Trans-Dioxorhenium(V)-Mediated Electrocatalytic Oxidation of DNA at Indium Tin-Oxide Electrodes: Voltammetric Detection of DNA Cleavage in Solution

doi:10.1021/ic00104a058

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Title:	Trans-Dioxorhenium(V)-Mediated Electrocatalytic Oxidation of DNA at Indium Tin-Oxide Electrodes: Voltammetric Detection of DNA Cleavage in Solution
Authors:	Johnston, Dean H.;Cheng, Chien-chung;Campbell, Katherine J.;Thorp, H. Holden
Contributors:	淡江大學化學學系
Date:	1994-12
Issue Date:	2011-10-15 23:40:10 (UTC+8)
Publisher:	American Chemical Society
Abstract:	The oxidative electrochemistry of truns-[Re(0)2(4-OMe-py)4]+ in the presence of DNA has been studied. The complex exhibits a reversible oxidation at E1/2(VW) = 1.00 V (vs Ag/AgCl) in buffer or in the presence of poly(dA)poly(dT). However, in the presence of calf thymus DNA or poly(dG)poly(dC), a dramatic catalytic enhancement is observed. An identical result is obtained with Fe(S-C1-~hen)3~+ (E1/2(IIIAI) = 1.02 V), but no electrocatalytic enhancement is observed with truns-[Re(0)2(py)2(dmap)2]+ (E112 = 0.90 V). Electrophoresis of plasmids electrolyzed at 1.2 V in the presence of trans-[Re(0)2(4-OMe-py)4]+ show relaxation from form I to form 11, and analogous reactions with 5'-end 32P-labeled synthetic oligonucleotides show piperidine-labile cleavage specifically at guanine. The combined results point to an electrocatalytic mechanism where the oxidized metal complex oxidizes guanine in DNA by one electron via an efficient, outer-sphere mechanism. Moreover, the experiments demonstrate a potential for the one-electron oxidation of guanine in double-helical DNA at neutral pH of between 0.90 and 1.00 V. This result should provide insight into the mechanisms of DNA oxidation by chemical agents and by ionizing radiation.
Relation:	Inorganic chemistry 33(26), pp.6388–6390
DOI:	10.1021/ic00104a058
Appears in Collections:	[Graduate Institute & Department of Chemistry] Journal Article

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