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Title: Electronic coupling through natural amino acids

Abstract

Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For both motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. Here, the unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green’s function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office (BETO); Swiss National Science Foundation (SNSF)
OSTI Identifier:
1235671
Alternate Identifier(s):
OSTI ID: 1228434
Report Number(s):
NREL/JA-2700-64983
Journal ID: ISSN 0021-9606; JCPSA6
Grant/Contract Number:  
AC36-08GO28308; MCB09159
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 22; Related Information: Journal of Chemical Physics; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 59 BASIC BIOLOGICAL SCIENCES; electron transfer; inductive effect; electron tunneling; Green's function; superexchange; peptide electron transfer; protein engineering; amino acid; electronic coupling; peptides; biosensors; chemical bonding; density functional theory; biological electron transfer; electronic structure methods

Citation Formats

Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Electronic coupling through natural amino acids. United States: N. p., 2015. Web. doi:10.1063/1.4936588.
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Berstis, Laura, Beckham, Gregg T., & Crowley, Michael F. Electronic coupling through natural amino acids. United States. https://doi.org/10.1063/1.4936588
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Berstis, Laura, Beckham, Gregg T., and Crowley, Michael F. Tue . "Electronic coupling through natural amino acids". United States. https://doi.org/10.1063/1.4936588. https://www.osti.gov/servlets/purl/1235671.
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@article{osti_1235671,
title = {Electronic coupling through natural amino acids},
author = {Berstis, Laura and Beckham, Gregg T. and Crowley, Michael F.},
abstractNote = {Myriad scientific domains concern themselves with biological electron transfer (ET) events that span across vast scales of rate and efficiency through a remarkably fine-tuned integration of amino acid (AA) sequences, electronic structure, dynamics, and environment interactions. Within this intricate scheme, many questions persist as to how proteins modulate electron-tunneling properties. To help elucidate these principles, we develop a model set of peptides representing the common α-helix and β-strand motifs including all natural AAs within implicit protein-environment solvation. Using an effective Hamiltonian strategy with density functional theory, we characterize the electronic coupling through these peptides, furthermore considering side-chain dynamics. For both motifs, predictions consistently show that backbone-mediated electronic coupling is distinctly sensitive to AA type (aliphatic, polar, aromatic, negatively charged and positively charged), and to side-chain orientation. Here, the unique properties of these residues may be employed to design activated, deactivated, or switch-like superexchange pathways. Electronic structure calculations and Green’s function analyses indicate that localized shifts in the electron density along the peptide play a role in modulating these pathways, and further substantiate the experimentally observed behavior of proline residues as superbridges.},
doi = {10.1063/1.4936588},
journal = {Journal of Chemical Physics},
number = 22,
volume = 143,
place = {United States},
year = {Tue Dec 08 00:00:00 EST 2015},
month = {Tue Dec 08 00:00:00 EST 2015}
}
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