Enhanced Photoinduced Electron Transfer Through a Tyrosine Relay in a De Novo Designed Protein Scaffold Bearing a Photoredox Unit and a FeIIS4 Site

被引：9

作者：

Tebo, Alison ^{[1
,2
]}

Quaranta, Annamaria ^{[3
]}

Pecoraro, Vincent L. ^{[2
]}

Aukauloo, Ally ^{[3
,4
]}

机构：

[1] Univ Michigan, Program Chem Biol, Ann Arbor, MI 48109 USA

[2] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

[3] Univ Paris Saclay, Inst Biol Integrat Cellule, CEA, Gif Sur Yvette, France

[4] Univ Paris Saclay, Inst Chim Mol & Mat Orsay, Orsay, France

来源：

CHEMPHOTOCHEM | 2021年 / 5卷 / 07期

基金：

美国国家卫生研究院;

关键词：

amino acids; electron relay; electron transfer; protein design; photoredox catalysis; REDOX PROPERTIES; COMPLEX; MIMICS;

D O I：

10.1002/cptc.202100014

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Electron transfer (ET) processes in biology over long distances often proceed via a series of hops, which reduces the distance dependence of the rate of ET. The protein matrix itself can be involved in mediating ET directly through the participation of redox-active amino acids. We have designed an electron transfer chain incorporated into a de novo protein scaffold, which is capable of photoinduced intramolecular electron transfer between a photoredox unit and a (FeS4)-S-II site through a tyrosine amino acid relay. The kinetics were characterized by nanosecond laser pulse photolysis and revealed that electron transfer from [Ru(III)bpymal](3+) proceeds most efficiently via a tyrosine located similar to 16 angstrom from Rubpymal (bpymal=1-((1-([2,2 '-bipyridin]-4-yl)-1H-1,2,3-triazol-4-yl)methyl)-1H-pyrrole-2,5-dione). Removal of the tyrosine as the electron relay station results in a 20-fold decrease in the apparent rate constant for the electron transfer.

引用

页码：665 / 668

页数：4

共 28 条

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