用于检测氨基葡萄糖的金属-有机大环化合物的合成及光谱分析

用于检测氨基葡萄糖的金属-有机大环化合物的合成及光谱分析 Synthesis and Spectral Analysis of Metal-organic Macrocyclic Compound for Detection of Glucosamine 吴红梅 WU Hong-mei first-author 郭宇 GUO Yu 曹建芳 CAO Jian-fang 陈强强 CHEN Qiang-qiang 张志华 ZHANG Zhi-hua 辽宁工业大学 化学与环境工程学院, 辽宁 锦州 121001 辽宁工业大学 化学与环境工程学院, 辽宁 锦州 121001 School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China 以5-氨基异酞酸为初始原料，通过酯化、肼解和席夫碱等反应合成了双三齿配体LD，并通过与锌离子（Zn 2+ ）自组装构筑了金属（锌）-有机大环化合物LD-Zn，利用紫外-可见光谱、核磁、电喷雾质谱等表征手段研究了LD-Zn对氨基葡萄糖的识别作用。核磁光谱和电喷雾质谱测试表明，氨基葡萄糖分子能够进入到大环LD-Zn内部，并且LD-Zn以1：1的比例包合了氨基葡萄糖分子。紫外-可见光谱表明，当向LD-Zn中加入氨基葡萄糖后，373 nm处的吸收峰强度增加，269 nm和303 nm处的吸收峰强度降低，平衡常数 K 达到4.1910 3 L/mol，最低检测限为5.010 -6 mol/L。通过对比测试发现，LD-Zn只对氨基葡萄糖有紫外光谱响应，而对葡萄糖和三乙胺无任何响应，说明氨基葡萄糖的结构与大环化合物LD-Zn的空腔更匹配，LD-Zn对氨基葡萄糖的识别不是单纯羟基（氢键）或者氨基（碱性）引起的，而是由LD-Zn限域的空腔效应和氨基的氢键协同作用实现了对氨基葡萄糖的识别。 Double-tridentate ligand LD was synthesized by 5-aminophthalic acid through esterification, hydrazinolysis and Schiff's base reactions. Then, a novel metal-organic macrocyclic LD-Zn was built by the assembly of LD and zinc ions for the recognition of glucosamine. The detection mechanism of glucosamine with LD-Zn was studied by UV-Vis, 1 H NMR and ESI-MS. The results of 1 H NMR and ESI-MS indicate that the glucosamine molecules could enter the LD-Zn. Moreover, 1:1 stoichiometric host-guest complexation between glucosamine and LD-Zn was formed. UV-Vis spectra show that the intensity of the absorption peak at 373 nm increased significantly after addition of glucosamine into LD-Zn. However, the absorption intensity at 269 nm and 303 nm decreases. The equilibrium constant K reaches 4.1910 3 L/mol, and the minimum detection limit is 5.010 -6 mol/L. For comparison, the detection tests of glucose and triethylamine with LD-Zn were carried out. The UV-Vis spectra do not show any response when glucose and triethylamine are added to LD-Zn. These results indicate that the structure of glucosamine is more compatible with the cavity of the macrocycle LD-Zn compared to glucose and triethylamine. The recognition of glucosamine by using LD-Zn is not attributed to pure hydroxyl(hydrogen bonding) or amino(alkaline), it is mainly caused by the joint effect of confined cavity of LD-Zn molecular and hydrogen bonds of amino. 氨基葡萄糖 大环化合物 光谱分析 检测 glucosamine macrocyclic compound spectral analysis detection ZAHEDIPOUR F, DALIRFARDOUEI R, KARIMI G, et al.. Molecular mechanisms of anticancer effects of glucosamine[J]. Biomed. Pharmacot., 2017, 95:1051-1058. ZHANG P, ROYTRAKUL S, SUTHEERAWATTANANONDA M. Production and purification of glucosamine and angiotensin-I converting enzyme (ACE) inhibitory peptides from mushroom hydrolysates[J]. J. Funct. Foods, 2017, 36:72-83. DALIRFARDOUEI R, KARIMI G, JAMIALAHMADI K. Molecular mechanisms and biomedical applications of glucosamine as a potential multifunctional therapeutic agent[J]. 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HE C, LIN Z H, HE Z, et al.. Metal-tunable nanocages as artificial chemosensors[J]. Angew. Chem. Int. Ed., 2008, 47(5):877-881. 10.3788/fgxb20183908.1163 O433.5 国家自然科学基金（21601075，21606118）;辽宁省自然科学基金（2015020249）;辽宁省高校基本科研项目（JZL201715403）资助 Supported by National Natural Science Foundation of China(21601075,21606118);Natural Science Foundation of Liaoning Province(2015020249);Fundamental Research Funds for The Universities of Liaoning Province(JZL201715403) 2018-01-24 2018-05-20 2018-08-05 2020-08-11 8 39