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Laboratoire d'Electrochimie Moleculaire, LEM, Paris

UMR CNRS - Université Paris Diderot - Paris France

   
 
Master Frontiers in Chemistry | UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie Université de Paris Master Chimie Sorbonne Paris Cité UFR de Chimie - Université Paris Diderot - Paris 7 CNRS - Institut de chimie
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Université Paris Diderot
Université de Paris CNRS, Centre National de la Recherche Scientifique
 
 


Le LEM - Publications: Abstracts

Publication 632

Chem. Rev. 108, 2622– 2645, 2008.
DOI: 10.1021/cr0680787
 

Electron transfer in DNA and in DNA related biological processes. Electrochemical insights

Fabien Boussicault and Marc Robert

Laboratoire d’Electrochimie Moléculaire, Université Paris Diderot Paris7, UMR CNRS 7591, 2 place Jussieu, 75251 Paris Cedex 05, France,

 


Introduction

Since the pioneering work of Berg, Paleček and Elving many studies have been devoted to the electrochemical investigation of the electrical properties of nucleic acids and DNA strands. Based on polarographic methods, these early works involved mercury electrodes, with which nucleic acids strongly interact, thus complicating analysis of the experimental signals. With the development of molecular electrochemistry, solid electrodes (metals, carbon-based electrodes, and semiconductors, for example, indium tin oxide) were later introduced. Interactions of these materials with biological molecules are therefore lessened or to some extent controlled, opening the door toward assembly-controlled nanometric architectures at the interface between electrode and solution. It has been demonstrated that both holes and electrons can migrate through the DNA helix over distances. Consequently, electrochemistry of nucleic acids and DNA constituents at electrodes may provide valuable insights into the mechanisms involved in these processes, complementary to photochemical methods, product studies, quantum calculations, and modeling. Such electrochemical studies may further improve the understanding of biological reactions such as aging, DNA oxidative lesion formation, and DNA repair. Charge transfer through DNA could also be exploited in the design of electrochemical DNA-based biosensors. For example, sensitive and selective sensors based on a single-strand DNA recognition interface to a sample containing a sequence target and a redox-active intercalator probe have been proposed. Description of this type of sensors stands beyond the scope of this review.

First, we intend to review electrochemical reduction and oxidation of DNA bases and constituents. Despite many works in this field and several recent reviews, it appears that mechanistic issues remain unsolved, in particular in the understanding of excess electron transfer through DNA, as well as in the understanding of proton-coupled electron transfer aspects of base oxidation (hole transfer). Second, we will review charge transfer processes through oligonucleotides and DNA duplexes assembled onto electrodes, a field within which the contribution of electrochemistry is of importance. Finally, we will discuss electrochemical input into biological aspects of electron transfer reactions in DNA repair related processes. Emphasis will be on the catalytic repair of ultraviolet-induced DNA lesions by redox photolyase enzymes, and on the detection of oxidative lesions involving charge transfer through DNA in glycosylase enzymes (MutY and EndoIII).

 
   
 
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