Zn(Ⅱ)金属有机骨架作为基质金属蛋白酶模拟物催化水解微囊藻毒素-LR  

A Zn(Ⅱ)metal-organic framework as a matrix metalloproteinase mimic to catalyze the hydrolysis of microcystin-LR

作　　者：方艳芬 贺玉婷[1,2] 赵丽 牛慧斌 陈春城 李悦[3] 黄应平[2] FANG Yan-Fen;HE Yu-Ting;ZHAO Li;NIU Hui-Bin;CHEN Chun-Cheng;LI Yue;HUANG Ying-Ping(College of Materials and Chemical Engineering,China Three Gorges University,Yichang,Hubei 443002,China;Engineering Research Center of Eco-environment in Three Gorges Reservoir Region,Ministry of Education,Three Gorges University,Yichang,Hubei 443002,China;College of Chemistry,Nankai University,Tianjin 300071,China;Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]三峡大学材料与化工学院,宜昌443002 [2]三峡大学三峡库区生态环境教育部工程研究中心,宜昌443002 [3]南开大学化学学院,天津300071 [4]中国科学院化学研究所,北京100190

出　　处：《无机化学学报》2023年第12期2265-2278,共14页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22076098,22136003,22376118,21577078)、湖北省自然科学基金杰出青年项目(No.2023AFA054);地方高校能源和环境材料化学学科创新引智基地(No.D20015)资助。

摘　　要：以3-氨基-1,2,4-三氮唑-5-羧酸(Hatz)和1,3,5-苯三甲酸(H3btc)为配体,制备了模拟基质金属蛋白酶(MMPs)结构的纳米片状Zn(Ⅱ)金属有机骨架Zn-MOF-1-NS。Zn-MOF-1-NS能成功实现对微囊藻毒素(MC-LR)肽键的水解。在常温条件下,7.5 h内Zn-MOF-1-NS催化水解了82.6%的MC-LR(k=0.23 h^(-1)),远高于目前报道的具有最高水解效率的菱铁矿(k=0.04 h^(-1))。研究发现,在该体系中即使添加10倍剂量的腐殖酸,也不会显著阻碍MC-LR的水解,证明Zn-MOF-1-NS对MC-LR的水解具有显著的选择性。通过原位衰减全反射傅里叶变换红外光谱(in-situ ATR-FTIR)、X射线光电子能谱(XPS)分析、理论计算以及与非羧基对应物的比较,发现Zn-MOF-1-NS表面Zn(Ⅱ)位点和羧基共同参与了MC-LR肽键的水解。Constructed by the ligands of 3-amino-1,2,4-triazole-5-carboxylic acid(Hatz)and 1,3,5-benzenetricarbox-ylic acid(H3btc),a Zn(Ⅱ)metal-organic framework with nanosheet morphology(Zn-MOF-1-NS)was prepared to mim-ic the structures of matrix metalloproteinases(MMPs).Zn-MOF-1-NS was highly effective in catalyzing the hydroly-sis of the peptide bonds of microcystin(MC-LR).Within just 7.5 h,82.6%of MC-LR was hydrolyzed(k=0.23 h^(-1)),which was much higher than the reported best hydrolysis efficiency of siderite(k=0.04 h^(-1)).This research has found that even when the amount of humic acid was increased tenfold,it did not significantly impede MC-LR decomposi-tion.This demonstrates the impressive ability of the catalyst to resist interference from natural organic matter(NOM).Through in-situ attenuated total reflectance Fourier transform infrared spectroscopy(in-situ ATR-FTIR)and X-ray photoelectron spectroscopy(XPS)analyses,theoretical calculations,and comparison with a non-carboxyl counterpart,it was discovered that the surficial Zn(Ⅱ)site and the carboxyl group of Zn-MOF-1-NS participate in the cleavage of the peptide bond.

关 键 词：微囊藻毒素-LR 选择性水解 模拟酶 金属有机骨架 基质金属蛋白酶 

分 类 号：O614.241[理学—无机化学]