The Structural Effect of Methyl Substitution on the Binding of Polypyridyl Ru-dppz Complexes to DNA
The Structural Effect of Methyl Substitution on the Binding of Polypyridyl Ru-dppz Complexes to DNA
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DOI：
10.1021/om501208x
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发表时间：
2015-06-08
期刊：
影响因子：
2.8
通讯作者：
Cardin, Christine J.
中科院分区：
文献类型：
--
作者：
Hall, James P.;Beer, Hanna;Cardin, Christine J.
多吡啶基钌配合物是近年来研究较多的一类具有物理化学性质的金属配合物。它们可以作为DNA的探针，结合时发射显著增强，并且可以在光照射时诱导DNA损伤。因此，合成和表征与DNA结合的新型复合物是一个激烈的研究活动领域。虽然非常需要了解衍生物与母体化合物的结合情况，但这一信息可能难以获得。本文报道了三种新的甲基化配合物[Ru（TAP）（2）（dppz-10-Me）]Cl-2、[Ru（TAP）（2）（dppz-10，12-Me-2）]Cl-2和[Ru（TAP）（2）（dppz-11-Me）]Cl-2（TAP = 1，4，5，8-tetraazaphenanthrene; dppz = dipyrido[3，2-a：2 '，3'-c]phenazine）的合成，并通过使用原子分辨率X射线晶体学研究了DNA结合的结果。我们发现，甲基基团位于离散的位置与一个完整的方向偏好。这可能有助于解释类似的[Ru（phen）（2）（dppz）]（2+）衍生物在溶液中的猝灭行为。
Polypyridyl ruthenium complexes have been intensively studied and possess photophysical properties that are both interesting and useful. They can act as probes for DNA, with a substantial enhancement in emission when bound, and can induce DNA damage upon photoirradiation. Therefore, the synthesis and characterization of DNA binding of new complexes is an area of intense research activity. While knowledge of how the binding of derivatives compares to that of the parent compound is highly desirable, this information can be difficult to obtain. Here we report the synthesis of three new methylated complexes, [Ru(TAP)(2)(dppz-10-Me)]Cl-2, [Ru(TAP)(2)(dppz-10,12-Me-2)]Cl-2, and [Ru(TAP)(2)(dppz-11-Me)]Cl-2 (TAP = 1,4,5,8-tetraazaphenanthrene; dppz = dipyrido[3,2-a:2',3'-c]phenazine), and examine the consequences for DNA binding through the use of atomic-resolution Xray crystallography. We find that the methyl groups are located in discrete positions with a complete directional preference. This may help to explain the quenching behavior found in solution for analogous [Ru(phen)(2)(dppz)](2+) derivatives.