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多孔 Cu 羟基金属双盐纳米花的形成源于金属-有机骨架,具有高效过氧化物酶样活性,可用于无标记检测葡萄糖。

Formation of porous Cu hydroxy double salt nanoflowers derived from metal-organic frameworks with efficient peroxidase-like activity for label-free detection of glucose.

机构信息

Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry Lanzhou University Gansu, Lanzhou, 730000, P.R. China.

出版信息

Nanoscale. 2018 Jul 5;10(25):11948-11954. doi: 10.1039/c8nr02832j.

DOI:10.1039/c8nr02832j
PMID:29901675
Abstract

Currently, nanomaterials with peroxidase activity have become an important colorimetric tool for biomolecular detection. However, compared with natural enzymes, the efficiency of most nanozymes is still lower. Here, with a leaf-like metal-organic-framework-5 as both a precursor and a template and copper acetate as a second precursor, hierarchical Cu hydroxy double salt (HDS) nanoflowers have been prepared and used as a label-free glucose colorimetric detection platform. We have demonstrated a scalable and facile synthesis of hierarchical Cu HDS nanoflowers, and density functional theory (DFT) calculations confirmed that there exists a hydrogen bond between the terephthalate anions and the layer OH group. The composition of Cu hydroxyl double salt is [Cu4(OH)6][BDC]·2H2O. Importantly, for the first time, the as-prepared Cu HDSs were demonstrated as peroxidase mimics to catalyze the oxidation of the enzyme substrate, 3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2, which accompanies a color change from colorless to blue and followed classic Michaelis-Menten models. Based on these findings, a colorimetric method based on Cu HDSs that is highly sensitive and selective for the detection of glucose was developed, with a low detection limit of 0.5 μM. The clinical applicability of the sensor is also proven to be suitable for sensing glucose in blood, suggesting that Cu HDSs could be used in the construction of portable sensors for point-of-care diagnosis and on-site tests.

摘要

目前,具有过氧化物酶活性的纳米材料已成为生物分子检测的重要比色工具。然而,与天然酶相比,大多数纳米酶的效率仍然较低。在这里,以叶状金属有机骨架-5 作为前体和模板,以醋酸铜作为第二前体,制备了分级 Cu 羟双盐(HDS)纳米花,并将其用作无标记葡萄糖比色检测平台。我们已经证明了分级 Cu HDS 纳米花的可扩展和简便合成,密度泛函理论(DFT)计算证实了对苯二甲酸阴离子和层 OH 基团之间存在氢键。Cu 羟基双盐的组成是 [Cu4(OH)6][BDC]·2H2O。重要的是,首次证明所制备的 Cu HDS 作为过氧化物酶模拟物,在 H2O2 存在下催化酶底物 3',5,5'-四甲基联苯胺(TMB)的氧化,伴随着颜色从无色变为蓝色,并且遵循经典的米氏-门坦模型。基于这些发现,开发了一种基于 Cu HDS 的比色法,用于检测葡萄糖,具有 0.5 μM 的低检测限。该传感器的临床适用性也被证明适用于血液中葡萄糖的检测,表明 Cu HDS 可用于构建用于即时诊断和现场测试的便携式传感器。

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