N-二(4-乙基苯-二氨基甲酰基)甲基磷酸与稀土配合物的合成及其与DNA作用的电化学研究  

Synthesis and Interaction of N-Bis( 4-ethylbenzene-diamidoformyl) methyl Phosphonic Acid and Eu( Ⅲ) Complex with DNA

作　　者：宋盼[1] 周通[1] 杨水兰[1] 杨天林[1] 纳鹏军[1] 倪刚[1] 

机构地区：[1]宁夏大学化学化工学院,宁夏银川750021

出　　处：《化学试剂》2016年第12期1141-1148,1156,共9页Chemical Reagents

基　　金：国家自然科学基金资助项目(21261018;21567021);教育部科学基金重点资助项目(208195)

摘　　要：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.

关 键 词：铕配合物 插入模式 DNA电化学传感器 

分 类 号：O614.3[理学—无机化学] O641.4[理学—化学]