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原位还原配位的Cu(I)-聚三硫氰尿酸用于HS比色检测和抗菌的即时氧化酶和过氧化物酶模拟活性

Instant oxidase- and peroxidase-mimic activities of in-situ reductive coordinated Cu(I)-polytrithiocyanuric acid for HS colorimetric detection and antibacterial.

作者信息

Gao Xiaoying, Li Zihan, Wen Huang, Zhao Jiahui, Zhou Mingyang, Yang Shenghong, Liu Jian

机构信息

School of Chemical Engineering, College of Chemistry and Materials, State Province Joint Engineering Laboratory of Zeolite Membrane Materials, Jiangxi Normal University, Nanchang 330022, China.

Shandong Provincial Key Laboratory of Molecular Engineering, School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353, China.

出版信息

J Hazard Mater. 2025 Feb 5;483:136722. doi: 10.1016/j.jhazmat.2024.136722. Epub 2024 Nov 30.

DOI:10.1016/j.jhazmat.2024.136722
PMID:39616844
Abstract

Integrating preparation and utilization of nanozymes in a "one-pot" approach offers advantages over conventional discrete synthesis and application methods by eliminating laborious syntheses, reducing energy consumption, and minimizing chemical waste. Herein, we revealed the instant oxidase- and peroxidase-mimic (OD-/POD-mimic) activities of in-situ formed Cu(I)-polytrithiocyanuric acid (i:Cu(I)-pTTCA) polymers. The polymers were assembled through reductive coordination between Cu and trithiocyanuric acid and immediately exhibited intrinsic OD- or POD-mimic activities. The presence of unsaturated Cu(I)···SC coordination moieties was identified as the underlying cause of the high OD-/POD-mimic activities of i:Cu(I)-pTTCA. This was confirmed by experiments and density functional theory calculations, which demonstrated that the coordination moieties facilitated the activation of O and HO into reactive oxygen species. The i:Cu(I)-pTTCA was formed in-situ and directly employed for the colorimetric detection of HS with a limit of detection of 0.032 μM and the visual array discrimination of HS and biothiols in the range of 0.5-10 μM. The i:Cu(I)-pTTCA was further demonstrated as a self-prescribed antibacterial agent capable of inactivating up to 98 % and 96 % of E. coli and S. aureus, respectively. Our findings provide an in-depth understanding of the direct formation-structure-catalysis relationship of nanozymes.

摘要

通过“一锅法”整合纳米酶的制备和应用,相对于传统的分步合成和应用方法具有诸多优势,包括消除繁琐的合成步骤、降低能耗以及减少化学废物产生。在此,我们揭示了原位形成的铜(I)-聚三硫氰尿酸(i:Cu(I)-pTTCA)聚合物具有即时的氧化酶和过氧化物酶模拟(OD-/POD-模拟)活性。这些聚合物通过铜与三硫氰尿酸之间的还原配位组装而成,并立即展现出固有的OD-或POD-模拟活性。不饱和的铜(I)···硫配位部分的存在被确定为i:Cu(I)-pTTCA具有高OD-/POD-模拟活性的根本原因。实验和密度泛函理论计算证实了这一点,表明这些配位部分促进了O和HO活化生成活性氧物种。i:Cu(I)-pTTCA原位形成后直接用于比色检测HS,检测限为0.032 μM,可对0.5 - 10 μM范围内的HS和生物硫醇进行视觉阵列区分。i:Cu(I)-pTTCA还进一步被证明是一种自行规定的抗菌剂,能够分别使高达98%和96%的大肠杆菌和金黄色葡萄球菌失活。我们的研究结果为深入理解纳米酶的直接形成-结构-催化关系提供了依据。

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