Directional Preference of DNA-Mediated Electron Transfer in Gold-Tethered DNA Duplexes: Is DNA a Molecular Rectifier?

被引：22

作者：

Kekedy-Nagy, Laszlo ^{[1
]}

Ferapontova, Elena E. ^{[1
]}

机构：

[1] Aarhus Univ, Interdisciplinary Nanosci Ctr iNANO, Gustav Wieds Vej 1590-14, DK-8000 Aarhus C, Denmark

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 10期

基金：

新加坡国家研究基金会;

关键词：

DNA; electrocatalysis; electron transfer; gold electrodes; Methylene Blue; METHYLENE-BLUE; CHARGE; CONDUCTANCE; TRANSPORT; DYNAMICS; END; ELECTROCHEMISTRY;

D O I：

10.1002/anie.201809559

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Electrical properties of self-assembling DNA nanostructures underlie the paradigm of nanoscale bioelectronics, and as such require clear understanding. DNA-mediated electron transfer (ET) from a gold electrode to DNA-bound Methylene Blue (MB) shows directional preference, and it is sequence-specific. During the electrocatalytic reduction of [Fe(CN)(6)](3-) catalyzed by DNA-bound MB, the ET rate constant for DNA-mediated reduction of MB reaches (1.32 +/- 0.2)10(3) and (7.09 +/- 0.4)10(3) s(-1) for (dGdC)(20) and (dAdT)(25) duplexes. The backward oxidation process is less efficient, making the DNA duplex a molecular rectifier. Lower rates of ET via (dGdC)(20) agree well with its disturbed pi-stacked sub-molecular structure. Such direction- and sequence-specific ET may be implicated in DNA oxidative damage and repair, and be relevant to other polarized surfaces, such as cell membranes and biomolecular interfaces.

引用

页码：3048 / 3052

页数：5

共 58 条

[1] Unmediated by DNA Electron Transfer in Redox-Labeled DNA Duplexes End-Tethered to Gold Electrodes [J].