Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble

Ardemis A. Boghossian, Jong Hyun Choi, Moon Ho Ham, Esther S. Jeng, Rachel A. Graff, Daniel A. Heller, Alice C. Chang, Aidas Mattis, Timothy H. Bayburt, Yelena V. Grinkova, Adam Scott Zeiger, Krystyn J. Van Vliet, Erik K. Hobbie, Stephen Sligar, Colin A. Wraight, Michael Strano

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Naturally occurring photosynthetic systems use elaborate pathways of self-repair to limit the impact of photo-damage. Here, we demonstrate a complex consisting of an aqueous solution containing photosynthetic reaction centers (RCs), membrane scaffold proteins (MSPs), phospholipids, and single-walled carbon nanotubes (SWCNTs) solubilized with the surfactant sodium cholate (SC) that mimics this process. The components reversibly self-assemble into a highly ordered structure upon dialysis of the surfactant. The resulting assembled structure is photoelectrochemically active and consists of 4-nm-thick lipid bilayer disks (nanodisks, NDs) arranged parallel to the surface of the SWCNT with the RC housed within the bilayer such that its hole injecting site faces the nanotube surface. The structure can be assembled and disassembled autonomously with the addition or removal of surfactant. We model the kinetic and thermodynamic forces that drive the dynamics of this reversible self-assembly process. The assembly is monitored using spectrofluorimetry during dialysis and subsequent surfactant addition and used to fit a kinetic model to determine the forward and reverse rate constants of ND and ND-SWCNT formation. The calculated ND and ND-SWCNT forward rate constants are 79 mM -1 s -1 and 5.4 × 10 2 mM -1 s -1, respectively, and the reverse rate constants are negligible over the dialysis time scale. We find that the reaction is not diffusion-controlled since the ND-SWCNT reaction, which consists of entities with smaller diffusion coefficients, has a larger reaction rate constant. Using these rate parameters, we were able to develop a kinetic phase diagram for the formation of ND-SWCNT complexes, which indicates an optimal dialysis rate of approximately 8 × 10 -4 s -1. The assembly is thermodynamically metastable and can only transition reversibly if the rate of surfactant removal exceeds a threshold value. Only in the assembled state do the complexes exhibit photoelectrochemical activity. We experimentally demonstrate a regeneration cycle that uses surfactant to switch between assembled and disassembled states, resulting in an increased photoconversion efficiency of more than 300% over 168 hours and an indefinite extension of the system lifetime. The system can disassemble and reassemble over an indefinite number of cycles. We also fit the model to these cyclic ND-SWCNT assembly and disassembly experiments and hence mimic the thermodynamic forces used in regeneration processes detailed previously. Such forces may form the basis of both synthetic and natural photoelectrochemical complexes capable of dynamic component replacement and repair.

Original languageEnglish (US)
Title of host publication11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings
StatePublished - Dec 1 2011
Event2011 AIChE Annual Meeting, 11AIChE - Minneapolis, MN, United States
Duration: Oct 16 2011Oct 21 2011

Publication series

Name11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings

Other

Other2011 AIChE Annual Meeting, 11AIChE
CountryUnited States
CityMinneapolis, MN
Period10/16/1110/21/11

Fingerprint

Single-walled carbon nanotubes (SWCN)
Energy conversion
Solar energy
Surface-Active Agents
Surface active agents
Dialysis
Rate constants
Kinetics
Repair
Sodium Cholate
Thermodynamics
Photosynthetic Reaction Center Complex Proteins
Lipid bilayers
Phospholipids
Scaffolds (biology)
Scaffolds
Self assembly
Nanotubes
Reaction rates
Phase diagrams

ASJC Scopus subject areas

  • Chemical Engineering(all)

Cite this

Boghossian, A. A., Choi, J. H., Ham, M. H., Jeng, E. S., Graff, R. A., Heller, D. A., ... Strano, M. (2011). Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble. In 11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings (11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings).

Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble. / Boghossian, Ardemis A.; Choi, Jong Hyun; Ham, Moon Ho; Jeng, Esther S.; Graff, Rachel A.; Heller, Daniel A.; Chang, Alice C.; Mattis, Aidas; Bayburt, Timothy H.; Grinkova, Yelena V.; Zeiger, Adam Scott; Van Vliet, Krystyn J.; Hobbie, Erik K.; Sligar, Stephen; Wraight, Colin A.; Strano, Michael.

11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings. 2011. (11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings).

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Boghossian, AA, Choi, JH, Ham, MH, Jeng, ES, Graff, RA, Heller, DA, Chang, AC, Mattis, A, Bayburt, TH, Grinkova, YV, Zeiger, AS, Van Vliet, KJ, Hobbie, EK, Sligar, S, Wraight, CA & Strano, M 2011, Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble. in 11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings. 11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings, 2011 AIChE Annual Meeting, 11AIChE, Minneapolis, MN, United States, 10/16/11.
Boghossian AA, Choi JH, Ham MH, Jeng ES, Graff RA, Heller DA et al. Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble. In 11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings. 2011. (11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings).
Boghossian, Ardemis A. ; Choi, Jong Hyun ; Ham, Moon Ho ; Jeng, Esther S. ; Graff, Rachel A. ; Heller, Daniel A. ; Chang, Alice C. ; Mattis, Aidas ; Bayburt, Timothy H. ; Grinkova, Yelena V. ; Zeiger, Adam Scott ; Van Vliet, Krystyn J. ; Hobbie, Erik K. ; Sligar, Stephen ; Wraight, Colin A. ; Strano, Michael. / Photoelectrochemical complexes for solar energy conversion that dynamically, reversibly and autonomously self-assemble. 11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings. 2011. (11AIChE - 2011 AIChE Annual Meeting, Conference Proceedings).
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abstract = "Naturally occurring photosynthetic systems use elaborate pathways of self-repair to limit the impact of photo-damage. Here, we demonstrate a complex consisting of an aqueous solution containing photosynthetic reaction centers (RCs), membrane scaffold proteins (MSPs), phospholipids, and single-walled carbon nanotubes (SWCNTs) solubilized with the surfactant sodium cholate (SC) that mimics this process. The components reversibly self-assemble into a highly ordered structure upon dialysis of the surfactant. The resulting assembled structure is photoelectrochemically active and consists of 4-nm-thick lipid bilayer disks (nanodisks, NDs) arranged parallel to the surface of the SWCNT with the RC housed within the bilayer such that its hole injecting site faces the nanotube surface. The structure can be assembled and disassembled autonomously with the addition or removal of surfactant. We model the kinetic and thermodynamic forces that drive the dynamics of this reversible self-assembly process. The assembly is monitored using spectrofluorimetry during dialysis and subsequent surfactant addition and used to fit a kinetic model to determine the forward and reverse rate constants of ND and ND-SWCNT formation. The calculated ND and ND-SWCNT forward rate constants are 79 mM -1 s -1 and 5.4 × 10 2 mM -1 s -1, respectively, and the reverse rate constants are negligible over the dialysis time scale. We find that the reaction is not diffusion-controlled since the ND-SWCNT reaction, which consists of entities with smaller diffusion coefficients, has a larger reaction rate constant. Using these rate parameters, we were able to develop a kinetic phase diagram for the formation of ND-SWCNT complexes, which indicates an optimal dialysis rate of approximately 8 × 10 -4 s -1. The assembly is thermodynamically metastable and can only transition reversibly if the rate of surfactant removal exceeds a threshold value. Only in the assembled state do the complexes exhibit photoelectrochemical activity. We experimentally demonstrate a regeneration cycle that uses surfactant to switch between assembled and disassembled states, resulting in an increased photoconversion efficiency of more than 300{\%} over 168 hours and an indefinite extension of the system lifetime. The system can disassemble and reassemble over an indefinite number of cycles. We also fit the model to these cyclic ND-SWCNT assembly and disassembly experiments and hence mimic the thermodynamic forces used in regeneration processes detailed previously. Such forces may form the basis of both synthetic and natural photoelectrochemical complexes capable of dynamic component replacement and repair.",
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AU - Boghossian, Ardemis A.

AU - Choi, Jong Hyun

AU - Ham, Moon Ho

AU - Jeng, Esther S.

AU - Graff, Rachel A.

AU - Heller, Daniel A.

AU - Chang, Alice C.

AU - Mattis, Aidas

AU - Bayburt, Timothy H.

AU - Grinkova, Yelena V.

AU - Zeiger, Adam Scott

AU - Van Vliet, Krystyn J.

AU - Hobbie, Erik K.

AU - Sligar, Stephen

AU - Wraight, Colin A.

AU - Strano, Michael

PY - 2011/12/1

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N2 - Naturally occurring photosynthetic systems use elaborate pathways of self-repair to limit the impact of photo-damage. Here, we demonstrate a complex consisting of an aqueous solution containing photosynthetic reaction centers (RCs), membrane scaffold proteins (MSPs), phospholipids, and single-walled carbon nanotubes (SWCNTs) solubilized with the surfactant sodium cholate (SC) that mimics this process. The components reversibly self-assemble into a highly ordered structure upon dialysis of the surfactant. The resulting assembled structure is photoelectrochemically active and consists of 4-nm-thick lipid bilayer disks (nanodisks, NDs) arranged parallel to the surface of the SWCNT with the RC housed within the bilayer such that its hole injecting site faces the nanotube surface. The structure can be assembled and disassembled autonomously with the addition or removal of surfactant. We model the kinetic and thermodynamic forces that drive the dynamics of this reversible self-assembly process. The assembly is monitored using spectrofluorimetry during dialysis and subsequent surfactant addition and used to fit a kinetic model to determine the forward and reverse rate constants of ND and ND-SWCNT formation. The calculated ND and ND-SWCNT forward rate constants are 79 mM -1 s -1 and 5.4 × 10 2 mM -1 s -1, respectively, and the reverse rate constants are negligible over the dialysis time scale. We find that the reaction is not diffusion-controlled since the ND-SWCNT reaction, which consists of entities with smaller diffusion coefficients, has a larger reaction rate constant. Using these rate parameters, we were able to develop a kinetic phase diagram for the formation of ND-SWCNT complexes, which indicates an optimal dialysis rate of approximately 8 × 10 -4 s -1. The assembly is thermodynamically metastable and can only transition reversibly if the rate of surfactant removal exceeds a threshold value. Only in the assembled state do the complexes exhibit photoelectrochemical activity. We experimentally demonstrate a regeneration cycle that uses surfactant to switch between assembled and disassembled states, resulting in an increased photoconversion efficiency of more than 300% over 168 hours and an indefinite extension of the system lifetime. The system can disassemble and reassemble over an indefinite number of cycles. We also fit the model to these cyclic ND-SWCNT assembly and disassembly experiments and hence mimic the thermodynamic forces used in regeneration processes detailed previously. Such forces may form the basis of both synthetic and natural photoelectrochemical complexes capable of dynamic component replacement and repair.

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