A University Hadan2-dong, Saha-gu, Busan 604-714, Republic of Korea

E-mail: sangho@dau.ac.kr

Organo-nanoclay are broadly used to improve the properties of polymer, such as mechanical strength, thermal stability, barrier properties, and flame resistance.[1] To maximize the improvement by organo-nanoclay, the silicate layers of the clay is required to be exfoliated and well-dispersed in the polymer. From adipic acid, excess diethylene glycol and Cloisite 30B, we have synthesized polyadipate-diol/Cloisite 30B composite with butyltin tris-2-ethylhexanoate catalyst through in-situ polymerization technique.[2,3]

The ammonium salt of Cloisite 30B has two 2-hydroxyethyl groups, one methyl group, and one dehadrogenated tallow. The tallow consists mainly of C18 carbon chain. The d001 spacing of Cloisite 30B was measured 18.5 Å. The estimeated chain diameter and length of adipic acid are ca. 3.0 Å and 9.3 Å, respectively, when it fully strectches at all trans structure. Therefore, adipic acid penetrated into the interlayer of Cloisite 30B, reacted with the 2-hydroxyethyl groups of the ammonium salt, and converted the the 2-hydroxyethyl groups to the ethyl-adipate, which have carboxylic acid groups at the both ends of the adipate. Through the esterification with diethylen-glycol and the ethyl-adipate, the molecular size of the ammonium salt increased and as the result, the silicate layer of Cloisite 30B delaminated. Without Cloisite 30B, the polyesterification between adipic acid and diethylene glycol is so simple that the esterification conversion reached at approximately 99% in 300 minutes at 423K. The condensated water, by product, was wasily distilled out from the reactant-product mixture during the esterification. Since the initial molar ratio of [COOH]/[OH] was 0.5, polyadipate-diol was mainly produced. When Closite 30B was mixed with adipic acd and diethylene glycol, the water vapor evolved from reactant mixture as by-product made small bubble layer on the top, which were extremly difficult to break into the atmosphere. The top bubble layer prevented the water from vaporizing out of the reactant-product mixture, as the consequence, the esterification rate significantly decreased and the conversion was not able to reach over 50%. To overcome the mass transfer limitation by the bubble layer, we modified the esterification reactor. To break the bubbles in the top layer, circulation line was installed to make the reactant-product mixture flow from the bottom to the top or vice versa. The degree of breaking the bubbles were mainly modulated with the shape of nozzle of the circulation line. The polyesterification rate between adipic acid and diethylene glycol with Cloisite 30B was almost identical to the esterification rate reacted without Cloisite 30B.

[1] Krishnamoorti, R.; Vaia, R. A. Chapter 2, ACS, Washinton DC, 2002.[2] Nalwa, H. S. ASP, CA, USA, 2004, 6, 237.[3] Giannelis, E. P. Appl. Organometal. Chem.1998, 12, 675–680.

184

INSIGHTS INTO CRYSTALLIZATION KINETICSOF POLYETHYLENE

Martine Slawinski1, Guillaume Jean², Jacques Michel1

1Total Petrochemicals Research Feluy, Zone C, 7181 Seneffe, Belgium2Faculté Polytechnique-Université de Mons, Rue de Houdain 9, 7000 Mons, Belgium

E-mail: martine.slawinski@total.com

Polyethylene has found a wide range of uses today from packaging for industrial and consumer goods to water- and gas-supply piping, fuel tanks for motor vehicles, cable jacketing, monofilament extrusion, rotational and injection moulding etc... Although polyethylene is not a novel polymer as such, it remains one of the most widely studied ones. Excellent understanding of the relationships between polymer microstructure and processing behaviour or final product properties is the key to the development of improved materials for constantly more demanding applications. Enhanced performance in terms of environmental properties (including light weighting), gloss and transparency, gas permeability, chemical resistance, mechanical properties and processability are achieved by tailoring the molecular design of the polymer chains.

The impact of molecular parameters like polymer density, molecular weight and molecular weight distribution of several metallocene-based polyethylene products on the crystallisation kinetics has been investigated. A comparative approach has been developed using both Differential Scanning Calorimetry (DSC) and Optical Microscopy. Some insights into the crystallization behaviour of polyethylene could be obtained.

185

SYNTHESIS AND HYDROLYSIS-CONDENSATION STUDY OF SELF-ASSEMBLE PENTACOORDINATE POLYSILYLAMIDES- A POLYPEPTIDE ANALOGUE

Muhammad Sohail,*a Alan R. Bassindale,a Peter G. Taylor,a Alexander A. Korlyukovband Dmitry E. Arkhipovb

aDepartment of Chemistry and Analytical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA, UK E-mail: muhammad.sohail@qatar.tamu.edu,

bX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, 28 Vavilov St., B-334, Moscow 119991, Russia

Polysilylamides with Si-Cl functionality containing pentacoordinate silicon as a backbone were produced in high yield by transilylation of bis(chloromethyl)methylchlorosilane and diketopiperazine, an amino acid derivative[1]. Pentacoordinate polysilylamides were highly soluble in water through the formation of protonated Si-OH2+ bonds from hydrolysis of the Si-Cl bond in each repeat unit. The protonated polysilanolamides were stable towards self-condensation and found to be pentacoordinated even in water by avoiding siloxane (Si-O-Si) bond formation. The polysilanolamides underwent intra-molecular stepwise hydrolysis-condensation plausibly as a result of Si=C double bond formation at each monomer unit in gas phase, observed by MALDI-TOF MS. New model compounds of pentacoordinated silicon derivatives of pyridones were synthesized, characterized and compared with polysilanolamides by NMR and X-ray crystallography. It is found that the partial hydrolysis of the model pentacoordinate chlorosilanes give pentacoordinate protonated silanols those resemble an intermediate in the aqueous hydrolysis of pentacoordinate polysilanolamides.

[1] Muhammad, Sohail.; Bassindale, A. R.; Taylor, P. G.; Male, L.; Coles, S. J.; Hursthouse, M. B., Study of Binuclear Silicon Complexes of Diketopiperazine at SN2 Reaction Profile. Organometallics 2011, 30 (3), 564-571.

186

THE INFLUENCE OF BACKBONE RIGIDITY ON THE FORMATION OF SINGLE-CHAIN NANOPARTICLES

Patrick J. M. Stals,1 Martijn A. J. Gillissen,1 Anja R. A. Palmans,1 E. W. Meijer1

1Institute for Complex Molecular Systems and Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Techonoly, Eindhoven, the Netherlands

E-mail: p.j.m.stals@tue.nl

Controlled folding of Single Chain Polymer Nanoparticles (SCNPs) is an emerging field of research receiving more and more attention.[1] By making use of specific and directional non-covalent interactions such as hydrogen bonding, single chains of synthetic polymers are folded into defined secondary structures.[2] Our goal is to obtain well-defined tertiary structures starting from these secondary structures, a field which is currently dominated by biological system such as DNA and proteins. Understanding the rules governing the folding of SCNPs, will not only lead to more insight in the fields of supramolecular chemistry but will serve as a simplified model system for understanding protein folding. We envision these nanoparticles as well-defined structures with potential for use in areas as catalysis, sensing, drug delivery and coating technology. [3]

In this contribution we will discuss the influence of solvent, supramolecular moiety and polymer backbone on the folding properties of a large set of SCNPs. We prepared a set of polymers differing in backbones and therefore rigidity; polymers with polybutylacrylate, polymethylmethacrylate, polystyrene and polynorbonene backbones where prepared. All polymers were functionalised with photoprotected 2-ureido-pyrimidinone (phUPy) units as self-assembling moieties, one of the most studied and used hydrogen-bonding motifs. [4] Upon UV-irradiation the photoprotecting group will fall off and the UPy-moieties will be able to dimerise and the polymer will form a SCNP.

Using dynamic light scattering (DLS) and size exclusion chromatography (SEC) techniques we can observe the change in hydrodynamic radius of these particles. Furthermore in atomic force microscopy (AFM) studies we see the appearance of well defined particles after initiation of the non-covalent interactions.

In this contribution we will show our latest insights in this fascinating research-area. We will show that polar solvents, such as DMF, that can partially break inter-particle interactions can help in obtaining single particles; furthermore we will show that the rigidity of the backbone is a key-parameter on the possibility to fold the polymeric backbone and to form SCNP.

[1] Ritter, S.; Becker, N.; Blair, T. Chem. Eng. News, 2009, 87 (51), 35[2] Foster, E. J.; Berda, E. B.; Meijer, E. W. J. Am. Chem. Soc. 2009, 131, 6964[3] Terashima, T.; Mes, T.; de Greef, T. F. A.; Gillissen, M. A. J.; Besenius, P.; Palmans, A. R. A.; Meijer, E. W. J. Am. Chem. Soc., 2011, 133, 4742–4745.[4] Sijbesma, R.P.; Beijer, F. H.; Brunsveld, L.; Folmer, B. J. B.; Hirschberg, J. H. K. K.; Lange, R. F. M.; Lowe, J. K. L.; Meijer, E. W. Science, 1997, 278, 1601

187

POLYMER-SUPPORTED METATHESIS CATALYST IN THE SYNTHESIS OF BILE ACID-BEARING MACROCYCLES

Satu Strandman,1 Hassan S. Bazzi,2 David Bergbreiter,3 X.X. Zhu1

1Department of Chemistry, Université de Montréal, CP 6128, succursale Centre-ville, Montreal, QC, H3C 3J7, Canada

2Chemistry Department, Texas A&M University at Qatar, Doha, Qatar 3Chemistry Department, Texas A&M University, College Station, TX 77843

E-mail: sstrandman@gmail.com, julian.zhu@umontreal.ca

Ruthenium-catalyzed metathesis reactions provide a useful methodology for synthesizing cyclic and macrocyclic compounds as well as main-chain functionalized polymers. It is not easy to remove the catalyst containing transition metals particularly from polymeric products to avoid contamination of the materials. Also the regeneration or reuse of the catalyst would be desirable. Therefore, several strategies on supported catalysts have been developed [1]. Soluble polymer-supported catalysts can mimic the chemistry of their low-molar-mass counterparts and allow the reactions to proceed under homogeneous conditions [2]. A poly(isobutylene)-supported metathesis catalyst has been synthesized, where a Hoveyda-Grubbs 2nd generation catalyst is anchored between two poly(isobutylene) (PIB) chains. The resulting PIB-supported catalyst is soluble in heptane, enabling the use of thermomorphic solvent mixtures with heptane as a reaction medium or the separation of the product by liquid/liquid extraction [3].

The successful ring-closing metathesis (RCM) of various low-molar-mass dienes with protected functional groups [3] encouraged us to apply the supported catalyst in a more complex system. Bile acid-based aliphatic-steroidal macrocycles (Scheme 1) have been previously synthesized by RCM and polymerized through entropy-driven ring-opening metathesis polymerization (ED-ROMP) to yield high-molar-mass polymers with shape memory properties [4]. Replacing Grubbs’ 1st generation catalyst with the PIB-supported one in the RCM of a cholic acid-based diene gives similar conversions and low ruthenium leaching under homogeneous conditions (in organic solvents such as DCM or THF), suggesting that cholic acid moieties do not increase leaching. Using a biphasic methanol/heptane solvent system allows higher diene concentration beyond the point where the ring-chain equilibrium would be shifted towards polymerization under homogeneous conditions, and as a result the cyclization can be driven to high conversions. The use of the supported catalyst on ED-ROMP of the macrocycle is also studied.

Scheme 1. Cholic acid-based macrocycle, n ≥ 1.

[1] Buchmeiser, M.R. Chem. Rev. 2009, 109, 303-321.[2] Su, H.L., Hongfa, C., Bazzi, H., Bergbreiter, D.E. Macromol. Symp. 2010, 297, 25-32.[3] Hongfa, C., Su, H.L., Bazzi, H., Bergbreiter, D.E. Org. Lett. 2009, 11, 665-667.[4] Gautrot, J.E., Zhu, X.X. Macromolecules 2009, 42, 7324-7331.

188

SYNTHESIS OF NITROXIDE RADICAL-CONTAINING POLYMERS VIA LIVING POLYMERIZATION

FOR ELECTRODE ACTIVE MATERIALS

Takashi Sukegawa, Hajime Omata, Kenichi Oyaizu, Hiroyuki Nishide

Department of Applied Chemistry, Waseda University, Tokyo 169-8555, JapanE-mail: su-ke.ta-ka.4@ruri.waseda.jp / nishide@waseda.jp

Electro-active polymers are attracting a great interest on energy devices such as secondary batteries, solar cells and capacitors because of their formability, flexibility and transparency suiting for various electronic portable instruments. We have proposed non-conjugated polymers containing radical sites, which work for charge transport and charge storage based on self-electron exchange mechanism and stable ionic states.[1] Among organic radicals, nitroxide radicals, especially 2,2,6,6-tetramethylpiperidin-N-oxy (TEMPO) and nitronyl nitroxide show p-type and both p- and n-type, respectively.[2, 3] Therefore, we applied TEMPO-substituted polymethacrylate (PTMA) 1 and nitronyl nitroxide-substituted polystyrene for cathode and anode active materials for Li ion battery and totally organic radical battery and have proved their availability for practical applications. However, these two polymers were synthesized via free radical polymerization of non-radical precursors, hence, resultant polymers underwent oxidation or deprotection processes to be radical states. Therefore, anionic polymerization and ring opening polymerization were adopted for polymerization of TEMPO and nitronyl nitroxide radical state monomers, respectively (Scheme). Molecular weight of 1 and nitronyl nitroxide-substituted polynorbornene 2 were well controlled and radical densities of both 1 and 2 are almost 1 unpaired electron / monomer unit, this result indicates that there are no degradation of radicals under polymerization. 1 and 2 show stable redox properties at corresponding potential [1: +0.8 V, 2: +0.8 V and -0.8 V]. Block copolymer, PS-b-PTMA is synthesized via anionic polymerization and its phase-separated structures were observed by AFM. Electrochemical properties of the block copolymer will be also discussed.

[1] Oyaizu, K.; Nishide, H. Adv. Mater. 2009, 21, 2339–2344.[2] Nakahara, K.; Oyaizu, K.; Nishide, H. Chem. Lett. 2011, 40, 222-227.[3] Suga, T.; Sugita, S.; Ohshiro, H.; Oyaizu, K.; Nishide, H. Adv. Mater. 2011, 23. 751-754.

1 2

Scheme

189

DIELECTRIC SPECTROSCOPY AS A TOOLTO INTERPRET THE CHARGE TRANSPORT

AND ELECTRODE POLARIZATION

G. Turky

Microwave Physics Dept, NRC, Bohoos Str., Dokki, Cairo, Egypt

Dielectric Spectroscopy is a very useful tool in studying the charge transport, electrode polarization as well as the molecular dynamics in different advanced polymeric systems. The dielectric properties of many synthesized hyperbranched polymeric systems were investigated using dielectric spectroscopy. In addition, the measurements were carried out on hb polyesters in different generations supplied by Perstorp, Sweden, under the trade name Boltorn H20 – H50 (indicating the second to the fifth generations).

At lower temperatures (higher frequencies) two different dynamic processes called α and α were investigated. The former is found to be due to the libration fluctuation of the end groups, where as the later is attributed to the functional ones. Both follow an Arrhenius behavior with activation energy remarkably higher than that of the linear polymers. It is also noticed that for all investigated polymers, the segmental motion related to the glass transition called α-dynamics is screened out due to the conductivity contribution. On the other hand, at higher temperatures (lower frequencies), the dielectric spectra are interpreted in terms of hopping conduction in a spatially randomly varying energy landscape. Despite a shift of more than three decades in the dc conductivity upon variation of the end groups, the Barton–Nakajima–Namikawa (BNN) relation is shown to be hold. Based on Einstein and Einstein- Smoluchowski relations, the diffusion coefficient extracted from the dielectric spectra is in quantitative agreement with independent PFG NMR measurements. Further decrease of frequencies showed that the net dielectric response increases by many orders of magnitude in these systems and the relaxation frequencies and permittivity enhancements are located in these low frequency regimes. The charge carriers mobility is drastically slowed down reflected by the reduction of conductivity at the metal/sample interface. It is important to compensate for this phenomenon. More effective electrode polarization is found in more conductive materials called ionic liquids. The deep insight and modeling of the electrode polarization and what is there in the double layer at the interface will lead to the improving and developing the technology of supercapacitors.

1. Turky GM, Sangoro J, Abdel Rehim MH, Kremer F., Polym Sci Part: B Polym Phys. 2010, 48, 1651.2. Turky GM, Shaaban Sh S, Schönhals A. J Appl Polym Sci 2009, 113, 2477.3. Sangoro JR, Turky GM., Abdel Rehim MH, Iacob C, Naumov S, Ghoneim AM, Kärger J, and Kremer F., Macromolecules 2009, 42, 1648.

190

POLYISOBUTYLENE-SUPPORTED RECYCLABLE CATALYSTS AND REAGENTS

Yun-Chin Yang, Christopher E. Hobbs, David E. Bergbreiter

Department of Chemistry, Texas A&M University, College Station, TX 77843E-mail: ycyang@mail.chem.tamu.edu

Phosphines are important as catalysts and reagents in organic synthesis but must be separated from products after a reaction. This poster shows that polyisobutylene (PIB)-bound alkyldiaryl- and triarylphosphines are useful as catalysts in alcohol addition and allylic amination reactions. They are also useful as reagents in aza-Wittig and Mitsunobu reactions. Heptane solutions of such phosphines and their oxidized byproducts can be easily separated from polar solutions of organic products, and PIB-phosphine oxides formed during a reaction can readily be reduced to PIB-phosphines for reuse. [1].

N-Heterocyclic carbenes (NHC) are also useful organocatalysts. However, efforts to recycle NHC catalysts are still being developed. This is probably due to air and moisture sensitivity of NHCs which makes recycling NHCs difficult. Reactions using latent NHC catalysts are recently reported. [2]. Synthesis of PIB-bound NHC-isothiocyanate adducts is an approach that is amenable to supported catalysts and catalytic activity and recyclability of these PIB-supported latent NHC catalysts in phenyl isocyanate trimerization will be discussed.

[1] Bergbreiter, D. E.; Yang, Y.-C.; Hobbs, C. E. J. Org. Chem. 2011, 76, 6912–6917.[2] Norris, B. C.; Sheppard, D. G.; Henkelman, G.; Bielawski, C. W. J. Org. Chem. 2011, 76, 301–304.

191

SYNTHESIS OF PH-RESPONSIVE AND PH-STABLE POLYMERSOMES AND THEIR APPLICATION AS DRUG

DELIVERY CARRIERS

Mohamed Yassin,1 Dietmar Appelhans,1 Rafael Mendes,2 Mark Rümmeli,2 Brigitte Voit1

1Polymer Structures, Leibniz Institute of Polymer Research Dresden e. V., Dresden,Germany2Molecular Nanostructures, Leibniz Institute for Solid State and Materials Research

Dresden,Dresden, Germany,E-mail: yassin@ipfdd.de

In the past years, polymersomes showed promising potential applications in medicine,pharmacy and biotechnology due to the increased strength and stability of polymersomes relative to their phospholipid vesicle analogues (liposomes) and their ability to deliver both of the hydrophilic and hydrophobic bioactive molecules.[1] The design of polymersomes with desired properties and the potential for attaching targeting groups on their surfaces can be achieved using controlled/living free radical polymerization (CRP) which allows the synthesis of functionalized block copolymer with the desired block length and with control over the end groups.[2]

Here, we present the synthesis of pH-responsive crosslinked polymersomes. They are achieved by self-assembly into a closed double layer membrane of an amphiphilic block copolymer synthesized via atom transfer radical polymerization (ATRP). Our block copolymer consists of a hydrophilic polyethylene glycol (PEG) block and the hydrophobic block is formed from a statistical copolymer within the 2-(diethylamino) ethyl methacrylate (DEA) monomer units provide pH sensitivity at 7.5, and the 2-hydroxy-4-(methacryloyloxy) benzophenone (PBMA) comonomer acts as photo active cross-linker providing a stable polymersomes against lower pH (scheme 1).

Scheme 1. Block copolymer synthesis

The photo cross-linked polymersomes showed a high stability over a large pH range from2-10 even after only five minutes of UV irradiation (Fig.1 a). Moreover, they also show a definite pH-responsivity around pH 7. Thus, at pH 3 the membrane undergoes swelling due to protonation of amino groups resulting in polymersomes of about 200 nm (Fig.1 b) which shrinkreversibly to 120 nm at pH 10. This feature provides polymersomes with controllable gates within the membrane, giving the possibility to control the diffusion of bioactive molecules through the polymersome membrane depending on the pH.

191

192

Figure 1: Swelling of photo cross-linked polymersomes after different time of irradiation (a),Photo cross-linked Polymersomes at pH 3 (b)

Benefiting from these features, the new polymersomes were used as a carriers to deliverribavirin which is used as nucleotide analogue in combination with interferon alpha as the only available treatment for Hepatitis C virus (HCV). Our polymersomes show the ability to encapsulate ribavirin and the release profile indicates a significant retarded release of ribavirin.

[1] Fenghua M.; Zhiyuan Z.; Jan F. Biomacromolecules, 2009, 10(2), 197-209.[2] Stefan E.; Martin N.; Vimalkumar B.; Mohamed C.; Nico B.; Cornelia P.; Wolfgang M. J. Am.Chem. Soc, 2011, 133(12), 4476-4483.

193

MERCERIZED NATURAL CELLULOSE BASED- SOLID POLYMER ELECTROLYTE.

Anis Tasnim M.Y. 3, Jahimin A.1 , Fauziah A. A.1 and Razali I2

1School of Science and Technology, Universiti Malaysia Sabah, Jalan UMS, 88400, Kota Kinabalu, Sabah.

Email: jthan@ums.edu.myafauziah@ums.edu.my

2Advanced Materials Research Centre (AMREC) SIRIM Berhad Lot 34, Jalan Hi-Tech 2/3. Kulim Hi-Tech Park 09000 Kulim Kedah Darul Aman MALAYSIA.

Email: razali@sirim.my

3School of Distance Education (Chemistry Department), Universiti Sains Malaysia, 11800 USM, Pulau Pinang, MALAYSIA.Email: anistasnim@usm.my

Cellulosic materials derived from three different types of local wood samples (sawmill woods sawdust, Acacia mangium and belian (Euxideroxilon zwagery) were extracted at atmospheric pressure using organosolv method. In an initial stage, the wood samples were delignified using peroxyacetic acid pulping to remove lignin. Then the pulp was bleached in 0.01 M solution of sodium hydroxide (NaOH) with addition of 4% hydrogen peroxide of absolute dry pulp (ODP). Conversion to alpha-cellulose or mercerized cellulose was achieved by soaking bleached cellulosic materials in 17.5% solution of NaOH for 15 minutes at 25ºC. The mercerized cellulose was thoroughly washed with large amount of distilled water until pH of the filtrate reached to natural, then vacuum dried at 60ºC. From Scanning electron microscope (SEM) all mercerized woods cellulose were differ in microfibril size with high irregularity observed in sawmill sawdust. Formation of cellulose II was confirmed with X-Ray Diffraction (XRD) and Fourier transform infrared spectroscopy (Ft-IR) analysis. Preparation of solid polymer electrolyte (SPE) membrane was obtained by dissolving dry mercerized cellulose in molten 1-butyl-3-methylimidazolium chloride ([bmim]Cl) in the presence of lithium perchlorate (LiClO4) to produce a transparent solid gel film. All SPE membranes exhibit conductivity in the range of 3.6 x 10-6 to 5.7 x 10-5 Scm-1 at room temperature. It was also observed that the conductivity of the SPE is affected by the size of cellulose microfibril and type of extraction. It was then further characterized with SEM, XRD, FTIR and TGA.

Keywords: Wood, Organosolv, Cellulose, mercerized, SPE, conductivity.

194

ELECTROSPUN NANOFIBERS CONTAINING DRUG- LOADED NANOPARTICLES WITH CORE- SHEATH MORPHOLOGY FOR PROGRAMMABLE DRUG RELEASE

Somayeh Zamani,1Sepideh Khoee,*1

Polymer Chemistry Department, School of Science, University of Tehran, Tehran, IranE-mail: somayehz@khayam.ut.ac.ir, khoee@khayam.ut.ac.ir

Fibers are remarkable structural entities having a wide range of applications in our everyday lives. They are an extraordinary form of matter, possessing superior mechanical properties compared with the same material in bulk form [1]. In recent years, electrospinning, as a simple technique has attracted great attention to produce ultrafine fibers with diameters ranging from several microns down to tens of nanometers, for biomedical applications (such as drug delivery, wound healing, tisue engineering, ...)[2].The second most abundant polysaccharide, chitosan, has beneficial properties such as its biodegradability, biocompatibility, mucoadhesiveness, and adsorption and antimicrobial properties, which make this material attractive in various applications. On the other hand, it has some drawbacks, such az poor processability. Blending is a common solution to address the poor processability of chitosan.

In this work a series of PEG-PCl-PEG and PCl-PEG-PCl triblock copolymers were synthesized from m-PEG and ε-caprolactone in the presence of Sn(oct)2. PEG-PCl-PEG triblock copolymers were obtained via the coupling reaction of m-PEG-PCl diblock copolymers by adipoyl chloride. The structure of resultant polymers were characterized by FT-IR and 1H-NMR. Quercetin-loaded nanoparticles prepared by nanoprecipitation method [3]. Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) were used to determine the size and morphology of nanoparticles. Release profile, encapsulation efficiency and drug loading of nanoparticles were investigated by UV-visible spectrophotometer.

In the second step, chitosan/PEG nanofibers and nanoparticles were prepared by electrospinning and simple emulsion technique. Different chitosan/PEG proportions were dissolved in 90% aqueous acetic acid solution and electrospun to obtain desired nanofibers. Morphology of nanofibers was studied by Scanning Electronic Microscopy. Nanofibers containing nanoparticles were also prepared by mixing an aqueous dispersion of hydrophobic drug-loaded PEG-PCl-PEG triblock copolymer nanoparticles and chitosan/PEG solution before electrospinning. A hydrophilic drug can be added to chitosan/PEG solution to have a dual drug delivery system in which the hydrophobic drug would be released slower than hydrophilic drug. The release profile of chitosan nanofibers containing drug loaded nanoparticles in phosphate buffer was also studied and compared to chitosan nanoparticles containing polymeric nanoparticles and chitosan-free nanoparticles. The results revealed that drug-loaded nanoparticles were encapsulated in the nanofibers, forming a core-sheath structure and hydrophobic drug release from this kind of morphology was quite different from shell-free nanoparticles and spherical chitosan containing polymeric nanoparticles.

[1] Malheiro, V. N.; et al, Acta Biomaterialia , 2010, 6, 418–428.[2] Jing A.; et al., Colloid. Polym. Sci.,2009, 287, 1425–1434.[3] Khoee, S.; Hassanzadeh, S., Nanotechnology, 2007, 175602.[4] Crini, G.; Badot, P. M.,Prog. Polym. Sci.,2008, 33(4),399–447.

195

NONCOVALENT INTERACTIONSOF AROMATIC MOLECULES

S. D. Zarića G. Janjićb, D. Sredojevića, D. Veljkovićb, J. Andrića,D. Ninkovića, P. Petrovića

aDepartment of Chemistry, University of Belgrade,bInstitut of Chemistry, Technology and Metallurgy, University of Belgrade

Njegoševa 12, Belgrade, SerbiaE-mail: szaric@chem.bg.ac.rs

Noncovalent interactions of aromatic molecules are very important in all molecular systems including polymers and organic molecules. Aromatic molecules can form several types of noncovalent interactions: stacking (face to face and displaced face to face), CH/π aromatic-aromatic interactions, XH/π, and CH/O interactions. Analyzing geometrical parameters in the crystal structures from Cambridge Structural Database and Protein Data Bank and using quantum chemical calculations we characterized several types of noncovalent interactions with π -systems.

Most of the studies stacking interactions consider organic aromatic molecules, however, other planar molecules and fragments can also be involved in stacking interactions. It has been observed that planar chelate rings with delocalized π -bonds can be involved in noncovalent interactions in a manner similar to that of organic aromatic rings. Both CH/π and stacking interactions with chelate rings were observed. Analysis of the crystal structures of the metal complexes and quantum chemical calculations showed that a chelate ring can be a hydrogen atom acceptor in CH/π interactions. Analysis of geometrical parameters in the crystal structure of square-planar complexes from Cambridge Structural Database showed phenyl-chelate [1] and chelate-chelate [2] stacking interactions.

Study of the interactions between water and C6-aromatic rings revealed the existence of conformations where the water molecule or one of its O-H bonds is parallel to the aromatic ring plane. Study showed that the water/aromatic parallel alignment interactions can be significantly strong at large horizontal displacements. We calculated the strongest energies for the water position with the large horizontal displacements, out of the aromatic ring and out of the C-H bond region. The calculated energies of the interactions are significant, up to ΔECCSD(T)(limit)= -2.45 kcal/mol (at horizontal displacement of 2.6 Å), and comparable with the energy of slipped-parallel benzene/benzene dimer [3].

Our resent result on the interactions of two benzene molecules in the parallel orientation has shown that in the crystal structures preferred parallel aromatic/aromatic interactions at large offsets were observed and not at the lowest calculated energy with offset of 1.5-2.0 Å. From the calculations we obtained significant interaction energy of about 2.0 kcal/mol (71% of the strongest interaction energy) for the large offsets of 3.5-5.0 Å. Moreover, at B2PLYP-D/def2-TZVP level we obtained new minimum for benzene/benzene parallel orientation, at the offset value of 4.53 Å, with interaction energy of 2.01 kcal/mol. At the large offsets the additional stabilization is achieved by other simultaneous interactions of benzene π system [4].

[1] Tomić, Z. D.; Sredojević, D. N.; Zarid, S. D. Crystal Growth & Design, 2006, 6, 29.[2] Sredojević, D. N.; Tomić, Z. D.; Zarić, S. D. Crystal Growth & Design, 2010 10, 3901.[3] Janjić, G. V.; Veljković, D. Ž.; Zarić, S. D. Crystal Growth & Design, 2011, 11, 2680.[4] Ninković, D. B.; Janjić, G. V.; Veljković, D. Ž.; Sredojević, D. N.; Zarić, S. D.ChemPhysChem, accepted

196

AN EFFICIENT THREE-COMPONENT SYNTHESISOF CHROMENE DERIVATIVES ON GRINDING

Adeleh Moshtaghi Zonouz, Somaieh Okhravi

Faculty of science, Azarbaijan University of Tarbiat Moallem, Tabriz, IranE-mail: adelehmz@yahoo.com

The chromene framework, particulary 4-aryl/alkyl-2-aminochromenes, is an importantmedicinal scaffold. Several compounds having this framework show pro-apoptotic activity against cancer cells as a single or in combination with chemo radiotherapy, as well as anticoagulant, spasmolytic, diuretic, insecticidal and antiunaphylacyin activity. Some of them can also be employed as cosmetics and pigments, and utilized as potential biodegradable agrochemicals [1,2]. Despite the several existing methods for the synthesis of chromene derivatives [3,4], there still is demand for general strategies which can efficiently provide variously substituted chromene systems.

We achieved to a practical, clean and highly efficient method for the combinatorial library synthesis of chromene derivatives 1 via a three-component reaction of aromatic aldehydes, dimedone, malononitrile, in the presence of ammonium acetate as basic catalyst under solvent-free conditions at room temperature on grinding. Despite using so much ammonium acetate, no 1,4-dihydropyridine product 2 was detected. The present method does not involve any hazardous organic solvent. The key advantages are the short reaction time, high yields, simple workup, and purification of products by non-chromatographic methods, i.e., by simple recrystallization from ethanol.

[1] Kumaravel, K.; Vasuki, G. Green Chem. 2009, 11, 1945-1947.[2] Kumar, S.; Sharma, p.; Kapoor, K. K.; Hundal, M. S. Tetrahedron 2008, 536-542.[3] Jin, T-S.; Wang, A-Q.; Shi, F.; Han, L-S.; Liu, L-B.; Li, T-Sh. ARKIVOC 2006, 78-86.[4] Wang, X. S.; D. Shi, Q.; Tu, S. J.; Yao, C. S. Synth. Commun. 2003, 33, 119.

197

INDEX

Abdel Rehim, Mona 178Aiymgul, Akimbaeva 117Akram, Shumalia 118Alamdarnejad, Ghazaleh 119Alameddine, Bassam 120Aleksandra, Pelczarska 121Al-Maadeed, Mariam 36Almutairi, Adah 96Appelhans, Dietmar 122Aqel, Ahmad 123

Bag, Braja B. 75Barner-Kowollik, Christopher 48Basset, Jean 33Bazan, Guillermo 62Bercaw, John 32Bergbreiter, David 20,91Berglund, Lars 73Bielawski, Christopher 83Bochmann, Manfred 38Burke, Dan 108Burts, Alan 124

Cappelletto, Elisa 125Carpentier, Jean-Francois 35Caruso, Frank 94Choi, Tae-Lim 119Connor, Eric 101Drockenmuller, Eric 49

Ebadi-Dehaghani, Hassan 126,127,129Ebrahimi, Rajabali 130ElMehbad, Noura 131El-Sayed, Mohamed 85El-Sayed, Heba 116

Farah, Manal 132Farooqi, Zahoor 133Fatemi, Mohammad 139Faycal, Dergal 135Firestone, Millicent Anne 57Ford, Warren 107Fracaroli, Alejandro 136Fréchet, Jean

Gaitzsch, Jens 137Ghorbani, Mohammandali 139Gillissen, Martijn A.J. 142Groschel, Andre 88Grubbs, Robert B. 44Grubbs, Robert H. 19, 29Gure, Baris 143

Hahn, Michael 69Haraguchi, Naoki 112

198

Hawker, Craig 20, 53Herrmann, Andreas 66Hongfa, Chanayant 144Huang, Xin 87

Ince, Ahmet 145Ismail, Ali Sami 180Ito, Shinzaburo 59Itsuno, Shinichi 52

Kachbi, Souad 97Kaminsky, Walter 37Kang, Eun-Sil 147Kawashima, Hirotsugu 148Keller, Michel 150Khakpour, Mazyar 151Kim, Jeongeun 152Koh, Moo-hyun 153Komiya, Gen 154Kostiainen, Mauri 71Kozlowska, Agnieszka 155Kuckling, Dirk 113Kurian, Joseph 21, 79

Labidi, Salima 156Leitch, David 46Leroux, Jean-Christophe 95

Maggini, Simona 157Maier, Gerhard 58Majumdar, Rakhi 158Mamlouk, Hind 159Mashhadizadeh, Mohammad 160McLaughlin, Christopher 162Mednova, Olga 164Meekum, Utai 165Meier, Michael 74Meijer, E.W. Bert 106Meyer, Nils-Christopher 166Mijalis, Alexander 167Min, Byung Gil 168Misra, Manju 76Mitsui, Ryosuke 169Mohanty, Amar 78Monteiro, Michael 84

Nagasawa, Atsushi 170Nishide, Hiroyuki 188, 21Nolte, Roeland 64Novák, Petr 54Nevaz, Shirin 181Oh Kim, Kyung 171Ojani, Reza 172O’Reilly, Rachel 43Ouderni, Mabrouk 173Oyaizu, Kenichi 56

Park, Kyeong-Kyu 174

199

Patel, Martin 80Petersen, Vibeke 175Poizot, Philippe 55

Rajbhandari-Nyachhyon, Armila 176Rasoul, Firas 98Razavi, Abbas 22, 40Rosen, Christian 65Rowan, Stuart 89

Saidi-Besbes, Salima 177Samarajeewa, Sandani 179Samumual, Peerada 144Seeman, Nadrian 63Serpell, Christopher 50Seuring, Jan 92Shafiee, Gholam 181Shin, Seung-Wook 183Skrobot, Jedrzej 81Slawinski, Martine 184Sleiman, Hanadi 20,68Sohail, Muhammad 185Stals, Patrick J. M. 186Strandman, Satu 187Streff , Jennifer 77Stupp, Samuel 67Sukegawa, Takashi 188Suspene, Clement 45, 61 Terano, Minoru 39Toy, Patrick 90Tuba, Robert 47Turky, Gamal 189Valiyaveettil, Suresh 110

Voit, Brigitte 23, 104 Weck, Marcus 100Wooley, Karen 23,102 Yang, Yun-Chin 190Yang, Zhongqiang 70Yassin, Mohamed 191Yokozawa, Tsutomu 111Yusof, Anis 193

Zamani, Somayeh 194Zaric, Snezan 195Ziegler, Tom 34Zonouz, Adeleh Moshtaghi 196

200