乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控
Copper(Ⅱ)-Tuned Photoluminescence of [Ru(bpy)2(dppz)]2+ Enhanced by SDS and DNA in Ethanol and Tris-water Mixtures
作者单位E-mail
陈琳琳 华南师范大学化学与环境学院,广州 510006  
刘俊辰 华南师范大学化学与环境学院,广州 510006  
江臻燊 华南师范大学化学与环境学院,广州 510006  
甘桂莲 华南师范大学化学与环境学院,广州 510006  
李红 华南师范大学化学与环境学院,广州 510006 lihong@scnu.edu.cn 
摘要: 应用荧光光谱、荧光显微镜和伏安法研究了乙醇/水体系中Cu(Ⅱ)对十二烷基硫酸钠(SDS)和鱼精DNA增强[Ru(bpy)2(dppz)]2+(bpy=2,2'-联吡啶,dppz=邻联二吡啶[3,2-a:2',3'-c]吩嗪)光致发光的调控。结果表明,在乙醇/三羟甲基氨基甲烷(Tris)-水(V乙醇:VTris=1:5)体系中,DNA和阴离子表面活性剂SDS均能增强[Ru(bpy)2(dppz)]2+的光致发光,其与[Ru(bpy)2(dppz)]2+间的键合常数分别为5.5×105和4.2×102 L·mol-1;Cu(Ⅱ)离子能通过DNA和SDS介导的光诱导电子转移淬灭乙醇/水溶液中[Ru(bpy)2(dppz)]2+的光致发光,DNA介导的Stern-Volmer淬灭常数为2.0×105 L·mol-1,远远大于SDS介导的淬灭常数(9.0×103 L·mol-1)。此外,结合SDS、DNA和Cu(Ⅱ)对[Ru(bpy)2(dppz)]2+在铟锡氧化物(ITO)电极上发生的氧化还原反应的影响,进一步探讨了乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控机理。该研究有助于更好地理解DNA嵌入剂的发光和淬灭机制,为生物分子光开关的构建提供新思路。
关键词: 多吡啶钌(Ⅱ)配合物  DNA  表面活性剂  铜(Ⅱ)离子  光致发光
基金项目: 国家自然科学基金(No.21271075)和广东省自然科学基金(No.10351063101000001)资助项目。
Abstract: The copper(Ⅱ)-tuned photoluminescence of [Ru(bpy)2(dppz)]2+ (bpy=2,2'-bipyridine and dppz=dipyrido[3,2-a:2',3'-c]phenazine) enhanced by DNA and sodium dodecylsulfate (SDS) has been investigated in ethanol and water mixtures by means of fluorescence spectroscopy, fluorescence microscopic imaging and voltammetry. The photoluminescence of [Ru(bpy)2(dppz)]2+ in the ethanol/Tris-water mixed system (VEthanol:VTris=1:5) is enhanced by DNA and anionic surfactant SDS, whose binding constants with the Ru(Ⅱ) complex are 5.5×105 and 4.2×102 L·mol-1, respectively. The presence of Cu(Ⅱ) ions can quench the photoluminescence of [Ru(bpy)2(dppz)]2+ in the DNA-containing mixed system via the DNA-mediated photoinduced electron transfer, in which the Stern-Volmer constant is 2.0×105 L·mol-1, being far larger than that in the SDS-containing system (9.0×103 L·mol-1). In addition, combined with the effects of SDS, DNA and Cu(Ⅱ) ions on the redox reactions of [Ru(bpy)2(dppz)]2+ on an indium-tin oxide (ITO) electrode, the copper(Ⅱ)-tuned mechanism for the photoluminescence of [Ru(bpy)2(dppz)]2+ enhanced by DNA and SDS is further explored. This study not only helps us better understand the luminescence and quenching mechanisms of DNA intercalators, but also provides a new idea for the fabrication of biomolecular light switches.
Keywords: polypyridyl ruthenium(Ⅱ) complex  DNA  surfactant  copper(Ⅱ) ion  photoluminescence
投稿时间:2012-12-19 修订日期:2013-02-06
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陈琳琳,刘俊辰,江臻燊,甘桂莲,李红.乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控[J].无机化学学报,2013,29(6):1176-1184.
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