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Title: Expanding Covalent Attachment Sites of Nonnative Chromophores to Encompass the C-Terminal Hydrophilic Domain in Biohybrid Light-Harvesting Architectures

Abstract

Increasing the solar spectral coverage of native photosynthetic antennas can be attained using biohybrid light-harvesting (LH) structures comprised of native-like bacterial photosynthetic peptides and synthetic bacteriochlorins with strong near-infrared absorption. Four such biohybrids have been prepared wherein synthetic maleimido-bearing bacteriochlorin BC1-mal is covalently attached to a Cys residue substituted at either the +1, +5 or +11 position (relative to His-0) of the 48-residue β-peptide of Rb. sphaeroides LH1. Furthermore, a β-peptide with Phe substituted for Tyr at the +4 position along with +1Cys was used to examine possible quenching of the excited BC1 by the Tyr. The β-peptide analogs, as well as their peptide-BC1 conjugates when combined with native α-peptide, and bacteriochlorophyll a (BChl a) self-assemble to form αβ-dyads and therefrom LH1-type cyclic (αβ) n oligomers. Here, static and time-resolved optical studies show that all of the oligomeric assemblies transfer excitation energy from the appended BC1 to the BChl a array (B875) with an average efficiency of 85 %.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Washington Univ., St. Louis, MO (United States)
  2. North Carolina State Univ., Raleigh, NC (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO (United States). Photosynthetic Antenna Research Center (PARC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470056
Alternate Identifier(s):
OSTI ID: 1419902
Grant/Contract Number:  
SC0001035
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhotoChem
Additional Journal Information:
Journal Volume: 2; Journal Issue: 3; 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 2367-0932
Country of Publication:
United States
Language:
English
Subject:
bacteriochlorin; bacteriochlorophyll; energy transfer; photosynthetic antennae; self-assembly

Citation Formats

Hood, Don, Sahin, Tuba, Parkes-Loach, Pamela S., Jiao, Jieying, Harris, Michelle A., Dilbeck, Preston, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Loach, Paul A., Bocian, David F., Lindsey, Jonathan S., and Holten, Dewey. Expanding Covalent Attachment Sites of Nonnative Chromophores to Encompass the C-Terminal Hydrophilic Domain in Biohybrid Light-Harvesting Architectures. United States: N. p., 2017. Web. doi:10.1002/cptc.201700182.
Hood, Don, Sahin, Tuba, Parkes-Loach, Pamela S., Jiao, Jieying, Harris, Michelle A., Dilbeck, Preston, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Loach, Paul A., Bocian, David F., Lindsey, Jonathan S., & Holten, Dewey. Expanding Covalent Attachment Sites of Nonnative Chromophores to Encompass the C-Terminal Hydrophilic Domain in Biohybrid Light-Harvesting Architectures. United States. doi:10.1002/cptc.201700182.
Hood, Don, Sahin, Tuba, Parkes-Loach, Pamela S., Jiao, Jieying, Harris, Michelle A., Dilbeck, Preston, Niedzwiedzki, Dariusz M., Kirmaier, Christine, Loach, Paul A., Bocian, David F., Lindsey, Jonathan S., and Holten, Dewey. Sun . "Expanding Covalent Attachment Sites of Nonnative Chromophores to Encompass the C-Terminal Hydrophilic Domain in Biohybrid Light-Harvesting Architectures". United States. doi:10.1002/cptc.201700182. https://www.osti.gov/servlets/purl/1470056.
@article{osti_1470056,
title = {Expanding Covalent Attachment Sites of Nonnative Chromophores to Encompass the C-Terminal Hydrophilic Domain in Biohybrid Light-Harvesting Architectures},
author = {Hood, Don and Sahin, Tuba and Parkes-Loach, Pamela S. and Jiao, Jieying and Harris, Michelle A. and Dilbeck, Preston and Niedzwiedzki, Dariusz M. and Kirmaier, Christine and Loach, Paul A. and Bocian, David F. and Lindsey, Jonathan S. and Holten, Dewey},
abstractNote = {Increasing the solar spectral coverage of native photosynthetic antennas can be attained using biohybrid light-harvesting (LH) structures comprised of native-like bacterial photosynthetic peptides and synthetic bacteriochlorins with strong near-infrared absorption. Four such biohybrids have been prepared wherein synthetic maleimido-bearing bacteriochlorin BC1-mal is covalently attached to a Cys residue substituted at either the +1, +5 or +11 position (relative to His-0) of the 48-residue β-peptide of Rb. sphaeroides LH1. Furthermore, a β-peptide with Phe substituted for Tyr at the +4 position along with +1Cys was used to examine possible quenching of the excited BC1 by the Tyr. The β-peptide analogs, as well as their peptide-BC1 conjugates when combined with native α-peptide, and bacteriochlorophyll a (BChl a) self-assemble to form αβ-dyads and therefrom LH1-type cyclic (αβ)n oligomers. Here, static and time-resolved optical studies show that all of the oligomeric assemblies transfer excitation energy from the appended BC1 to the BChl a array (B875) with an average efficiency of 85 %.},
doi = {10.1002/cptc.201700182},
journal = {ChemPhotoChem},
number = 3,
volume = 2,
place = {United States},
year = {2017},
month = {12}
}

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