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

doi:10.1002/cbic.201800098

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

^*Corresponding author for this work

Inflammation, Metabolism and Oxidation

12 Citations (Scopus)

Abstract

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.

Original language	English
Journal	ChemBioChem
Volume	19
Issue number	9
Pages (from-to)	922-926
Number of pages	5
ISSN	1439-4227
DOIs	https://doi.org/10.1002/cbic.201800098
Publication status	Published - 4 May 2018

Keywords

density functional calculations
electron transfer
kinetics
neighboring-group effects
peptides
radical cations

Access to Document

10.1002/cbic.201800098

viewcontent.cgi?article=1222&context=fac-chemistryFinal published version, 3.93 MB

Cite this

@article{c5c8bd68b98c4dfd8eeaf2140ce69f1a,

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

abstract = "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.",

keywords = "density functional calculations, electron transfer, kinetics, neighboring-group effects, peptides, radical cations",

author = "Nathanael, {Joses G.} and Gamon, {Luke F.} and Meike Cordes and Rablen, {Paul R.} and Thomas Bally and Fromm, {Katharina M.} and Bernd Giese and Uta Wille",

year = "2018",

month = may,

day = "4",

doi = "10.1002/cbic.201800098",

language = "English",

volume = "19",

pages = "922--926",

journal = "ChemBioChem",

issn = "1439-4227",

publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

number = "9",

}

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 -

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

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this