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Title: Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides

Abstract

Two synthetic strategies for incorporating diiron analogues of [FeFe]-hydrogenases into short peptides via phosphine functional groups are described in this paper. First, utilizing the amine side chain of lysine as an anchor, phosphine carboxylic acids can be coupled via amide formation to resin-bound peptides. Second, artificial, phosphine-containing amino acids can be directly incorporated into peptides via solution phase peptide synthesis. The second approach is demonstrated using three amino acids each with a different phosphine substituent (diphenyl, diisopropyl, and diethyl phosphine). In total, five distinct monophosphine-substituted, diiron model complexes were prepared by reaction of the phosphine-peptides with diiron hexacarbonyl precursors, either (μ-pdt)Fe2(CO)6 or (μ-bdt)Fe2(CO)6 (pdt = propane-1,3-dithiolate, bdt = benzene-1,2-dithiolate). Formation of the complexes was confirmed by UV/Vis, FTIR and 31P NMR spectroscopy. Electrocatalysis by these complexes is reported in the presence of acetic acid in mixed aqueous-organic solutions. Addition of water results in enhancement of the catalytic rates.

Authors:
 [1];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Arizona State Univ., Tempe, AZ (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Solar Fuel Production (BISfuel)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1369647
Grant/Contract Number:  
SC0001016
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 33; Related Information: BISfuel partners with Arizona State University.; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Roy, Souvik, Nguyen, Thuy-Ai D., Gan, Lu, and Jones, Anne K. Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides. United States: N. p., 2015. Web. doi:10.1039/c5dt01796c.
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Roy, Souvik, Nguyen, Thuy-Ai D., Gan, Lu, & Jones, Anne K. Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides. United States. https://doi.org/10.1039/c5dt01796c
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Roy, Souvik, Nguyen, Thuy-Ai D., Gan, Lu, and Jones, Anne K. Thu . "Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides". United States. https://doi.org/10.1039/c5dt01796c. https://www.osti.gov/servlets/purl/1369647.
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@article{osti_1369647,
title = {Biomimetic peptide-based models of [FeFe]-hydrogenases: utilization of phosphine-containing peptides},
author = {Roy, Souvik and Nguyen, Thuy-Ai D. and Gan, Lu and Jones, Anne K.},
abstractNote = {Two synthetic strategies for incorporating diiron analogues of [FeFe]-hydrogenases into short peptides via phosphine functional groups are described in this paper. First, utilizing the amine side chain of lysine as an anchor, phosphine carboxylic acids can be coupled via amide formation to resin-bound peptides. Second, artificial, phosphine-containing amino acids can be directly incorporated into peptides via solution phase peptide synthesis. The second approach is demonstrated using three amino acids each with a different phosphine substituent (diphenyl, diisopropyl, and diethyl phosphine). In total, five distinct monophosphine-substituted, diiron model complexes were prepared by reaction of the phosphine-peptides with diiron hexacarbonyl precursors, either (μ-pdt)Fe2(CO)6 or (μ-bdt)Fe2(CO)6 (pdt = propane-1,3-dithiolate, bdt = benzene-1,2-dithiolate). Formation of the complexes was confirmed by UV/Vis, FTIR and 31P NMR spectroscopy. Electrocatalysis by these complexes is reported in the presence of acetic acid in mixed aqueous-organic solutions. Addition of water results in enhancement of the catalytic rates.},
doi = {10.1039/c5dt01796c},
journal = {Dalton Transactions},
number = 33,
volume = 44,
place = {United States},
year = {Thu Jul 23 00:00:00 EDT 2015},
month = {Thu Jul 23 00:00:00 EDT 2015}
}
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https://doi.org/10.1039/c5dt01796c
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