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DNA 结合的[Ru(bpy)₂(mbpibH2)]²+ 薄膜的制备及其通过铜(II)离子和 EDTA 的双模发光调控。

Preparation of a DNA-bound [Ru(bpy)₂(mbpibH2)]²+ film and its two-mode luminescence tuning by copper(II) ions and EDTA.

机构信息

Key Lab of Technology on Electrochemical Energy Storage and Power Generation in Guangdong Universities, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, PR China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2012 Nov;97:297-305. doi: 10.1016/j.saa.2012.06.016. Epub 2012 Jun 17.

DOI:10.1016/j.saa.2012.06.016
PMID:22771565
Abstract

An imidazophenanthroline-containing ruthenium(II) complex Ru(bpy)(2)(mbpibH2) (bpy=2,2'-bipyridine, mbpibH2=1,3-bis([1,10]phenanthroline[5,6-d]imidazol-2-yl)benzene) can bind DNA through groove-binding and/or non-classical intercalation modes, revealed by spectrophotometric methods, viscosity measurements and variable ionic strength experiments. On the basis of binding interactions between cationic Ru(bpy)(2)(mbpibH2) and anionic DNA at a molar ratio of 1:1, a yellow transparent cast film has been assembled on an indium-tin oxide (ITO) surface using a solution-based self-standing method. The prepared DNA-Ru(bpy)(2)(mbpibH2) film shows a bi-exponential luminescence decay with τ(1)=62.1 ns (8.0%) and τ(2)=594.5 ns (92.0%), whose lifetimes become much shorter than those of DNA-bound Ru(bpy)(2)(mbpibH2) in buffer solutions. The Ru(II) complex with a free bi-dentate coordination site in the DNA cast film shows tunable luminescence, quenched dynamically by Cu(2+) and restored by using EDTA to eliminate two modes of Cu(2+)-binding. The results from this study provide a significant foundation for better understanding the fabrication and modulation of a DNA-based solid luminescence device using the Ru(II) complexes as DNA-concentrating and signal-sensing agents.

摘要

一种含咪唑并菲咯啉的钌(II)配合物Ru(bpy)(2)(mbpibH2)(bpy=2,2'-联吡啶,mbpibH2=1,3-双([1,10]菲咯啉[5,6-d]咪唑-2-基)苯)可以通过光谱法、粘度测量和可变离子强度实验表明,通过沟结合和/或非经典嵌入模式结合 DNA。基于阳离子Ru(bpy)(2)(mbpibH2)与阴离子 DNA 之间的结合相互作用,在摩尔比为 1:1 的情况下,使用基于溶液的自支撑方法在铟锡氧化物(ITO)表面组装了黄色透明的铸造膜。制备的 DNA-Ru(bpy)(2)(mbpibH2)膜表现出双指数荧光衰减,τ(1)=62.1 ns(8.0%)和τ(2)=594.5 ns(92.0%),其寿命比缓冲溶液中 DNA 结合的Ru(bpy)(2)(mbpibH2)短得多。在 DNA 铸造膜中具有游离双齿配位位的 Ru(II)配合物表现出可调谐的发光,被 Cu(2+)动态猝灭,并通过使用 EDTA 消除两种 Cu(2+)结合模式来恢复。这项研究的结果为更好地理解使用 Ru(II)配合物作为 DNA 浓缩和信号传感剂的基于 DNA 的固态发光器件的制造和调制提供了重要基础。

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