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RACI- 2014 National Congress of Chemistry Dr. Ahmed Khudhair Hassan
Ministry of Science & TechnologyEnvironment & Water Directorate
Baghdad - Iraq
Event Name: The Royal Australian Chemical Institute (RACI)
2014 National Congress.
Event location: Adelaide / Australia.
Event date: 7-12 December 2014.
The meeting held every five years.
There are over 1000 delegates at the meeting and many of these
are students and early career scientists.
More than 550 Oral Presentations and more than 250 Poster
Presentations.
Theme 1: Synthetic Chemistry. Theme 2: Fundamental Interactions in Chemistry. Theme 3: Advanced Materials. Theme 4: Chemical Health and Safety. Theme 5: Chemistry in Health. Theme 6: Chemical Analysis and Sensing. Theme 7: Community Engagement.
Themes
Theme 3: Advanced Materials
OUTSTANDING ADSORPTION OF ARSENIC FROM CONTAMINATED WATERS USING GRAPHENE/IRON OXIDE NANOPARTICLES-AEROGLES.
NANOPOROUS LAYERED GRAPHENE HYDROGELS OF CONTROLLED PORE SIZES: DESIGN, SYNTHESIS, CHARACTERIZATION AND APPLICATIONS.
GRAPHENE: A NOVEL MATERIAL FOR ELECTRONICS AND OPTOELECTRONICS.
LOW COST SOLUTION PROCESSED GRAPHENE-SILICON SOLAR.
DEVELOPMENT OF POLYMERIC COATINGS TO PRODUCE ANTI-BIOFOULING WATER TREATMENT MEMBRANES.
ELECTROCHEMICAL FABRICATION OF CATALYTICALLY ACTIVE ORGANIC SEMICONDUCTORS WITH ENVIRONMENTAL APPLICATIONS
Adsorption and reduction for heavy metal ions using Graphene
Heavy metal ions, such as lead (Pb2+), cadmium (Cd2+), chromium
(Cr3+, Cr6+), mercury (Hg2+), copper (Cu2+) and arsenic (As3+), have
severe risks to environment and human health, and need to be removed
from soil and water.
Graphene and its derivatives with high surface areas and many
functional groups, which benefit to the adsorption or preconcentration
of heavy metal ions, are given great attention in the present researches.
Graphene oxide (GO) and reduced graphene oxide (RGO) with many
functional groups such as –O–, –OH, and –COOH, which can form
complexes with metal ions, are used to remove heavy metal ions.
(a) The synthesis and application for removing Cr6+of MCGNs. (b) The comparison of adsorption mechanisms on GO and MCGN
Schematic illustration of silanization of Graphene
Anti-biofouling polymeric coatings for polyamide (PA) thin film composite (TFC) reverse osmosis (RO) (PA – TFC – RO) membranes was used to desalt water.
Poly ((2-methacryloxyethyl) trimethyl ammonium chloride) (MTAC) modified membranes were tested for their ability to permeate water and reject salt.
Poly(MTAC) modified membranes were found to exhibit a significant decrease in biofouling (93.2% after six days).
DEVELOPMENT OF POLYMERIC COATINGS TO PRODUCE ANTI-BIOFOULING WATER TREATMENT MEMBRANES
SEM images of (a) CuTCNQ, (b) AgTCNQ (d), CuTCNQF4, and (e) AgTCNQF4
ELECTROCHEMICAL FABRICATION OF CATALYTICALLY ACTIVE ORGANIC SEMICONDUCTORS WITH ENVIRONMENTAL APPLICATIONS
The metal nanoparticle metal-7,7,8,8-tetracyanoquinodimethane (MTCNQ) materials have properties that allow them to be employed in environmental remediation processes such as the removal of harmful Cr(VI) ions from aqueous solution using environmentally friendly reductants at room temperature with good reuse ability.
ION DETECTION USING POLYMER FUNCTIONALIZED ALGAN/GAN TRANSISTOR DEVICES WITHOUT A REFERENCE ELECTRODE
AlGaN/GaN high electron mobility transistors (HEMTs) are the result of a 2-dimensional electron gas layer (2DEG) that forms at the AlGaN/GaN interface.
The conductivity of this 2DEG layer is sensitive to charges on the surface, thus forming the basis for an ion sensor.
For the first time that an AlGaN/GaN device without a reference electrode can be used as a Nitrate Sensor with the appropriate ion selective membrane.
ULTRA-POROUS MATERIALS FOR GAS SEPARATION AND STORAGE APPLICATIONS
This presentation highlighted the recent experimental and
theoretical discoveries in the areas of H2, CH4 and CO2 storage plus
separations using ultra porous materials like Porous Aromatic
Frameworks (PAFs) and Metal-Organic Frameworks (MOFs).
Atomistic representation of (a) PAF-303 and (b) PAF-304 impregnated with Li6C60. The PAF unit cell is highlighted in red, and Li6C60 is highlighted in blue (lithium) and green (carbon).
(a) Hydrogen production and storage by renewable resource.(b) hydrogen storage in metal doped carbon nanotubes
GRAPHENE OXIDE ENCAPSULATION OF BACTERIA USING VORTEX FLUIDS
There is increasing research interest in hybrid bio-nano materials, for example in the hybridization of bacteria with nanomaterials. Also of interest, is to develop economically efficient and environmentally friendly processing for sustainable technologies for the future.
A Vortex Fluidic Device (VFD) allows rapid micro-mixing of reagents within thin films in a rapidly rotating tube, and we have used the microfluidic device to prepare multilayer graphene-algae and graphene oxide (GO)-algae hybrid materials. In this study we report on the wrapping of bacteria Staphylococcus aureus and Rhodococcus opacus with GO sheets using the VFD.
GO wrapped bacteria using a VFD
SCALABLE CONTROL OF REACTIONS USING VORTEX FLUIDICS
Flow chemistry offers scope for incorporating scalability at the inception of the science, as part of the drive towards developing more benign technology, high in green chemistry metrics. There is also the potential for moving beyond diffusion control, in operating under turbulent flow regimes.
A vortex fluidic device (VFD) generates dynamic thin films with intense shear, with the microfluidic platform being distinctly different to conventional channel based microfluidics which usually operate under laminar flow conditions.
We have established that the VFD has application in controlling chemical reactivity and selectivity which is at the core of gaining access to new compounds and materials.
Vortex fluidic device (VFD)
Vortex fluidic device (VFD)
Theme 4: Chemical Health and Safety
MODIFIED CLAYS AS EFFECTIVE ADSORBENTS FOR REMOVAL OF WATER CONTAMINANTS
Naturally occurring clay minerals have been suggested as environmentally friendly adsorbents due to their unique features:
(i) High cation exchange capacity (CEC). (ii) Swelling properties.(iii) High surface areas. For example, montmorillonite (MMT) is
readily available in several countries, and its use as an adsorbent for the environmental protection appears to be economically feasible.
MMT is hydrophilic and unsuitable for the removal of organic contaminants. When its permanent negatively charged surface is modified with quaternary ammonium cations (QACs), it is converted to a hydrophobic organoclay that can attract organic pollutants.
RECENT ADVANCES IN CONTAMINATED SITES REMEDIATION: GREEN AND NANO-REMEDIATION TECHNOLOGIES Contaminated sites can pose significant risks to human
health and the wider environment, and the costs of cleaning up contaminated sites are enormous. The US EPA estimated in 2004 that over the following 30 years, national clean-up costs could reach $250 billion, while the estimate for Europe is around EUR 6 billion.
As recently as the mid-1990s the most common remediation strategy merely shifted the problem to later generations by excavation and transport of contaminated material to landfill sites (‘dig and dump’). This approach is also ineffective once contaminants reach groundwater and are transported away from the source.
Over the past decade, the focus has shifted to technologies that are sustainable and green (i.e. environmentally beneficial in their application as well as their outcomes), with nano-remediation also becoming more widespread.
In situ groundwater treatment by the hybrid fibre-optic photocatalytic system
CHEMICAL INVENTORY MANAGEMENT: IMPLEMENTING A UNIVERSITY WIDE SYSTEM AT UNSW
University of New South Wales (UNSW) is in 2014 implementing a new system for the management of hazardous materials and dangerous goods (HMDG).
The system Enterprise Reagent Manager (ERM) has been developed by a US based company called SciQuest and is being used at 70 Universities worldwide mostly in the United States and Europe. It is used for tracking chemicals from purchasing to disposal.
This system will replace an older legacy system for Chemical ordering system inventory (COSI)·
The key component of this is SciQuest-ERM. This software will:
Manage our chemical and other HMDG inventory in real time with the aid of barcode scanners in each lab.
Allow us to simultaneously search across all UNSW labs, our internal stores and the catalogues of our key external vendors of HMDG's.
Manage our external ordering of HMDG's, including safety warnings and approvals.
Manage purchasing from our internal store.
Theme 6: Chemical Analysis and Sensing
A HYBRID BIONANOSTRUCTURE OF GOLD NANOPARTICLES AND MULTIWALLED CARBON NANOTUBES WITH ENZYMES FOR ULTRASENSITIVE DETECTION OF CHOLESTEROL
There has been an increasing interest in recent years in the synthesis and utilization of polymer nanocomposites for fabrication of biosensors.
A novel strategy for co-entrapment of MWCNTs and AuNPs in polypyrrole (PPy) films and for utilization of their synergistic effect for fabrication of ultrasensitive cholesterol amperometric nanobiosensors for detection of free and total cholesterol in blood samples.
MOBILE PHONE READABLE PAPER FLUIDIC ELECTRO- CHEMILUMINESCENCE SENSORS
Microfluidic devices :Very small quantities of sample, Limit reagent use, High resolution and sensitivity, Low cost, Short times.
What is microfluidics? “It is the science and technology of systems that process or manipulate small (10-9 to 10-18 liters) amounts of fluids, using channels with dimensions of tens to hundreds of micrometres.”
Glucose assay reagen
ts
Color: from colorless to
brown (I− to I2)
Protein assay
reagents
Color: from yellow to blue(NPB of TBPB
to proteins. )
Microfluidic paper-based analytical devices (μPADs)
μPADs for analysis of glucose and BSA (bovine serum albumin) protein in urine.
Microfluidic Sensor
The electrogenerated chemiluminescence (ECL) is a phenomenon that a light emission arises from the high energy electron transfer reaction between electrogenerated species, which is usually accompanied with the regeneration of emitting species.
A chemiluminescence reaction initiated and controlled by the application of an electrochemical potential.
ECL reagent: Tris(2,2’-bipyridyl)ruthenium(II), (Ru(bpy)3
2+) Good stability and ECL efficiency in aqueous
media, Favorable electrochemical properties, Compatibility with a wide range of analytes.
Electrogenerated Chemiluminescence (ECL)
Screen-printed Electrodes (SPEs)
Screen-printed Carbon Electrodes
http://www.dropsens.com/en/screen_printed_electrodes_pag.html
Calibration curve between 0.5 mM and 20 mM for 2-(dibutylamino)ethanol (DBAE) using paper microfluidic ECL sensor with mobile camera phone as the detector. The magnitude of the ECL signal is proportional to the intensity of the red pixels in the digital image.
GREEN CHEMISTRY DEFINITION
Green Chemistry is the utilization of a set of principles that reduces or eliminates
the use or generation of hazardous substances in the design, manufacture and
application of chemical products *.
GREEN CHEMISTRY IS ABOUT• Waste Minimisation at Source• Use of Catalysts in place of Reagents• Using Non-Toxic Reagents• Use of Renewable Resources• Improved Atom Efficiency• Use of Solvent Free or Recyclable Environmentally Benign Solvent systems
* Green Chemistry Theory & Practice, P T Anastas & J C Warner, Oxford University Press 1998
1. Prevention
It is better to prevent waste than to treat or clean up waste after it has been created.
2. Atom Economy Synthetic methods should be designed to maximise the incorporation of all materials used in the process into the final product.
3. Less Hazardous Chemical Synthesis Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to people or the environment.
4. Designing Safer Chemicals Chemical products should be designed to effect their desired function while minimising their toxicity.
5. Safer Solvents and Auxiliaries The use of auxiliary substances (e.g., solvents or separation agents) should be made unnecessary whenever possible and innocuous when used.
6. Design for Energy Efficiency
Energy requirements of chemical processes should be recognised for their environmental and economic impacts and should be minimised. If possible, synthetic methods should be conducted at ambient temperature and pressure.
The 12 Principles of Green Chemistry (1-6)
The 12 Principles of Green Chemistry (7-12)
7 Use of Renewable FeedstocksA raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable.
8 Reduce DerivativesUnnecessary derivatization (use of blocking groups, protection/de-protection, and temporary modification of physical/chemical processes) should be minimised or avoided if possible, because such steps require additional reagents and can generate waste.
9 CatalysisCatalytic reagents (as selective as possible) are superior to stoichiometric reagents.
10 Design for DegradationChemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment.
11 Real-time Analysis for Pollution PreventionAnalytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.
12 Inherently Safer Chemistry for Accident PreventionSubstances and the form of a substance used in a chemical process should be chosen to minimise the potential for chemical accidents, including releases, explosions, and fires.
Less Hazardous Chemical Synthesis
Disadvantages phosgene is highly toxic, corrosive requires large amount of CH2Cl2 polycarbonate contaminated with Cl impurities
OH OHCl Cl
O
+NaOH
O O *
O
* n
Polycarbonate Synthesis: Phosgene Process
Less Hazardous Chemical Synthesis
OH OH
+ O O *
O
* n
O O
O
Advantages diphenylcarbonate synthesized without phosgene eliminates use of CH2Cl2 higher-quality polycarbonates
Polycarbonate Synthesis: Solid-State Process
Polymers from Renewable Resources:Poly(lactic acid)
http://www.natureworksllc.com/corporate/nw_pack_home.asp
Raw Materials from Renewable Resources:The BioFine Process
O
HO
O
Paper mill sludge
Levulinic acid
Municipal solid wasteand waste paper
Agricultural residues,Waste wood
Green Chemistry Challenge Award1999 Small Business Award
Levulinic acid as a platform chemical
O
HO
O
O
H2NOH
O
O
HO
DALA (-amino levulinic acid)(non-toxic, biodegradable herbicide)
O
HO
O
OH
C
CH3
CH2
CH2
C
O
OHHO
Diphenolic acid
Acrylic acidSuccinic acid
O
THF
O
MTHF(fuel additive)
HOOH
butanediol
OO
gamma butyrolactone
Green Chemistry Is About...
Waste
Materials
Hazard
Environmental Impact
COST
Risk
Energy
Catalysis
Process
Intensification
Separation
Processes
Energy
Efficiency
Solvent
Replacement
Safer Reactions
& Reagents
Use of
Renewable
Feedstocks
Waste
Minimisation
Some Aspects of Green Chemistry
Green
Chemistry
Multidimensionality in Gas Chromatography
A typical multidimensional separation GC system, combined with multidimensional analysis using spectroscopic detection
CRYSTALLINE SPONGE METHOD: X-RAY STRUCTURE ANALYSIS WITHOUT CRYSTALLIZATION
The Epsilon 3XLE handles a wide variety of sample types, including solids, pressed and loose powders, liquids and filters. It performs non-destructive quantitative analysis of elements from carbon (C) to americium (Am), in concentrations from 100% down to sub-ppm levels, on samples weighing anything from a few milligrams to kilograms.
XRF- Ready for any sample type
Dr Ahmed Khudhair Hassan would like to thank the Chemical Security Engagement Program (CSP) sponsored by the Department of State of the USA and managed by the CRDF Global for all the financial and administrative support.
Acknowledgments
THANK YOU FOR YOUR
ATTENTION