【作者】 孙伟；

【导师】 孙世国；

【作者基本信息】 大连理工大学 ， 应用化学， 2015， 硕士

【摘要】 电化学发光(ECL)也称电致化学发光,是一种将电化学与化学两种发光方法相结合的技术,通过在电极表面发生的电化学氧化还原反应,产生一种特殊物质从而与体系中的其它组分发生反应,产生一种光辐射,出现发光现象。传统的ECL体系主要是利用过渡金属配合物与还原剂三丙胺(TPA)、2.(二丁基氨基)乙醇等的分子间作用,这种分子间作用会产生背景干扰,降低了检测的准确性。本文利用饱和碳链将钌、锇两种过渡金属连接,合成了异核双金属新型标记物Ru-Cn-Os,其中n=10,14,并且对其可见光吸收光谱、发射光谱、电化学性能以及ECL性能进行了分析。当使用Xex=456nm对配合物激发,Ru-Cn-Ir可以观察到双发射性能,同时产生钌发光团(520 nm左右)和锇发光团(730nm左右)的发光。而且配合物Ru-C14-Os双发射ECL强度比值(I731 nm/I618nm)与TPA浓度呈现良好的线性,通过这种比率检测的方法,能够彻底消除背景干扰。在此基础上,进一步合成了利用饱和碳链将钌、铱两种过渡金属连接的异核双金属新型标记物Ir-Cn-Ru,其中n=10,12,14。并且对其可见光吸收光谱、发射光谱以及ECL性能进行了详细的分析。当扫描电压在0.5-0.95 V范围内,钌发光团与铱发光团的发光光谱强度比值(I618 nm / I543 nm)与扫描电压呈现良好的线性。当扫描电压在0.95-1.6 V范围内,铱发光团绿色发光完全被钌发光团的红色发光掩盖,而钌发光团红色发光强度(I618nm)与扫描电压呈现良好的线性关系,利用扫描电势的改变实现了两种颜色的“开.关”,在降低医疗检测成本、开发电子发光器件方面具有潜在的应用价值。更多还原

【Abstract】 Elctrochemiluminescence (ECL) is a kind of technology that combine the electrochemical and chemical luminescence method, which produces a kind of light irradiation and luminescence, through electrochemical reaction occurred on the electrode surface, generating a special material by reaction with other components in the system. The traditional ECL system is mainly the use of transition metal complexes with a reducing agent such as propylamine (TPA),2-(two amino propylamine butyl alcohol) (DBAE), etc. Howere, the intermolecular interaction can produce background interference, reduce the detection accuracy.In order to solve the problem, [(bpy)2Ru(bpy)(CH2)n(bpy)Os(bpy)2]4+(where bpy is 2,2’-bipyridinyl, n=10,14), shorted as Os-C10-Ru and Os-C14-Ru, have been synthesized, in which two hererodinuclear osmium-ruthenium ECL labels were linked together through different saturated carbon chain. Their absorption and luminescence, electrochemical and ECL properties have been studied. Both Os-Cio-Ru and Os-C14-Ru showed dual luminescence and dual ECL, especially, a good linear calibration curve between the ECL intensity ratio (I731 nm/I618nm) and TPA concentration can be established over a TPA concentration range of 1 mM to 12 mM, providing a general methodology to eliminate the ECL background noise aroused by TPA, which improved the detection efficiency and lead to some fundamental understandings for dual emission and ratio ECL detection method.Then, a series of heterodinuclear complexes [(bpy)2Ru(bpy)(CH2)n(bpy)Ir(df-ppy)2]3+ (where bpy is 2,2’-bipyridyl, df-ppy is 2-(2,4-difluorophenyl)pyridine, n= 10,12,14) have been synthesized. Both red (from Ru moiety) and green (from Ir moiety) ECL can be acquired simultaneously through alternating of the scanning potentials. When the scanning voltage is in the range of 0.5-0.95 V, photoluminescence intensity ratio of ruthenium and iridium (I6i8nm/ I543 nm) and the scanning voltage showed a good linear relationship. When the scanning voltage is in the range of 0.95-1.6 V, the green emitting of iridium was completely quenched by the red emission of ruthenium, and a good linearity can be observed between the red emission intensity (I618 nm) and the scanning voltage, the two colors can be easily turned "on-off through alternating the scanning potential, which has the advantages in reducing medical cost and the utilization of electronic light emitting device.更多还原