Amide Neighbouring-Group Effects in Peptides: Phenylalanine as Relay Amino Acid in Long-Distance Electron Transfer

TY - JOUR

T1 - Amide Neighbouring-Group Effects in Peptides

T2 - Phenylalanine as Relay Amino Acid in Long-Distance Electron Transfer

AU - Nathanael, Joses G.

AU - Gamon, Luke F.

AU - Cordes, Meike

AU - Rablen, Paul R.

AU - Bally, Thomas

AU - Fromm, Katharina M.

AU - Giese, Bernd

AU - Wille, Uta

PY - 2018/5/4

Y1 - 2018/5/4

N2 - 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.

AB - 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.

KW - density functional calculations

KW - electron transfer

KW - kinetics

KW - neighboring-group effects

KW - peptides

KW - radical cations

UR - http://www.scopus.com/inward/record.url?scp=85045341917&partnerID=8YFLogxK

U2 - 10.1002/cbic.201800098

DO - 10.1002/cbic.201800098

M3 - Journal article

C2 - 29460322

AN - SCOPUS:85045341917

SN - 1439-4227

VL - 19

SP - 922

EP - 926

JO - ChemBioChem

JF - ChemBioChem

IS - 9

ER -