三元有机-钴大环化合物的组装及其识别性能

Assembly of Co-based Organic-metal Cyclohelicate Compound for Recognition of Glutathione

以5-氨基-1,3-苯二甲酸为母体,通过系列衍生引入苄基和喹啉基团合成配体HL[5-N,N-二苄基氨基-N,N＇-双（2-喹啉亚甲基）-1,3-苯二甲酰肼],其与钴离子自组装构筑了有机-钴三元大环化合物HL-Co。利用电喷雾质谱和紫外光谱考察了HL-Co对谷胱甘肽的识别过程与传感作用。结果表明,HL-Co在溶液中可形成稳定的[3＋3]大环结构,并且能够以物质的量比1∶1包合谷胱甘肽分子。通过紫外滴定测试发现,当向HL-Co中加入谷胱甘肽后,在320 nm处的吸光度逐渐增加,而425 nm处吸光度逐渐减弱,直至平衡,等吸收点为357 nm。而且,采用Benesi-Hildebrand数据拟合得到平衡常数lgK（GSH）=4.41,对谷胱甘肽识别的最低检测限达到1.0×10^（–5） mol/L,实现了对谷胱甘肽的有效识别。

A novel organic-cobalt ternary macrocyclic compound HL-Co was constructed by cobalt ion with 5-N,N-dibenzylamino-N1,N＇3-bis（quinolin-2-ylmethylene） isophthalohydrazide, which was synthesized by introduction of quinoline and dansylamide groups into 5-aminoisophthalic acid. The recognition process and sensing effect of glutathione（GSH） were studied with HL-Co by electrospray ionization mass spectrometry（ESI-MS） and ultraviolet spectroscopy（UV-vis）. The results showed that HL-Co formed a stable [3＋3] macrocyclic structure in solution and could encapsulate glutathione at a molar ratio of 1∶1. The absorbance at 320 nm was gradually increased when glutathione was added into the solution of HL-Co, while the absorbance at 425 nm gradually decreased until the equilibrium. The isosbestic point occurred at a wavelength of 357 nm. The equilibrium constant, lg K（GSH）=4.41, was calculated by using BenesiHildebrand plot. The minimum detection limit of glutathione was 1.0×10^（–5） mol/L, which indicated that HL-Co had good recognition of glutathione.