新型铕、铽配合物的合成及电致化学发光性能与应用研究

Due to its excellent luminescent properties, the rare earth complexes have been extensively applied in the Electrogenerated Chemiluminescence (ECL) field. In this proposal, a series of binary or ternary Eu(Ⅲ) and Tb(Ⅲ) complexes with different structures will be designed and synthesized using amino acids, aromatic carboxylic acids, and β-diketones as ligands. Using cyclic voltammetry (CV) method, the ECL properties of these complexes in aqueous solution will be investigated at conventional electrodes, such as gold electrode, platinum electrode and glassy carbon electrode, or electrodes modified with these complexes . Based on the experimental results, some Eu(Ⅲ) and Tb(Ⅲ) complexes with excellent luminescent properties will be chosed as new luminescence materials to be used in the ECL systems, and the ECL properties of the complexes with different ligands will also be investigated, which can provide a theoretical guide for the further study of their applications. Several new methods with high sensitivity for the detection of Quinolone drugs or some biochemicals (e.g. DNA) will be established by investigating the effect of quinolones ligands on the ECL properties of the binary rare earth complexes or marking the Double functional group ligands of the rare earth complexes. Furthermore, this new methodology will be used to the detection of real samples. The successful implementation of this work can not only provide new materials for ECL, but also establish several new ECL systems and expand the applications of ECL methodology.

稀土配合物因其优良的发光性能，在电致化学发光(ECL)领域具有广阔的应用前景。本项目以稀土铕(Ⅲ)、铽(Ⅲ)为中心离子，用氨酸类、芳香羧酸类和β-二酮类等络合剂作为配体来设计合成系列结构不同的二元或三元稀土配合物；采用循环伏安方式，在水相中探测该系列配合物的ECL性能，筛选出ECL性能优良的稀土配合物，为建立ECL体系提供新型发光材料；探究不同配体结构对合成产物ECL性能影响的规律，为进一步研究其应用提供理论依据。通过考察喹诺酮类药物对合成的二元稀土配合物ECL性能的影响或采用稀土配合物中的双功能团配体标记的方式，尝试建立喹诺酮类药物或一些生化物质（如DNA等）高灵敏度定量检测的新方法，并应用于实际样品的分析检测。该项目的成功实施不仅可以为ECL提供新材料，而且可以构建一些ECL的新体系，拓展ECL的应用范围。

本项目以稀土元素铽(Tb)、铕(Eu)为中心离子，分别用吡啶系列、噻吩系列、喹啉系列、吡嗪系列、萘系列、苯二甲酸系列、β-二酮类化合物为配体，主要采用水浴加热法合成了系列二元或三元稀土配合物。通过元素分析、滴定分析、IR、X-单晶衍射等分析手段进行了表征，推测了其可能的分子式或结构式。较为详细地研究了合成的稀土配合物在不同介质中或加入常见共反应剂时的电致化学发光(ECL)性能，采用CV、荧光光谱和ECL光谱等分析手段对ECL机理进行了推测，初步得出一些配体结构与ECL性能之间关系的结论，构建了一些ECL新体系，利用一些生化物质、药物或重金属离子对其ECL的增敏或猝灭作用，实现了岩白菜素、烟酸、2,6-吡啶二甲酸、鸟嘌呤(Guanine)、诺氟沙星、盐酸左氧氟沙星、Cd2+等物质的定量检测。相关部分研究工作已在Journal of Luminescence， Journal of Electroanalytical Chemistry，Luminescence，Electrochimica Acta，安徽师范大学学报（自然科学版）等杂志上发表学术论文8篇。