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仿生过氧化物酶模型:用低对称三嗪多羧酸盐配体构建的铜有机框架材料,作为生物传感平台用于视觉应用。

Biomimetic Peroxidase Model: Copper-Organic Framework Material Constructed with a Low-Symmetry Triazine Polycarboxylate Ligand for Visual Application as a Biosensing Platform.

作者信息

Wang Zi Yang, Wang Chen, Li Jiaru, Wang Yufei, Chi Yuxian, Jiang Shan, Bai Feng Ying, Xing Yong Heng

机构信息

College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China.

出版信息

Inorg Chem. 2025 Jun 30;64(25):12507-12517. doi: 10.1021/acs.inorgchem.5c00386. Epub 2025 Jun 16.

Abstract

Metal-organic frameworks (MOFs) have recently emerged as fascinating enzymatic mimics due to their active metal-redox centers and attractive structural adjustability. However, the design of MOFs based on low-symmetry triazine polycarboxylate ligands as peroxidase-like mimics remains largely unexplored. Herein, a novel Cu-MOF (complex ) was prepared using [5,5'-((6-(bis(carboxymethyl)amino)-1,3,5-triazine-2,4-diyl)bis(azanediyl))diisophthalic acid, HBATD] by a solvothermal method. Complex presented a better affinity for the hydrogen peroxide substrate compared with the natural horseradish peroxidase (HRP) enzyme. Its peroxidase-like activity is related to the production of hydroxyl radicals (•OH) and superoxide radicals (•O), and the brief conversion mechanism is speculated based on XPS data. Based on this, the colorimetric method was utilized for the detection of HO and partial biological molecules, especially ascorbic acid (AA) and glutathione (GSH), and the detection limits were as low as 0.38 μM for AA and 0.44 μM for GSH. In addition, smartphone-assisted recognition for AA sensing was realized, and complex was employed as a peroxidase nanozyme for AA detection in fruits and pharmaceuticals. These findings not only throw light on the construction of MOFs with high enzyme-like activity but also on the structural expansion of novel MOFs based on a low-symmetry family of triazine derivative linkers.

摘要

金属有机框架材料(MOFs)由于其活性金属氧化还原中心和吸引人的结构可调性,近来已成为引人关注的酶模拟物。然而,基于低对称三嗪多羧酸盐配体作为过氧化物酶样模拟物的MOFs设计在很大程度上仍未得到探索。在此,通过溶剂热法使用[5,5'-((6-(双(羧甲基)氨基)-1,3,5-三嗪-2,4-二基)双(氮杂二基))二间苯二甲酸,HBATD]制备了一种新型的铜-MOF(配合物)。与天然辣根过氧化物酶(HRP)相比,配合物对过氧化氢底物表现出更好的亲和力。其过氧化物酶样活性与羟基自由基(•OH)和超氧自由基(•O)的产生有关,并基于XPS数据推测了简要的转化机制。基于此,采用比色法检测H₂O₂和部分生物分子,尤其是抗坏血酸(AA)和谷胱甘肽(GSH),AA的检测限低至0.38 μM,GSH的检测限低至0.44 μM。此外,实现了智能手机辅助的AA传感识别,并且配合物被用作过氧化物酶纳米酶用于水果和药物中AA的检测。这些发现不仅为具有高酶样活性的MOFs的构建提供了思路,也为基于低对称三嗪衍生物连接体家族的新型MOFs的结构扩展提供了思路。

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