Polymers as Organizers - Renewable Bioproducts Institute

Polymers as Organizers--Russo
Biopolymers assume structural and functional roles in nature and in
commercial applications. The ability to organize other molecules is an
underutilized function that will be discussed in the context of two different
biopolymers. Cellulose nanocrystals (CNCs) align in parallel fashion to
produce liquid crystals. The potential exists for semiconducting polymers to
follow CNCs into the aligned state, thereby leading to materials with
enhanced optoelectronic performance. Having achieved their organizational
objective, the CNCs will remain to confer mechanical strength. A different
route to organization uses biosurfactant proteins known as hydrophobins.
Produced by fungi in the forest and on the farm, these small proteins
assemble into strong films that can encapsulate many fluids, including
semiconducting polymer solutions. Improved alignment and attendant
performance gains may be realized as the solvent leaks out of the capsules,
progressively concentrating the polymers into waterborne latex particles for
easy and environmentally friendly application.
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Brad Blalock
Michael Pham
Wayne Huberty
Melissa Collins
Javoris Hollingsworth
Francisco Hung
Yuwu Chen
Qinglin Wu
Polymers as Organizers
Paul Russo
[email protected]
Xujun Zhang
Cornelia Rosu
Elsa Reichmanis
Jinxin Fu
Bailey Risteen
Drew Gorman
Shelley Anna
Lynn Walker
Stephanie Kirby
Executive Conference
Renewable Bioproducts Institute
Georgia Institute of Technology
Tuesday, April 5, 2016
Georgia Tech Foundation and the Hightower Family
Renewable Bioproducts Institute PSE Fellowship
Gulf of Mexico Research Institute
LSU Office of Research
Brandeis MRSEC: Zvonimir Dogic, Seth Fraden, Tim Sanchez
LSU Foundation and the Daniels Family
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Some pairings are particularly powerful organizers.
Pairing #1: Cellulose
nanocrystals and
polythiophenes.
CNC
Fleming, Gray, Prasannan & Matthews
JACS 2000 (10.1021/ja000764e)
Sigourney Weaver as Gatekeeper
Rick Moranis as Keymaster
(Ghostbusters, 1989)
Together they organized the spirit world.
P3HT in pi-stacks
Maybe together they
can organize electron flow.
Spano & Silva
Annu.Rev.P.Chem. 2014
10.1146/annurev-physchem-040513-103639
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https://pbs.twimg.com/media/CV3iojbWsAE6tsS.jpg
We are having trouble with hydrocarbon-soluble CNCs, so we
have begun with this water-soluble semiconducting polymer.
M=16,000 g/mol polymer
Mo = 206 g/mol monomer
N  80
L  300 Å  30 nm
poly[3-(potassium-4-butanoate)thiophene-2,5-diyl]
4`
Mix 3 mg/mL PPBT in aqueous CNCs at 5%
After one week, liquid crystal domains appear under
Polarized Optical Microscopy.
P
P
A
A
3 mg/mL PPBT + 5 wt% CNCs
Average Pitch = 4.36 ± 0.27 μm
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Water-soluble PPBT polythiophene does not
alter CNC phase transition points.
X marks the spots when we mixed 3 mg/mL PPBT (structure below)
with varying amounts of CNCs (0, 2, 5, 8 wt%)`
x
Volume Fraction Anisotropic
Phase
1
0.8
0.6
0.4
0.2
0
x
x
0
1
x
2
3
4
5
6
7
8
Total CNC Concentration (wt%)
9
10
poly[3-(potassium-4-butanoate)thiophene-2,5-diyl]
6`
Solution UV-Vis shows increased ordering
with addition of CNCs.
3 mg/mL PPBT
A0-1 (540 nm)
A0-0 (578 nm)
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Same thing at higher PPBT loading.
5 mg/mL PPBT
A0-1 (540 nm)
A0-0 (578 nm)
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A model by Spano correlates increase in effective conjugation
length of the semiconducting polymer with addition of CNCs.
A0-0
A0-1
æ 1- 0.24W / E ö
p
÷÷
= çç
è 1+ 0.73W / E p ø
2
W = free exciton bandwidth
Ep = energy of main intramolecular transition
(0.18 eV for symmetric
C=C stretch = 4.5 X kBT)
** Decrease in W represents an increase in conjugation length**
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PSE Fellow Bailey Risteen’s future work:
 Time dependence of PPBT/CNC pitch,
compare with pure CNC pitch
 Depletion studies: maintain CNC wt% but
increase PPBT concentration to see if it
induces LC phase
 UV-Vis of PPBT/CNC films (spin coating,
blade coating)
 Make/test devices?
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Part I Conclusion:
It does seem that CNC Liquid Crystals improve alignment of PPBT.
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Some pairings are so crazy they just have to be tried.
Pairing #2: Fungal
hydrophobins and P3HT.
Hydrophobin
HFBII
The Adobe
Saturday Night Live (1986)
$179
“The Sassy New Mexican Import that’s Made out of Clay”
“The Combination of German Engineering and Mexican Know-How”
Together they re-organized the global economy.
P3HT in pi-stacks
Spano & Silva
Annu.Rev.P.Chem. 2014
10.1146/annurev-physchem-040513-103639
Again, the idea is to organize electron flow.
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https://pbs.twimg.com/media/CV3iojbWsAE6tsS.jpg
Hydrophobins are nature’s most surface-active
proteins.
↓Sequence for Cerato ulmin
Met. Gln. Phe.Ser. Ile. Ala. Thr. Ile. Ala. Leu. Phe. Leu. Ser.Ser. Ala. Met. Ala. Ala.
Pro. Tyr. Ser. Gly. Asn. Ser. Asn.* Ser. Asp. Ser. Tyr. Asp. Pro. Cys32. Thr. Gly.
Leu. Leu. Gln. Lys. Ser. Pro. Gln. Cys42. Cys43. Asn. Thr. Asp. Ile. Leu. Gly. Val.
Ala. Asn. Leu. Asp. Cys55. His. Gly. Pro. Pro. Ser. Val. Pro. Thr. Ser. Pro. Ser. Gln.
Phe. Gln. Ala. Ser. Cys72. Val. Ala. Asp. Gly. Gly. Arg. Ser. Ala. Arg. Cys82. Cys83.
Thr. Leu. Ser. Leu. Leu. Gly. Leu. Ala. Leu. Val. Cys94. Thr. Asp. Pro. Val. Gly. Ile.
Nature’s Janus particle.
Hydrophobin HFBII
green = hydrophobic
Temple B, Horgen PA
Biological roles for cerato-ulmin, a hydrophobin secreted by the elm pathogens, Ophiostoma ulmi and O-novo-ulmi
Mycol 2000;92:1-9
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Hydrophobins are secreted by fungi; no one knows why, but yesterday here at
RBI Gregg Beckham from NREL demonstrated that fungal enzymes have a role in
converting biomass. Those fungi will also be producing hydrophobins.
A
Edible ‘shrooms in a Manhattan Market
Giant mushroom found under
a tree at Georgia Tech!!!
Aspergillus niger
photo is 5 inches (12.5 cm) across.
http://microculture.tumblr.com/post/919722584/mycology-a-fungus-as-a-living-factory-the
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Hydrophobins have 8 crosslinked cysteine residues.
L-Cysteine:
virtually
insoluble
slightly more
soluble
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The particular hydrophobin called cerato ulmin has been
implicated in the death of American elm trees (Dutch elm disease)
Dutch elm disease a.k.a. Elm wilt
Thousands of these beautiful shade trees die each year.
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CU traps air and oil into stable (but not equilibrium)
cylindrical structures.
Fibrillar air bubbles: rocking
Half-moon polymer gel drops (PSLG/dodecane): Sonication
Tubular oil blobs: rocking
Russo Lab
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Sample prep determines the shape of the bubbles.
CU aqueous solution
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In this video, cylindrical bubbles fatten under tension, then go
spherical. They crinkle on reducing the pressure.
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A slide showing unusual
structures was removed here:
contact
[email protected]
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If CU captures air, it should
capture oils.
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CU Biofilms must be strong! Let’s begin with how
surface tension is determined.
Single hydrophobin
=
Grey: Hydrophilic patch
Green: Hydrophobic patch
Pressure
Radius
Aqueous phase
air
Air or Oil
Schematics of CU molecules at air/water
or oil/water interface at a capillary tip.
Surface tension
P1: PT (transducer)
P2: PH (hydrostatic)
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In this case, the microtensiometer is not oscillating…just watching bubble
radius with time. CU takes about one hour to lower air/water surface
tension from 72.8 mN/m to 53 mN/m at 1 mg/mL .
Single hydrophobin
80
Surface tension
Early rinse with DI H2O
76
75
Grey: Hydrophilic patch
Green: Hydrophobic patch
 / mN/m
74
 / mN/m
70
=
72
Aqueous phase
65
70
0
800
Time / s
1600
60
Air or Oil
55
50
0
1000
2000
Time / s
3000
4000
Schematics of CU molecules
at air/water or oil/water
interface at a capillary tip.
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Walker-Anna dynamic tensiometer oscillates bubble.
Carnegie-Mellon University
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The CU membrane at air/water interface becomes solid-like and more rigid.
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66
46
64
44
62
42
60
40
58
38
56
1800
1820
1840
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70
60
Time (s)
70
50
60
40
50
0
500
1000
Time (s)
1500
30
2000
-1
-1
E' or E" / mN·m |E| / mN·m
80
68
Radius (mm)
 (mN/m)
Surface tension
Radius
 (mN/m)
0
80
Radius (mm)
90
700
1400
700
1400
|E|
750
500
250
0
E'
E"
750
500
250
0

 / °
13
0
-13
where f is the phase difference between the area and
surface stress, E′ is the in-phase (elastic) contribution,
and E″ is the out-of-phase (viscous) contribution.
0
Time / s
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How do cylindrical bubbles form?
We don’t know, but….
Bing
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We can polymerize styrene in CU blobs.
CU hydrophobin aqueous solution
Styrene
Azobisisobutyronitrile (AIBN)
C18 coated SiO2 tracer particles
70 oC, 14h
scale bars: 200 mm
before
after
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Biofilm bag (it’s a biomaterial!) securely
contains spill oil.
Macondo spill oil
Magnetic field is applied
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Hydrophobins have captured rodlike poly(3-hexylthiophene) semiconducting
polymer in benzene. What happens to the polymer if the solvent evaporates?
100 mm
100 mm
epifluorescence
brightfield
http://www.sigmaaldrich.com/catalog/product/aldrich/445703?lang=en&region=US
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Control experiment: Toluene escapes with time.
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Click to add results, patents, $$$
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We have a little bit more complete results on NON-volatile
solvents, such as trichlorobenzene (TCB).
Protein-Assisted Assembly of π-Conjugated Polymers
Cornelia Rosu, Nabil Kleinhenz, Dalsu Choi, Christopher J. Tassone, Xujun Zhang,
Jung Ok Park, Mohan Srinivasarao, Paul S. Russo, and Elsa Reichmanis
Chem. Mater., 2016, 28 (2), pp 573–582
DOI: 10.1021/acs.chemmater.5b04192
Huge 640-nm shoulder bespeaks exceptional alignment.
It’s huge!
Protein-Assisted Assembly of π-Conjugated Polymers
Cornelia Rosu, Nabil Kleinhenz, Dalsu Choi, Christopher J. Tassone, Xujun Zhang,
Jung Ok Park, Mohan Srinivasarao, Paul S. Russo, and Elsa Reichmanis
Chem. Mater., 2016, 28 (2), pp 573–582
DOI: 10.1021/acs.chemmater.5b04192
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Grazing incidence SAXS confirms excellent alignment.
Protein-Assisted Assembly of π-Conjugated Polymers
Cornelia Rosu, et al. DOI: 10.1021/acs.chemmater.5b04192
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In time, blobs evolve into dendritic structures that “bleb out” bits of
CU-encapsulated P3HT…a latex-like route to processing P3HT?
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Protein-Assisted Assembly of π-Conjugated Polymers
Cornelia Rosu, et al.
DOI: 10.1021/acs.chemmater.5b04192
Part II Conclusion:
Again, we see an altogether different biopolymer
organize a different functional polymer, P3HT.
We are chasing a feather, and it seems to be leading somewhere.
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CONTACT ME FOR A COPY
[email protected]
Not for Commercial Use
For Additional GT Artwork
Xiuxiu Yuan
[email protected]
Xiuxiu Yuan
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