Amide Neighbouring-Group Effects in Peptides: Phenylalanine as Relay Amino Acid in Long-Distance Electron Transfer
Joses G Nathanael, Luke F Gamon, Meike Cordes, Paul R Rablen, Thomas Bally, Katharina M Fromm, Bernd Giese, Uta Wille
CHEMBIOCHEM | WILEY-V C H VERLAG GMBH | Published : 2018
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 el..View full abstract
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Awarded by Australian Research Council
Awarded by Swiss National Science Foundation
This work was supported by the Australian Research Council (project IDs LE0989197 and CE0561607) and by the Swiss National Science Foundation (project no. 152777).