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Sidney J.L. Ribeiro Institute of Chemistry
São Paulo State University -UNESP
Araraquara, São Paulo
Brazil
Green Multifunctional
Organic-Inorganic Hybrids
based on Biopolymers and
Recyclable materials
Brazilian ChemComm Symposium
Chemistry and Sustainable Energy
University of the State of São Paulo
UNESP
32 schools / 23 cities
169 undergraduate programs
35,000 undergraduate students
10,000 graduate students
9,000 Diplomas per year
3,400 Academic staff (95% PhDs – 87% full
time)
7,000 Non academic staff
270KM
ARARAQUARA
“City of the Sunshine”
“World capital of oranges”
200.000 inhabitants
18th in São Paulo
1st in quality of life
Undergraduate and Graduate Chemistry Studies 80 prof/res, 1000 undergaduated students, 500 graduated students (>1000 theses)
Biomaterials
Photonics
Energy
Biofuels
Natural products
Biochemistry
Ceramics, glasses
Nanotechnology Biophotonics
Materials science
Catalysis
Our Institute..
Laboratory of Photonic Materials
7 pos-docs, 10 grad- std, 10 undergrad. std
Sidney J.L. Ribeiro
Full Professor, Researcher Class 1A CNPq
Member of the Academy of Sciences of the
State of SP
Younes Messaddeq
On leave from UNESP
Canada Excelence Research Chair
PhD- Univ. Rennes- France
Development of novel photonic materials
Health Agriculture Environment Telecom Education
Tecnology Transfer
Science dissemination
electronics Opto-electronics Photonics
20th century 21th century
Photonics- photons as information carriers
Photophone
1880
Lasers
Optical fibers
Efficient detectors
modulators
Optical fibers
Materials for Photonics
How new are the “state of the art materials” we are using?
Lycurgus cup
"the most spectacular glass of the period,
fittingly decorated, which we know to have existed"
Venetian
red glasses
Can we control the light by using metal NP´s in order
to enhance Si solar cells efficiency??
Roman and Venetian Glasses
Au/Ag nanoparticles
Absorption and scattering effects
in the control of the colors we see
Maya blue
8th to15th centuries
Can we enhance resistance to weathering of
organic devices (OLEDs, solar cells, etc??)
Materials for Photonics
How new are the “state of the art” materials we are using?
1st Organic-Inorganic Hybrid
(indigo blue dye + clays)
Amazing resistance to weathering
over more than 15 centuries!!!
We still don´t know how Maya artists prepared their blue pigment!!
Down-converters Up-converters
Summary-I
Buterflies
Optical properties
Cellulose from Bacteria
Gluconacetobacter xylinus
Silk based materials
Bombix mori
Green materials for Photonics
Summary- II
Down-converters Up-converters
Can we enhance the efficiency of Si photovoltaic cells?
Chem.Rev. 2004, 304, 139
Upconversion and anti-Stokes Process with f and d ions in Solids
F François Auzel
UP-CONVERTERS
Up-conversion
Si
Up-converter
mirror
Surface plasmons from metal NP´s can enhance luminescence
(similar to SERS)
2012
Ce3+-Yb3+ Tb3+-Yb3+ Pr3+-Yb3+
Down-conversion
Down-converter
Si
Down-conversion or Quantum Cutting
2 IR emited photons for 1 UV-VIS absorbed photon
200% quantum yield
NRD are lower in
low-phonon hosts
Silica- 1100 cm-1
Fluorides- 500-600 cm-1
Fluoride Glasses- Low phonon glasses
Two important optical properties governed by the phonon energy of the host:
Fluoroindate glasses InF3-BaF2-SrF2 –ZnF2
Pr3+-Yb3+
Pr3+ emission as a function of [Yb3+]
Energy transfer Pr3+Yb3+
Energy transfer Pr3+Yb3+
Pr3+ decay time as a function of [Yb3+]
IR emission
Energy transfer Pr3+Yb3+
Front face illumination
Rear illumination
1 m
Bragg diffraction of visible light
PHOTONIC CRYSTALS
Solar Cells and photocatalysts to yield hydrogen Significant strategies for utilizing clean and sustainable solar energy
to replace conventional fossil fuels.
Light manipulation and harvesting abilities play a dominant role in the
conversion efficiencies.
Butterflies inspiring new solar cells and sunlight water-splitting catalysts
Nipple arrays in butterfly compound eyes
Ridge and hole arrays
Photonic crystal structures in butterfly wings
SWG- subwavelength gratings
Cellulose produced by bacteria
All requirements from "green" approaches;
Excelent perspective for new "green polymers";
Cellulose
Most abundant polymer on earth;
Fantastic rich chemistry
Cellulose is:
scientifically interesting,
eco-friendly material,
green,
biocompatible,
obtained from renewable sources,
recyclable...
BUT, YOU NEED TO BE
FAR, FAR, AWAY
FROM
THE CELLULOSE PRODUCTION PLANT!!!
CELLULOSE IS OK!!
Argentina
Uruguay
International Conflit- since 2006 in International Court, The Hague
Where to install a cellulose plant??
http://en.wikipedia.org/wiki/Pulp_mill_dispute
Uruguay river
“Potentially negative environmental, social, and economic impacts
that the installation of cellulose plants on the margins of the
Uruguay River can have for the local residents of the area involved”
The problem
28 July 2011
binational commission CARU (Spanish: Comisión Administradora del Río Uruguay)
monitoring the river pollution - official end of the dispute
Fortunately, plants are not the only cellulose source available...
Bacteria
algae
fungi
Gluconacetobacter xylinus
cellulose
fibrils
ribons- tight assembly of fibrils
BACTERIAL CELLULOSE
or
BIOCELLULOSE
SUGAR
Bacterial cellulose (biocellulose) hydrogel
-high mechanical resistance
-98% water- 2% pure cellulose
-3D nanometric network
-open structure, easy to functionalize
Biocellulose electrospun
poly(styrene-co-dimethylsiloxane)
50 m 1 m
The nanometric structure leads to better
chemical and mechanical properties
BC fibrils - (1/100) of those from plants cellulose
W6+ W5+
Phosphotungstic acid- PWA
chiral nematic
phase
cellulose
reflective films
Bombix mori
SILK PRODUCERS
Bombyx mori
"Silk spinners"
Fibroin-based optical materials
"Silk Bio-Optronics"
mulberry
protein-based
materials
"Reverse engineering"
"Silk valley"
Japanese immigration
to Brazil- 1920´s
Biggest production in the Occident
In the world- 3rd place (after China and India)
The silk road
SILK= FIBROIN + SERICIN
glue-like protein
fibrous
protein
composed
of -sheets
silk cocoon silk yarn
Fibroin solution
extraction
of sericin
Na2CO3
Fibroin
dissolution
CaCl2
water
dialysis
8%wt
50% yield 2 days
Magnetic sponges
[fibroin]
T
2Fe3+(aq) + Fe2+(aq) + 8OH-(aq) Fe3O4(s) +
4H2O(l)
Inverse spinel fcc structure
FeO.Fe2O3
Fe3O4(s) g-
Fe2O3
O2
Superparamagnetic maghemite nanoparticles
Magnetite or Iron Ferrite
Maghemite Inverse spinel fcc structure
g-Fe2O3
Ionic Ferrofluid Colloidal stability by oleic acid
Coprecipitation method
Maghemita (g-Fe2O3)
Silk Fibroin Solution
Silk Ferrogels
"magnetic squeezing"
M.Zrinyi et al., Polymer Gels and Networks (1997) 5, 415
Luminescent diffraction gratings
Silk replicas
Master
(commercial DVD)
Fibroin solution +
Eu3+ complex or
Rhodamine 6G
poured onto the master and dried
Luminescent silk replica
Track Pitch- CD- 0.740 m DVD- 1.6 m
UV pointer laser Green pointer laser
Eu3+ emission
Conventional laser
1916 - Einstein
1958 Schawlow – Townes
1960 Maiman
Spontaneous
emission
Stimulated emission
Cavity
modes
photon
Narrow linewidth
Long coherence time
Large spatial coherence
Directionality
speckle beam profile
Cid Araujo- Recife- Brazil
Rhodamine with TiO2
nanoparticles
emission
thresholdlaser
paint
fluorescence
Multiple scattering inside the cell -
stimulated emission
Lawandy et al. Nature (1994) Laser paint – Random lasers
D.S.Wiersma, Nature Physics 4, 359, 2008
Random Laser
“laser paint” or “photon bomb”
Large linewidth
Short coherence time
Small spatial coherence
NO speckle Cid Araujo- Recife- Brazil
Random lasers- a new kind of light source
for imaging.
High photon degeneracy/spectral radiance
and low spatial coherence
It is the ideal combination
for full-field imaging
Random lasers produce spekle-free images
Random lasers- a new kind of light source
for imaging.
High photon degeneracy/spectral radiance
and low spatial coherence
It is the ideal combination
for full-field imaging
Random lasers produce spekle-free images
http://www.cstf.kyushu-u.ac.jp/~adachilab/images/dfb.jpg
DFB (Distributed Feedback) or DBR (Distributed Bragg Reflector)
DFB + Random lasers
Fibroin Bragg gratings
doped with rhodamine 6G
Silica (Stober) particles (scatterers)
0 1 2 3 4 5
0
100
200
300
400
without silica NPs
Pe
ak in
ten
sity (
arb
. u
nits)
Pumping energy (mJ/pulse)
1.7 × 1010
cm-3
3.5 × 1010
cm-3
8.8 × 1010
cm-3
(a)
0,1 1
0
10
20
30
40
50
60
without silica NPs
Lin
ew
idth
(n
m)
Pumping energy (mJ/pulse)
1.7 × 1010
cm-3
3.5 × 10
10 cm
-3
8.8 × 1010
cm-3
DFB-Random lasers
F.G.Omenetto, D.L.Kaplan
New Opportunities for an Ancient Material, Science (2010) 329, 528
-Younes Messaddeq (UNESP e COPL-Univ. Laval- Quebec-Canada)
-Luis D. Carlos, Rute A.S. Ferreira, Paulo S. André- Aveiro, Portugal
-Verónica Zéa-Bermudez- Trás-os-Montes, Portugal
-Jeannette Dexpert-Ghys, Marc Verelst, Marie-Joëlle Menu- Toulouse, France
-Cid B. Araújo, Anderson Gomes, Oscar L. Malta, Gilberto Sá- Recife
-Lauro J.Q. Maia- Goiânia
-Rogéria R. Gonçalves, J.Maurício A. Caiut, Antonio C. Tedesco- Ribeirão Preto
-Marco Cremona, Karim Dahmouche, Bluma G. Soares- Rio de Janeiro
-Luiz Fernando Cappa de Oliveira, Flavia C. Machado,
Marcone AL Oliviera- Juiz de Fora
-Hermi F. Brito, Maria Cláudia F. C. Felinto- São Paulo
-Marcos Antonio Couto dos Santos- Aracajú
-Luiz A. O. Nunes- São Carlos
Acknowledgements
Nanobiotec
Capes, Brazil
Danilo Sybele Edison Silvia Eliane César
Maristela Elaine Adriana Denise
Hernane Tâmara
Rafael Andréa Robson Karina Leandro Daniele Molíria Rafael
Carolina Marianas Laís Larissa Gustavo
Marli
International Partnerships
Castor Oil- a multifunctional “green precursor” in materials science
12-hydroxy-(cis)- 9-octadecenoic acid
Ricinoleic acid
4
5 7
6 8
9
10
11 12 13
14 15
16 17
18
3
2 1
Polymers, cosmetics, coatings, resins, biodiesel…
Castor oil
Ricinus Communis ("Castor plant")
90% of hydroxy, unsaturated C18 fatty acid
ORGANIC-INORGANIC HYBRIDS
Organic counterpart
Inorganic counterpart
Hybrids Materials
Composites at the molecular scale
4
5 7
6 8
9 10
11 12 13
14 15
16 17
18
3
2 1
Amidosil
Synthesis of the monoamidosil precursor
Ricinoleic acid APTS
Water (hydrolysis and condensation)
Amidosil hybrid
Amide formation confirmed by FTIR and NMR
Eu3+ compounds
Strong red light emitters
under excitation of
light, high energy radiation,
electric field, mechanical stress, etc.
The spectroscopic study
allows one to obtain
important information
on the structure and nature
of the host
Structural probe for:
-new amorphous or crystalline
hosts
-compounds of spectroscopically
inert ions like Ca2+
Luminescent materials
Lasers, optical amplifiers,
Labels for imaging and dignostics
sensors, etc
Adv.Mater. 2009, 21, 509
7F6
7F2
7F1
7F0
7F5
7F4
7F3
5D0
Luminescence excitation
ff transitions - low absorption coeficient (10)
dd transitions - 1000
organic molecules - 106
Organic Ligands
Enhancement of the light absorption
efficiency,
followed by energy transfer to Eu3+,
and enhancement of the light output
Antenna effect
ET
Energy levels
Ligand Eu3+
tta- [Eu(tta)3(H2O)2
+
Sample under UV illumination
350 400 450 500 550 600 650 7000,0
0,5
1,0
exc300nm
exc
330nm
exc
360nm
exc
380nm
exc
400nm
exc
430nm
exc
460nm
Inte
nsid
ad
e (
u.a
.)
Comprimento de onda (nm)
Luminescence
Pure hybrid
Broad band shifting with the excitation wavelength
Electron-hole recombinations
550 600 650 700
In
ten
sid
ade
(u. a.
)
Comprimento de onda (nm)
250 300 350 400 450 500 550 600
In
ten
sid
ade
(u. a.
)
Comprimento de onda (nm)
[Eu(TTA)3(H2O)2]
em = 612nm
exc = 350nm
Excitation Emission
5D0 quantum efficiency:
(EXP/RAD)=22%
7FJ
5D0
kRAD kNRAD- non-radiative
250 300 350 400 450 500 550 600
Wavelength (nm)
Excitation- Antenna effect enhanced in
the amidosil host (water molecules are substituted by functional groups from the host)
Host+tta ligand
Eu3+ ff line
Amidosil+[Eu(TTA)3(H2O)2]
5D0 quantum efficiency:
50% Increase due to interactions with the host
(water molecules are substituted by
functional groups from the host)
no broad band
detected
Amidosil+[Eu(TTA)3(H2O)2]
International Partnerships
ABWA- artificial butterfly wings architecture
