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基于唑类配体构建用于识别卤代酚类污染物的pH依赖性传感器阵列的两种新型漆酶样纳米酶。

Two novel laccase-like nanozymes based on azole ligands for constructing pH-dependent sensor array for recognizing halogenated phenolic pollutants.

作者信息

Han Qing, Chen Xixingchi, Wang Yunlong, Li Ke, Huang Hui, Li Yongxin

机构信息

Key Laboratory of Groundwater Resources and Environment (Jilin University), Ministry of Education, College of New Energy and Environment, Jilin University, Changchun 130021, PR China; Jilin Provincial Key Laboratory of Water Resources and Water Environment, College of New Energy and Environment, Jilin University, Changchun 130021, PR China.

College of Food Science and Engineering, Jilin University, Changchun 130025, PR China.

出版信息

J Hazard Mater. 2025 Aug 15;494:138436. doi: 10.1016/j.jhazmat.2025.138436. Epub 2025 Apr 28.

DOI:10.1016/j.jhazmat.2025.138436
PMID:40311429
Abstract

Halogenated phenolic compounds are widely used in industrial processes such as paper manufacturing and pesticide production. They are priority pollutants that need to be controlled and are discharged with industrial wastewater. Halogenated phenolics have much greater environmental impacts than phenolics due to elevated toxicity and reduced biodegradability caused by halogen substitution. Since the type and location of halogens have great influence on their toxicity and existing differentiation methods rely on large-scale instruments, there is an urgent need to develop new and convenient sensing technologies for the simultaneous identification and detection of halogenated phenols (including fluorophenols, chlorophenols and bromophenols) for more targeted pollution control. In this work, we prepared two novel laccase-like nanozymes using asymmetric azole ligands (thiazole-2-carboxylic acid and imidazole-2-carboxylic acid) coordinated with Cu, and constructed a four-channel sensor array by taking advantage of the difference in their ability to catalyze the color development of halogenated phenols and 4-aminoantipyrine under pH = 7 and pH = 8 conditions. The sensor array was able to accurately discriminate eight halogenated phenols in the range of 5-100 μM, and allowing for accurate quantitative analysis. The method has good anti-interference ability to other non-target phenols, and can realize accurate differentiation of halogenated phenols in real water bodies. Even in the presence of high concentrations of common ions or heavy metal ions, halogenated phenolic pollutants can be accurately identified. The good stability and anti-interference ability make the senor array has a great potential for application and is expected to provide a basis for environmental pollution control.

摘要

卤代酚类化合物广泛应用于造纸和农药生产等工业过程中。它们是需要控制的优先污染物,并随工业废水排放。由于卤代作用导致毒性升高和生物降解性降低,卤代酚类对环境的影响比酚类大得多。由于卤素的类型和位置对其毒性有很大影响,且现有的区分方法依赖大型仪器,因此迫切需要开发新的便捷传感技术,用于同时识别和检测卤代酚(包括氟酚、氯酚和溴酚),以实现更有针对性的污染控制。在这项工作中,我们使用与铜配位的不对称唑类配体(噻唑 - 2 - 羧酸和咪唑 - 2 - 羧酸)制备了两种新型类漆酶纳米酶,并利用它们在pH = 7和pH = 8条件下催化卤代酚和4 - 氨基安替比林显色能力的差异构建了一个四通道传感器阵列。该传感器阵列能够在5 - 100 μM范围内准确区分八种卤代酚,并实现准确定量分析。该方法对其他非目标酚类具有良好的抗干扰能力,能够实现实际水体中卤代酚的准确区分。即使在存在高浓度常见离子或重金属离子的情况下,也能准确识别卤代酚类污染物。良好的稳定性和抗干扰能力使该传感器阵列具有很大的应用潜力,有望为环境污染控制提供依据。

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