polymers as organizers--russo
TRANSCRIPT
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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.
Polymers as Organizers
Paul Russo
Executive Conference
Renewable Bioproducts Institute
Georgia Institute of Technology
Tuesday, April 5, 2016
Brad Blalock
Michael Pham
Wayne Huberty
Melissa Collins
Javoris Hollingsworth
Francisco Hung
Yuwu Chen
Qinglin Wu
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Elsa Reichmanis
Jinxin Fu
Bailey Risteen
Drew Gorman
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
Xujun Zhang
Cornelia Rosu
Shelley Anna
Lynn Walker
Stephanie Kirby
Some pairings are particularly powerful organizers.
Pairing #1: Cellulose nanocrystals and polythiophenes.
3https://pbs.twimg.com/media/CV3iojbWsAE6tsS.jpg
Sigourney Weaver as Gatekeeper
Rick Moranis as Keymaster
(Ghostbusters, 1989)
Together they organized the spirit world.
CNCFleming, Gray, Prasannan & Matthews
JACS 2000 (10.1021/ja000764e)
P3HT in pi-stacksSpano & Silva
Annu.Rev.P.Chem. 2014
10.1146/annurev-physchem-040513-103639
Maybe together they
can organize electron flow.
We are having trouble with hydrocarbon-soluble CNCs, so we have begun with this water-soluble semiconducting polymer.
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poly[3-(potassium-4-butanoate)thiophene-2,5-diyl]
M=16,000 g/mol polymer
Mo = 206 g/mol monomer
N 80
L 300 Å 30 nm
Mix 3 mg/mL PPBT in aqueous CNCs at 5%After one week, liquid crystal domains appear under Polarized Optical Microscopy.
3 mg/mL PPBT + 5 wt% CNCs
P
A
P
A
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Average Pitch = 4.36 ± 0.27 μm
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%)`
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0
0.2
0.4
0.6
0.8
1
0 1 2 3 4 5 6 7 8 9 10
Vo
lum
e F
ract
ion
An
iso
tro
pic
P
has
e
Total CNC Concentration (wt%)
xx
x
x
poly[3-(potassium-4-butanoate)thiophene-2,5-diyl]
A0-0 (578 nm)A0-1 (540 nm)
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3 mg/mL PPBT
Solution UV-Vis shows increased ordering
with addition of CNCs.
A0-0 (578 nm)A0-1 (540 nm)
8
5 mg/mL PPBT
Same thing at higher PPBT loading.
A model by Spano correlates increase in effective conjugation length of the semiconducting polymer with addition of CNCs.
A0-0
A0-1
=1- 0.24W / Ep
1+ 0.73W / Ep
æ
èçç
ö
ø÷÷
2
W = free exciton bandwidth
Ep = energy of main intra-
molecular 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.
Some pairings are so crazy they just have to be tried.
Pairing #2: Fungal hydrophobins and P3HT.
12https://pbs.twimg.com/media/CV3iojbWsAE6tsS.jpg
The AdobeSaturday 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.
Hydrophobin
HFBII
P3HT in pi-stacksSpano & Silva
Annu.Rev.P.Chem. 2014
10.1146/annurev-physchem-040513-103639
Again, the idea is to organize electron flow.
Hydrophobins are nature’s most surface-active proteins.
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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.
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
Hydrophobin HFBII
green = hydrophobic
↓Sequence for Cerato ulmin
Nature’s Janus particle.
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
14http://microculture.tumblr.com/post/919722584/mycology-a-fungus-as-a-living-factory-the
Aspergillus niger
photo is 5 inches (12.5 cm) across.
Edible ‘shrooms in a Manhattan Market
Giant mushroom found under
a tree at Georgia Tech!!!
Hydrophobins have 8 crosslinked cysteine residues.
L-Cysteine:
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slightly more
solublevirtually
insoluble
Dutch elm disease a.k.a. Elm wilt
Thousands of these beautiful shade trees die each year. 13
The particular hydrophobin called cerato ulmin has been
implicated in the death of American elm trees (Dutch elm disease)
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CU traps air and oil into stable (but not equilibrium) cylindrical structures.
Russo Lab 17
Fibrillar air bubbles: rocking
Tubular oil blobs: rocking
Half-moon polymer gel drops (PSLG/dodecane): Sonication
Sample prep determines the shape of the bubbles.
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CU aqueous solution
In this video, cylindrical bubbles fatten under tension, then go
spherical. They crinkle on reducing the pressure.
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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.
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=Grey: Hydrophilic patch
Green: Hydrophobic patch
Single hydrophobin
P1: PT (transducer)
P2: PH (hydrostatic)
Air or Oil
Aqueous phase
Schematics of CU molecules at air/water
or oil/water interface at a capillary tip.
air
Pressure Radius
Surface tension
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 .
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0 1000 2000 3000 400050
55
60
65
70
75
80
/ m
N/m
Time / s
Surface tension
0 800 160070
72
74
76
Early rinse with DI H2O
/ m
N/m
Time / s
=Grey: Hydrophilic patch
Green: Hydrophobic patch
Single hydrophobin
Air or Oil
Aqueous phase
Schematics of CU molecules
at air/water or oil/water
interface at a capillary tip.
Walker-Anna dynamic tensiometer oscillates bubble.
24Carnegie-Mellon University
The CU membrane at air/water interface becomes solid-like and more rigid.
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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.
0 500 1000 1500 2000
50
60
70
80
90
Surface tension
Radius
Time (s)
(
mN
/m)
30
40
50
60
70
80
1800 1820 184056
58
60
62
64
66
68
(m
N/m
)
Time (s)
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40
42
44
46
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Ra
diu
s (mm
)
Radiu
s (mm
)
0
250
500
750
0 700 1400
0
250
500
750
0 700 1400
-13
0
13
|E| /
mN
·m-1
|E|
E' o
r E
" /
mN
·m-1 E'
E"
/
°
Time / s
How do cylindrical bubbles form?
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We don’t know, but….
Bing
We can polymerize styrene in CU blobs.
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before
after
CU hydrophobin aqueous solution
Styrene
Azobisisobutyronitrile (AIBN)
C18 coated SiO2 tracer particles
70 oC, 14h
scale bars: 200 mm
Biofilm bag (it’s a biomaterial!) securely contains spill oil.
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Magnetic field is appliedMacondo spill oil
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100 mm 100 mm
Hydrophobins have captured rodlike poly(3-hexylthiophene) semiconducting
polymer in benzene. What happens to the polymer if the solvent evaporates?
epifluorescence brightfield
http://www.sigmaaldrich.com/catalog/product/aldrich/445703?lang=en®ion=US
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.
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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
Grazing incidence SAXS confirms excellent alignment.
34Protein-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?
Protein-Assisted Assembly of π-Conjugated Polymers
Cornelia Rosu, et al. DOI: 10.1021/acs.chemmater.5b04192
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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.
Xiuxiu Yuan
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Xiuxiu Yuan