腺嘌呤锌钴双金属有机框架的合成及其对含硫氨基酸的识别  

Synthesis of a zinc⁃cobalt bimetallic adenine metal⁃organic framework for the recognition of sulfur⁃containing amino acids

作　　者：才红 巫洁雯 黎静芸 陈力衔 肖思琪 李丹 CAI Hong;WU Jiewen;LI Jingyun;CHEN Lixian;XIAO Siqi;LI Dan(School of Chemical and Environmental Engineering,Hanshan Normal University,Chaozhou,Guangdong 521041,China;College of Chemistry and Materials Science,Jinan University,Guangzhou 510632,China)

机构地区：[1]韩山师范学院化学与环境工程学院,潮州521041 [2]暨南大学化学与材料学院,广州510632

出　　处：《无机化学学报》2025年第1期114-122,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金重点项目(No.21731002);广东省自然科学基金(No.2023A1515010868);韩山师范学院重点实验室平台项目(No.PNB2101)资助。

摘　　要：采用腺嘌呤(HA)作为主配体,以间苯二羧酸(H_(2)IP)为第二配体,在水热条件下,成功制备了一例双金属有机框架(C_(2)H_(8)N)(NH_(4))[Zn_(4)Co_(2)(μ‑O)(IP)_(4)(A)_(4)]·1.25H_(2)O(ZnCoIPA)。单晶X射线衍射表征结构显示三维的ZnCoIPA保留了HA上的Watson‑Crick位点,并沿着a轴和b轴方向形成一维的螺旋通道。X射线光电子能谱显示ZnCoIPA中钴离子的变价性质,结合其独特的限域空间使其表现出对含硫氨基酸的快速和可见的识别。紫外可见吸收光谱表明主客体之间发生了显著的电子转移。Using adenine(HA)and isophthalic acid(H_(2)IP)as ligands,a bimetallic organic framework,(C_(2)H_(8)N)(NH_(4))[Zn_(4)Co_(2)(μ‑O)(IP)_(4)(A)_(4)]·1.25H_(2)O(ZnCoIPA),was successfully synthesized under hydrothermal conditions.Singlecrystal X‑ray diffraction analysis revealed that the 3D ZnCoIPA retains the Watson‑Crick sites of HA,with sinusoidal channels along the a‑axis direction having diameters of approximately 0.42‑0.49 nm and a narrow pore size distribution of about 0.07 nm.The channel diameters along the b‑axis vary from 0.38 to 0.50 nm with a relatively wider pore size distribution of around 0.12 nm.X‑ray photoelectron spectroscopy demonstrated the valence‑varying nature of cobalt ions in ZnCoIPA,combined with its unique confined space,enabling selective recognition of sulfurcontaining amino acids.UV‑Vis absorption spectroscopy indicated the electronic transfer between the host and guest,resulting in a color change from colorless to yellow in solution,providing a visual recognition effect.Furthermore,time‑dependent UV‑Vis absorption spectroscopy tests on reduced and oxidized forms of glutathione(GSH)showed that the absorption peak intensity of the smaller‑sized reduced GSH increased gradually over time,while the larger‑sized oxidized GSH exhibited a slower change,enhancing only after a delay of approximately 16 min,further demonstrating the influence of the channel properties on the color change behavior of sulfur‑containing amino acids.CCDC:2390216.

关 键 词：金属有机框架 主客体化学 氨基酸 分子识别 

分 类 号：O614.812[理学—无机化学] O614.241[理学—化学]