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[Ru(TAP)₂(dppz)]²⁺:一种DNA嵌入复合物,它在水中强烈发光,并与5'-单磷酸鸟苷发生光诱导质子耦合电子转移。

[Ru(TAP)2(dppz)]2+: a DNA intercalating complex, which luminesces strongly in water and undergoes photo-induced proton-coupled electron transfer with guanosine-5'-monophosphate.

作者信息

Ortmans Isabelle, Elias Benjamin, Kelly John M, Moucheron Cécile, Kirsch-DeMesmaeker Andrée

机构信息

Service de Chimie Organique et Photochimie, CP 160/08, Université Libre de Bruxelles, 50 Avenue F. D. Roosevelt, B-1050 Bruxelles, Belgium.

出版信息

Dalton Trans. 2004 Feb 21(4):668-76. doi: 10.1039/b313213g. Epub 2004 Jan 19.

Abstract

The lowest excited state of [Ru(TAP)2(dppz)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene, dppz = dipyrido[3,2-a:2',3'-c]phenazine) 1 is strongly luminescent, even in water, and very oxidizing. Therefore it is able to oxidise not only guanosine-5'-monophosphate (GMP), as demonstrated by laser flash photolysis, but also guanine-containing polynucleotides such as calf thymus DNA and [poly(dG-dC)]2. The luminescence quenching was found to be faster in H2O than in D2O, as is the back reaction, indicating that both processes probably proceed by proton-coupled electron transfer. These properties, that are controlled by the triplet MLCT state in which the charge has been transferred from the Ru to a TAP ligand, contrast with those of the well known [Ru(phen)2(dppz)]2+ 2.

摘要

[Ru(TAP)2(dppz)]2+(TAP = 1,4,5,8 - 四氮杂菲,dppz = 二吡啶并[3,2 - a:2',3'- c]吩嗪)1的最低激发态即使在水中也具有很强的发光性,且具有很强的氧化性。因此,如激光闪光光解所证明的,它不仅能够氧化鸟苷 - 5'- 单磷酸(GMP),还能氧化含鸟嘌呤的多核苷酸,如小牛胸腺DNA和[聚(dG - dC)]2。发现发光猝灭在H2O中比在D2O中更快,逆反应也是如此,这表明这两个过程可能都是通过质子耦合电子转移进行的。这些由三重态MLCT态控制的性质,其中电荷已从Ru转移到TAP配体,与著名的[Ru(phen)2(dppz)]2+ 2的性质形成对比。

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