期刊
CHEMBIOCHEM
卷 19, 期 9, 页码 922-926出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cbic.201800098
关键词
density functional calculations; electron transfer; kinetics; neighboring-group effects; peptides; radical cations
资金
- Australian Research Council [LE0989197, CE0561607]
- Swiss National Science Foundation [152777]
- Australian Research Council [LE0989197, CE0561607] Funding Source: Australian Research Council
In nature, proteins serve as media for long-distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single-step superexchange or through a multi-step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long-distance electron hole transfer through peptides. The considerably increased susceptibility of the aromatic ring to oxidation is caused by the lone pairs of neighbouring amide carbonyl groups, which stabilise the Phe radical cation. This neighbouring-amide-group effect helps improve understanding of the mechanism of extracellular electron transfer through conductive protein filaments (pili) of anaerobic bacteria during mineral respiration.
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