College of Environment and Resources, Hunan Provincial University Key Laboratory for Environmental and Ecological Health, Xiangtan University, Xiangtan 411105, Hunan, China.
Hunan Institute of Advanced Sensing and Information Technology, Hunan Provincial Key Laboratory of Smart Carbon Materials and Advanced Sensing, Xiangtan University, Xiangtan 411105, Hunan, China.
J Hazard Mater. 2024 Sep 15;477:135292. doi: 10.1016/j.jhazmat.2024.135292. Epub 2024 Jul 24.
Laccases are the most commonly used agents for the treatment of phenolic pollutants. To address the instability and high cost of natural laccases, we investigated nucleobase-modulated copper nanomaterial with laccase-like activity. Various nucleobases, including adenine, guanine, cytosine, and thymine, were investigated as templates for Cu reduction and copper nanomaterials formation due to their coordination capacity. By comparing structure and catalytic activity, the cytosine-mediated copper nanomaterial (C-Cu) had the best laccase-like activity and other nucleobase-templated copper nanomaterials exhibited low catalytic activity under the same conditions. The mechanism of nucleobase regulation of the catalytic activity of copper nanomaterials was further analyzed using X-ray photoelectron spectroscopy and density functional theory. The possible catalytic mechanisms of C-Cu, including substrate adsorption, substrate oxidation, oxygen binding, and oxygen reduction, were proposed. Remarkably, nucleobase-modulated copper nanozymes showed high stability and catalytic oxidation performance at various pH values, temperatures, long-term storage, and high salinity. In combination with electrochemical techniques, a portable electrochemical sensor for measuring phenolic pollutants was developed. This novel sensor exhibited a good linear response to catechol (10-1000 μM) with a limit of detection of 1.8 μM and excellent selectivity and anti-interference ability. This study provides not only a new strategy for the regulation of the laccase-like activity of copper nanomaterials but also a novel tool for the effective removal and low-cost detection of phenolic pollutants.
漆酶是处理酚类污染物最常用的试剂。为了解决天然漆酶的不稳定性和高成本问题，我们研究了具有漆酶样活性的碱基调控铜纳米材料。由于其配位能力，各种碱基，包括腺嘌呤、鸟嘌呤、胞嘧啶和胸腺嘧啶，都被研究作为铜还原和铜纳米材料形成的模板。通过比较结构和催化活性，发现胞嘧啶介导的铜纳米材料（C-Cu）具有最好的漆酶样活性，而在相同条件下，其他碱基模板化的铜纳米材料表现出低的催化活性。进一步利用 X 射线光电子能谱和密度泛函理论分析了碱基调控铜纳米材料催化活性的机制。提出了 C-Cu 的可能催化机制，包括底物吸附、底物氧化、氧结合和氧还原。值得注意的是，碱基调控的铜纳米酶在各种 pH 值、温度、长期储存和高盐度下表现出高稳定性和催化氧化性能。结合电化学技术，开发了一种用于测量酚类污染物的便携式电化学传感器。该新型传感器对儿茶酚（10-1000 μM）表现出良好的线性响应，检测限低至 1.8 μM，具有优异的选择性和抗干扰能力。本研究不仅为调控铜纳米材料的漆酶样活性提供了新策略，也为有效去除和低成本检测酚类污染物提供了新工具。
