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Title: Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles

Abstract

Lipid vesicles are used as the organizational structure of self-assembled light-harvesting systems. Following analysis of 17 chromophores, six were selected for inclusion in vesicle-based antennas. The complementary absorption features of the chromophores span the near-ultraviolet, visible, and near-infrared region. Although the overall concentration of the pigments is low (~1 μM for quantitative spectroscopic studies) in a cuvette, the lipid-vesicle system affords high concentration (≥10 mM) in the bilayer for efficient energy flow from donor to acceptor. Energy transfer was characterized in 13 representative binary mixtures using static techniques (fluorescence–excitation versus absorptance spectra, quenching of donor fluorescence, modeling emission spectra of a mixture versus components) and time-resolved spectroscopy (fluorescence, ultrafast absorption). Binary donor–acceptor systems that employ a boron-dipyrrin donor (S 0 ↔ S 1 absorption/emission in the blue-green) and a chlorin or bacteriochlorin acceptor (S 0 ↔ S 1 absorption/emission in the red or near-infrared) have an average excitation-energy-transfer efficiency (Φ EET) of ~50%. Binary systems with a chlorin donor and a chlorin or bacteriochlorin acceptor have Φ EET ~ 85%. The differences in Φ EET generally track the donor-fluorescence/acceptor-absorption spectral overlap within a dipole–dipole coupling (Förster) mechanism. Substantial deviation from single-exponential decay of the excited donor (due to the dispersionmore » of donor–acceptor distances) is expected and observed. The time profiles and resulting Φ EET are modeled on the basis of (Förster) energy transfer between chromophores relatively densely packed in a two-dimensional compartment. Initial studies of two ternary and one quaternary combination of chromophores show the enhanced spectral coverage and energy-transfer efficacy expected on the basis of the binary systems. Collectively, this approach may provide one of the simplest designs for self-assembled light-harvesting systems that afford broad solar collection and efficient energy transfer.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [4];  [2];  [1]
  1. North Carolina State Univ., Raleigh, NC (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States)
  4. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC); Washington Univ., St. Louis, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1386028
Grant/Contract Number:  
SC0001035
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 119; Journal Issue: 32; Related Information: PARC partners with Washington University in St. Louis (lead); University of California, Riverside; University of Glasgow, UK; Los Alamos National Laboratory; University of New Mexico; New Mexico Corsortium; North Carolina State University; Northwestern University; Oak Ridge National Laboratory; University of Pennsylvania; Sandia National Laboratories; University of Sheffield, UK; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar (fuels); photosynthesis (natural and artificial); biofuels (including algae and biomass); bio-inspired; charge transport; membrane; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Sahin, Tuba, Harris, Michelle A., Vairaprakash, Pothiappan, Niedzwiedzki, Dariusz M., Subramanian, Vijaya, Shreve, Andrew P., Bocian, David F., Holten, Dewey, and Lindsey, Jonathan S. Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles. United States: N. p., 2015. Web. doi:10.1021/acs.jpcb.5b04841.
Sahin, Tuba, Harris, Michelle A., Vairaprakash, Pothiappan, Niedzwiedzki, Dariusz M., Subramanian, Vijaya, Shreve, Andrew P., Bocian, David F., Holten, Dewey, & Lindsey, Jonathan S. Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles. United States. doi:10.1021/acs.jpcb.5b04841.
Sahin, Tuba, Harris, Michelle A., Vairaprakash, Pothiappan, Niedzwiedzki, Dariusz M., Subramanian, Vijaya, Shreve, Andrew P., Bocian, David F., Holten, Dewey, and Lindsey, Jonathan S. Fri . "Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles". United States. doi:10.1021/acs.jpcb.5b04841. https://www.osti.gov/servlets/purl/1386028.
@article{osti_1386028,
title = {Self-Assembled Light-Harvesting System from Chromophores in Lipid Vesicles},
author = {Sahin, Tuba and Harris, Michelle A. and Vairaprakash, Pothiappan and Niedzwiedzki, Dariusz M. and Subramanian, Vijaya and Shreve, Andrew P. and Bocian, David F. and Holten, Dewey and Lindsey, Jonathan S.},
abstractNote = {Lipid vesicles are used as the organizational structure of self-assembled light-harvesting systems. Following analysis of 17 chromophores, six were selected for inclusion in vesicle-based antennas. The complementary absorption features of the chromophores span the near-ultraviolet, visible, and near-infrared region. Although the overall concentration of the pigments is low (~1 μM for quantitative spectroscopic studies) in a cuvette, the lipid-vesicle system affords high concentration (≥10 mM) in the bilayer for efficient energy flow from donor to acceptor. Energy transfer was characterized in 13 representative binary mixtures using static techniques (fluorescence–excitation versus absorptance spectra, quenching of donor fluorescence, modeling emission spectra of a mixture versus components) and time-resolved spectroscopy (fluorescence, ultrafast absorption). Binary donor–acceptor systems that employ a boron-dipyrrin donor (S0 ↔ S1 absorption/emission in the blue-green) and a chlorin or bacteriochlorin acceptor (S0 ↔ S1 absorption/emission in the red or near-infrared) have an average excitation-energy-transfer efficiency (ΦEET) of ~50%. Binary systems with a chlorin donor and a chlorin or bacteriochlorin acceptor have ΦEET ~ 85%. The differences in ΦEET generally track the donor-fluorescence/acceptor-absorption spectral overlap within a dipole–dipole coupling (Förster) mechanism. Substantial deviation from single-exponential decay of the excited donor (due to the dispersion of donor–acceptor distances) is expected and observed. The time profiles and resulting ΦEET are modeled on the basis of (Förster) energy transfer between chromophores relatively densely packed in a two-dimensional compartment. Initial studies of two ternary and one quaternary combination of chromophores show the enhanced spectral coverage and energy-transfer efficacy expected on the basis of the binary systems. Collectively, this approach may provide one of the simplest designs for self-assembled light-harvesting systems that afford broad solar collection and efficient energy transfer.},
doi = {10.1021/acs.jpcb.5b04841},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 32,
volume = 119,
place = {United States},
year = {2015},
month = {7}
}

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Works referencing / citing this record:

Proteoliposomes as energy transferring nanomaterials: enhancing the spectral range of light-harvesting proteins using lipid-linked chromophores
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Proteoliposomes as energy transferring nanomaterials: enhancing the spectral range of light-harvesting proteins using lipid-linked chromophores
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  • Hancock, Ashley M.; Meredith, Sophie A.; Connell, Simon D.
  • Nanoscale, Vol. 11, Issue 35
  • DOI: 10.1039/c9nr04653d

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  • Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S.
  • Photochemistry and Photobiology, Vol. 94, Issue 2
  • DOI: 10.1111/php.12862