合成了一种结构易控、化学稳定性好、呈电中性及电化学活性高的含磷三足配体N-二(4-乙基苯-二氨基甲酰基)甲基磷酸及其稀土Eu(Ⅲ)配合物,采用了^1HNMR、^(13)CNMR、红外光谱、元素分析、差热-热重及连续物质的量比法对其组成进行表征并推断其结构,确定了配体与稀土离子形成了1∶1型配合物Eu(pic)3L。在进行配合物与DNA相互作用实验中,考察了扫描速率ν、p H、配合物浓度和离子强度因素对其的影响。实验结果表明,Eu(pic)3L与DNA碱基进行相互结合从而形成非电活性物质,使游离的Eu(pic)3L浓度降低,Eu(pic)3L的峰电流减小,说明Eu(pic)3L与DNA的相互作用是以嵌插形式结合的。根据Eu(pic)3L的电化学活性研究了以该配合物为杂交探针在DNA电化学传感器方面的应用。结果发现,Eu(pic)3L在修饰单链DNA的电极检测作用时,并无明显的电化学信号响应;检测杂交双链DNA时,却出现了明显信号,与此同时Eu(pic)3L的DNA电化学传感器对DNA的互补、碱基错配及非互补序列均有良好的识别功能。
A novel of water-soluble phosphorus-containing tripod ligand N-bis( 4-ethylbenzene-diamidoformyl) methyl phosphonic acid and its europium complex has been synthesized and confirmed by nuclear magnetic resonance( NMR),infrared spectroscopy( IR),elemental analysis( EA),thermal gravimetric and thermal gravimetry and differential scanning calorimetry( TG-DSC) and continuous molar ratio method. The ligand and its rare earth picrate had formed a 1∶ 1 complex( Eu( pic)3L). The interaction between complex and DNA was investigated by cyclic voltammetry. The influences of p H,scanning speed,ionic strength and concentration of complex on the interaction were described. The results indicated that complex can interact with the bases of DNA to form non-electroactive complex,which can decrease the anodic peak current of complex. The complex react with DNA mainly in a mode of intercalation. The electrochemical sensor performance of( Eu( pic)3L) were observed,there was no obvious electrochemical response for the single-strand DNA,while with the obvious electrochemical response for the double-stranded DNA. The hybridization specificity experiments further indicated that the biosensor could well discriminate the complementary sequences from the basemismatched and the non-complementary sequences.