Photo-reduction of polyazaaromatic Ru(II) complexes by biomolecules and possible applications
Photo-reduction of polyazaaromatic Ru(II) complexes by biomolecules and possible applications
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DOI：
10.1016/j.ccr.2005.11.011
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发表时间：
2006-07-01
影响因子：
20.6
通讯作者：
Kirsch-De Mesmaeker, Andree
中科院分区：
文献类型：
--
作者：
Elias, Benjamin;Kirsch-De Mesmaeker, Andree
含有多氮杂芳族配体如TAP（1，4，5，8-四氮杂菲）和HAT（1，4，5，8，9，12-六氮杂苯并菲）的Ru（II）配合物的一个重要性质是（MLCT）-M-3（金属到配体电荷转移）状态的非常高的氧化电位。因此，在光照下，它们甚至能够从相当差的电子供体中提取电子。在这项工作中，我们将展示如何利用这一特性的应用程序的光诱导电子转移这些激发复合物和生物聚合物，如DNA，寡核苷酸和oligopeptides.的电荷转移过程的后果之一是质粒DNA的光裂解，证明了几年前通过琼脂糖凝胶电泳和最近检测和定量的AFM。光诱导电子转移的另一个作用是形成金属络合物与寡核苷酸的鸟嘌呤单元或与寡肽的色氨酸部分的光加合物。在与鸟嘌呤核碱基的光加合物中，在多氮杂芳族配体之一与鸟嘌呤碱基之间形成共价键，而不破坏金属离子周围的配体球。有趣的是，可以利用这些光加合物的形成来光交联两个单链寡核苷酸。这种通过金属配合物的光交联可能导致在生物诊断测试中的应用，并可能在体内的基因光疗领域。(c)2005 Elsevier B. V.保留所有权利。
An important property of the Ru(II) complexes that contain polyazaaromatic ligands such as TAP (1,4,5,8-tetraazaphenanthrene) and HAT (1,4,5,8,9,12-hexaazatriphenylene) is the very high oxidation potential of the (MLCT)-M-3 (Metal to Ligand Charge Transfer) state. Therefore, under illumination, they are able to abstract an electron even from rather poor electron donors. In this work, we show how it is possible to take advantage of this property for applications of photo-induced electron transfer between these excited complexes and biopolymers such as DNA, oligonucleotides and oligopeptides.One of the consequences of the charge transfer processes is photocleavage of plasmid DNA, demonstrated some years ago by agarose gel electrophoresis and more recently detected and quantified by AFM. Another effect of the photo-induced electron transfer is the formation of photoadduct(s) of the metal complex with the guanine units of oligonucleotides or with the tryptophan moieties of oligopeptides. In the photo-adducts with the guanine nucleobases, a covalent bond is formed between one of the polyazaaromatic ligands and the guanine base without destruction of the ligands sphere around the metal ion. Interestingly, the formation of these photo-adducts can be exploited in order to photo-crosslink two single-stranded oligonucleotides. Such photo-crosslinking via the metal complexes could lead to applications in biological diagnostic tests and possibly in vivo in the area of gene phototherapy. (c) 2005 Elsevier B.V. All rights reserved.