Conjugated

Oligoelectrolytes for
Bioelectrochemical Applica9ons
Guillermo C. Bazan
University of California
Santa Barbara

General Perspective and

Outline!

!
Conjugated Oligoelectrolytes! (a) Incorporation into living
!
microorganisms!
(a) Background!
(b) Impact on abiotic/
interfaces!
!
(c) Facilitation of electron
equivalent transfer!

CPOS

!
(a) Improved function of
bioelectrochemical
devices!
!

Very Early Work!

CPOS

Galvani, L.. De bononiensi scientiarum et artium instituto atque academia Comentarrii 7, 363418, 1791.
(images) http://en.wikipedia.org/wiki/Luigi_Galvani

Very Early Work!

CPOS

Increasing
biocatalyst
(yeast)!
concentration!
increases
voltage!
This content downloaded from 128.111.107.218 on Thu, 12 Sep 2013 14:58:30 PM
All use subject to JSTOR Terms and Conditions

Potter, M.C.. Proceedings of the Royal Society B, vol. 84, p. 260, 1911

Applications!
Wastewater Treatment!

CPOS

Remote Sensing!

Oceanographic !
Instrument!

Adapted from http://sbi.oregonstate.edu/news/200901.htm!

The First Demonstration of a Microbial Fuel Cell as a Viable Power

Supply: Powering a Meteorlogical Buoy" J. Power Sources 1 May
2008, 179 (2), pp 571-575. - See more at: http://
www.nrl.navy.mil/techtransfer/available-technologies/energy/
benthic-fuel-cell#sthash.iMxMakRh.dpuf!

Conjugated Polyelectrolytes!

CPOS

Me3N

NMe3

Me3N

Br

Br

NMe3
Br

Br

-backbone

Conjugated
Oligoelectrolytes!

CPOS

NMe3 I
I

Me3N

NMe3 I

DSBN+
I

Me3N
NMe3 I
N

DSSN+

NMe3 I

Me3N
N

Me3N

Two-Photon Absorption in Three-Dimensional Chromophores based on [2.2]-Paracyclophane, Bartholomew,

G.P.; Rumi, M.; Pond, S.J.K.; Perry, J.W.; Tretiak, S.; Bazan, G.C., J. Am. Chem. Soc., 2004, 126,
11529-11542.!
!
Solvent Effects on the Two-Photon Absorption of Distyrylbenzene Chromophores, Woo, H.Y.; Liu, B.; Kohler,
B.; Korystov, D.; Mikhailovsky, A.; Bazan, G.C., J. Am. Chem. Soc., 2005, 127, 14721-14729 !
!

Solvatochromic Features!
NMe3 I
N
I

Me3N

Me3N

NMe3 I
N
I
N
I

I
N
I

CPOS

Membrane Intercalation!

CPOS

NMe3 I
I

DSBN+

Me3N

NMe3 I

N
I

Me3N
NMe3 I
N

DSSN+

Me3N

Me3N

NMe3 I
N

Membrane Intercalation!

CPOS

NMe3 I
I

DSBN+

Me3N

NMe3 I

N
I

Me3N
NMe3 I
N

DSSN+

Me3N

Me3N

NMe3 I
N

Amphiphilic molecular structure:

~3.6 nm

Commensurate dimensions:

N
N

N
N

Confirmation of Orientation!

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Polarized confocal microscopy!

A

NMe3 I
N

Me3N

N
Me3N

Axis Normal to Plane

of Excitation h!
Plane of Polarized
Excitation h!

C
N

!"

N
N

!"

N
N

h!ex

h!ex

N
N
N

"

!"

h!em

N
N

h!ex
h!ex

h!em

!"

NMe3 I

Living Systems: Yeast!

CPOS

Spontaneous and Fast

Insertion into Yeast
confocal fluorescence
(excitation of DSSN+ at 488nm)

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brightfield image with overlaid

confocal fluorescence

Yeast
Cell Tomography
Surface-Specificity
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COS-1 Mammalian Cell

confocal fluorescence
(excitation of DSSN+ at 488nm)

Emission Recovery Indicates

Diffusion in Membrane
confocal fluorescence
(excitation of DSSN+ at 488nm)

brightfield image

CPOS

Summary
of Observations
!
Yeast
Stain!

CPOS

Conjugated oligoelectrolytes have an affinity for membrane

intercalation.
Works for living microorganisms across a useful toxicity
window.
What about the bioelectrochemical properties of the
modified microorganisms?

Microbial Fuel Cell

e -!

e -!

Glucose!
Bacterium!

e -!

e -!
H2O!

O2!
!
CO2!
H+!
Anode!

H+!

Cathode!

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Effect of COEs on Yeast

MFCs!

CPOS

e
Septum(allows
anaerobic
environment)

SubmergedGraphite
FeltAnode

Load

H+

Abio8cGraphite
FeltCathode
(AerobicChamber)

NaonMembrane

0.20
No Med.
No Med.
MB
MB
DSBN+
DSBN+
DSSN+
DSSN+

Potential (V)

0.15
0.10
0.05
Collaboration with Dr.
James Sumner, Army
Research Laboratory

0.00

10
20
30
40
Time (a.u., total time = ~5 days)

50

Spontaneous and Fast

Insertion into E. coli
confocal fluorescence
(excitation of DSSN at 488nm)

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brightfield image with overlaid

confocal fluorescence

E. Coli MFC Performance!

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Power Generation!

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V
R1!
R2
R3
R4
R5
R6
R7
e-

Power density!

R4!
eH+

H+
H 2O

Substrate
Anode
Microbe

PEM

Cathode

R5!

R3!

R6!

R2!
R1!

R7!
Current density!

COE Labeled E. coli!

CPOS

Me3N(H2C)6
N
Me3N(H2C)6

(CH2)6NMe3

N
#14-140h-Device2-20111220

Power Density (mW/m2)

(CH2)6NMe3

1,2,3

12
10

EC-(Control)-2

EC-(COE2-5C)
EC-(COE2-3C)

EC-(COE2-4C)

4
2
0
0

50

100

150

200

250

300

350

Current Density (mA/m2)

Microbial fuel cells with COE-modified E. coli deliver higher power

densities compared to normal, wild type containing devices. !

Wastewater MFC!

CPOS

e
Septum(allows
anaerobic
environment)

SubmergedGraphite
FeltAnode

Load

H+

NaonMembrane

Collaboration with Dr. Steve Harvey:

Edgewood Chemical Biological Center and
Dr. James Sumner: SEDD ARL

Graphite
FeltBiocathode
(AerobicChamber)

Current Generation Occurs

only with COE!

CPOS

Conjugated Oligoelectrolytes Increase Current Response and Organic Contaminant Removal in Wastewater
Microbial Fuel Cells, Garner, L.E.; Thomas, A.W.; Sumner, J.J.; Harvey, S.P.; Bazan, G.C., Energy & Environ. Sci.,
2012, 5, 9449-9452.!

Examination of Electrodes!
SEM Images!

Confocal Fluorescence
Microscopy!
anode!

cathode!

CPOS

Brightfield
Microscopy!

Yeast
Stain!
Summary
of Observations
!

CPOS

Conjugated oligoelectrolytes (COEs) can modify living

microorganisms.
Microbial fuel cells containing these modified
microorganisms provide higher power because of lower
internal resistance.
Wastewater communities can evolve electrogenic properties
in the presence of COEs.
What about electron injection?

Electrons"(mmol)"

Current#(mA)#

Greater Current Uptake!

CPOS

0#
!1#
!2# innocula9on COE
fumarate addn
Shewanella Oneidensis MR-1 can
addn
!3#
use an electrode as the sole eNo COE
!4#
donor in the presence of COE.
10 M DSSN+
!5#
1 M DSSN+
!6#
!7#
!8#
6"
!9#
Electrons appearing in succinate
2#
8#
Electrons
from 4#
cathode 6#
5" 0#
+ 2e- + 2H+
Time%(days)%
4"

3"
2"
1"
0"
0"

2"

4"

Time"(days)"

6"

8"

Greater Current Uptake!

none
1M DSSN+
10M DSSN+

CPOS

Shewanella Oneidensis MR-1 can

use an electrode as the sole edonor in the presence of COE.

+ 2e- + 2H+

Collaboration with the group of Professor Derek Lovley. !

DSSN+ Emission in
Shewanella Oneidensis!
A

CPOS

B
250 !M

20 !M

C
2.5 !M
NMe3
N
NMe3

Me3N
N
Me3N

A Lipid Membrane Intercalating Conjugated Oligoelectrolyte Enables Electrode Driven Succinate Production in
Shewanella, Thomas, A. W.; Garner L. E.; Nevin, K. P.; Woodard, T. L.; Franks, A. E.; Lovley, D. R.; Sumner, J.
J.; Sund, C. J.; Bazan, G. C., Energy & Environmental Science, 2013, 6, 1761-1765.!

Summary
of Observations
!
Yeast
Stain!

CPOS

Bioelectrosynthesis devices with conjugated oligoelectrolyte

containing Shewanella oneidensis more readily uptake
current. The injected charge correlates to the production of
anticipated product.
Improvements of both electron equivalent injection and
extraction have been demonstrated.
What about other microbial communities?

Microbial
Electrolysis
Cells
!
Yeast Stain!
http://www.nsf.gov/news/mmg/media/images/biohydrogen_h.jpg!

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Biogas Production with

COE-Added MECs!

Air-tight
chamber!

Graphite
anode!

Cathode!

Single chamber mini MEC!

CPOS

Microbial Electrolysis Cells

- Biogas from wastewater!

PS
eBiofilm from
wastewater

CH4

H+
H2
H+

Substrate

Hydrogen
recycling

Cathode

Anode

CO2

H2
H+

Hydrogenotrophic
methanogenesis

Single chamber
MECs!
Collaboration with the group of Professor Bruce Logan. !

CPOS

Biogas
Production
with
COE Repress Hydrogenotrophic
COE-Added
MECs!
Methanogenesis

CPOS

CPOS

Me N(H C)
- Mixed
Culture MECs"
N
3

(CH2)6NMe3

Me3N(H2C)6
N

(CH2)6NMe3

10
9
8
7
6
5
4
3
2
1
0

Mixed Culture MECs. Biological

film produced from waste water.!

H2, CH4 gas volume (ml)

H2-DSBN+

COE in mixed culture

MECs:!
o Repressed methane
production!
o Enhanced hydrogen
production!
o Sustained effect when
no COE added in cycles
#4-#9!

CH4-DSBN+
H2-Control
CH4-Control

#1

#2

#3

#4

#5 #6
Cycle #

#7

#8

COE in mixed culture MECs:"

#9

Yeast
Stain!
Summary
of Observations
!

CPOS

Conjugated oligoelectrolytes modify the selectivity of

communities in microbial electrolysis by modifying the
specificity of the process.
In combination with the generation of electricity from
wastewater, the results provide a vision for improving the ability
to electrically stimulate biofilms, while at the same time
changing the products generated by the microbial communities.

Influence of Molecular
Structure!
I- NMe3
Me3N I-

N
S

Br

Br

S N
S

Br
N

Normalized+Absorbance+and+Emission+

0.8"
0.6"
0.4"
0.2"

500"

600"
700"
Wavelength+(nm)+

800"

900"

Br
N

1"

400"

ZCOE!

DSSN+!

0"
300"

N S

I- NMe3
Me3N I-

CPOS

1000"

Br

Synthesis of ZCOE!

Br

Br

Br

Br

Br
Br

KOH
C6H12Br2
S

N
Sn

2. Me3SnCl, THF, -78 C

Sn

Br
Br

Pd(PPh3)4

N
N

S N

N S
S

Br

Br

Br

Pd(PPh3)4
toluene, 150 C

Br

Br

1. n-BuLi, THF, -78 C

DMSO
80 C

CPOS

Sn

S N

N S
S

N
S

toluene
150 C

pyridine
100 C

3
Br

Br

Br

Br

ZCOE

N
Br

Final Thoughts
CPOS

Acknowledgements
Alex Thomas!

Xiaofen Chen!

Chelsea Catania!
Dr. Hengjing Yan!

Nate Kirchhofer!

Dr. Logan Garner!

(NREL)!
Dr. Jenny Du!
(aPeel Tech)!
Dr. Huijie Hou!
(Penn State)!

Thank you!!