Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China.
Key Laboratory of Eco-environments in Three Gorges Reservoir Region (Ministry of Education), College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China.
Anal Chim Acta. 2023 Dec 1;1283:341959. doi: 10.1016/j.aca.2023.341959. Epub 2023 Oct 31.
Nanozymes are one of the ideal substitutes for natural enzymes because of their excellent chemical stability and simple preparation methods. However, due to the limited catalytic ability of most reported nanozymes, constructing nanomaterials with low cost and high activity is gradually becoming an exploration focus in the field of nanozymes. Heteroatom doping of metal-organic frameworks is one of potential approaches to design nanozymes with high catalytic performance. Due to their multiple valence states properties, V-doped metal-organic framework (MOF)-derived LDH is expected to be a good enzyme-like catalyst. To our knowledge, the V-doped MOF-derived LDH as nanozyme is not explored before.
We report the in-situ synthesis of NiV-layered double hydroxides (LDHs) on nickel-based MOF, i.e. Ni-MOF@NiV-LDHs. The MOF surface is covered by 2D nanosheets. This unique structural design increases the specific surface area of the material, enables more exposure of catalytic active sites to participate in reactions and accelerates the electron transfer rate. The Ni-MOF@NiV-LDHs have high peroxidase-like activity able to catalyze TMB oxidation by HO via the generation of •OH and O. Relative to Ni-MOF, the Ni-MOF@NiV-LDHs shows 47-fold peroxidase-like activity rise. It had good affinity to TMB and HO, with the Michaelis-Menten constants of 0.12 mM and 0.007 mM, respectively. The hydroquinone (HQ) consumed the reactive oxygen species generated in the TMB + HO+Ni-MOF@NiV-LDHs system to inhibit the TMB oxidation. On this basis, a sensitive and rapid assay for determining HQ was developed, with a linear range of 0.50-70 μM and a LOD of 0.37 μM.
This work provided some clues for the further development of novel nanozymes with high catalytic performance via a strategy of heteroatom doping. And the constructed colorimetric analysis method was successfully utilized for the determination of HQ in actual waters, which has the potential for practical application in the analysis of environmental pollutants.
由于纳米酶具有优异的化学稳定性和简单的制备方法，因此成为天然酶的理想替代品之一。然而，由于大多数报道的纳米酶的催化能力有限，因此构建低成本、高活性的纳米材料逐渐成为纳米酶领域的探索重点。金属有机骨架的杂原子掺杂是设计具有高催化性能的纳米酶的潜在方法之一。由于其多种价态特性，V 掺杂的金属-有机骨架（MOF）衍生的层状双氢氧化物（LDH）有望成为一种良好的类酶催化剂。据我们所知，以前尚未探索过 V 掺杂的 MOF 衍生 LDH 作为纳米酶。
我们报告了在镍基 MOF 上原位合成 NiV 层状双氢氧化物（LDHs），即 Ni-MOF@NiV-LDHs。MOF 表面被 2D 纳米片覆盖。这种独特的结构设计增加了材料的比表面积，使更多的催化活性位点暴露出来参与反应，并加速了电子转移速率。Ni-MOF@NiV-LDHs 具有高过氧化物酶样活性，能够通过生成•OH 和 O 来催化 TMB 被 HO 的氧化。与 Ni-MOF 相比，Ni-MOF@NiV-LDHs 的过氧化物酶样活性提高了 47 倍。它对 TMB 和 HO 具有良好的亲和力，米氏常数分别为 0.12 mM 和 0.007 mM。对苯二酚（HQ）消耗 TMB+HO+Ni-MOF@NiV-LDHs 体系中产生的活性氧物质来抑制 TMB 的氧化。在此基础上，建立了一种灵敏快速测定 HQ 的方法，线性范围为 0.50-70 μM，LOD 为 0.37 μM。
这项工作通过杂原子掺杂策略为进一步开发具有高催化性能的新型纳米酶提供了一些线索。并且构建的比色分析方法成功用于实际水样中 HQ 的测定，在环境污染物分析中具有实际应用的潜力。
