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具有优异对硝基苯酚降解性能和辣根过氧化物酶样活性的多功能铜-谷胱甘肽簇合物。

Multifunctional copper-glutathione clusters with superior -nitrophenol degradation and horseradish peroxidase-like activity.

作者信息

Oyebanji Mayowa, Yang Xuejiao, Chen Ling, Sun Wencai, Qian Ruru, Yu Haizhu, Zhu Manzhou

机构信息

Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Physical Science and Information Technology, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University Hefei 230601 China

出版信息

RSC Adv. 2025 Mar 24;15(12):8889-8900. doi: 10.1039/d5ra00897b. eCollection 2025 Mar 21.

Abstract

Copper nanoclusters (Cu NCs) are emerging as highly promising nanomaterials due to their unique physicochemical properties, making them an ideal platform for catalysis, sensing, and environmental remediation. This study explores the development of ultrasmall, water-soluble copper-glutathione (Cu-SG) nanoclusters, focusing on their catalytic capacity for the degradation of -nitrophenol (-NP), horseradish peroxidase (HRP)-like activity, and hydrogen peroxide (HO) detection. During synthesis, a combination of one-pot synthesis and acid-etching strategy was employed. The acid-etching approach was specifically utilized as an essential method to precisely regulate the structural properties of the clusters. The water-soluble ultrasmall Cu-SG nanoclusters show superior catalytic efficiency, achieving 98% conversion of -NP to -aminophenol (-AP) within six minutes. The reaction followed first-order kinetics with a rate constant of 0.44 min, consistent with the Langmuir-Hinshelwood model. Notably, the Cu-SG retained catalytic efficiency across multiple reaction cycles, highlighting their recyclability and long-term stability. Additionally, Cu-SG exhibited excellent sensitivity and selectivity for rapid colorimetric HO detection due to the strong HRP-like activity, achieving a detection limit of 6.03 μM with high resistance to interference from other ions and compounds. Thermodynamic analysis demonstrates an enthalpy driven spontaneous reduction of -NP with Cu-SG, wherein the van der Waals and hydrogen bonding interactions are predominant. By contrast, the interaction of Cu-SG with HO is an entropy-driven, spontaneous process, and the dominating hydrophobic forces drive the HRP-like catalytic mechanism. This study demonstrates the potential of the Cu-SG as an efficient, stable, and recyclable water-soluble copper nanocatalyst for pollutant degradation and as a sensitive sensor for reactive species.

摘要

铜纳米团簇(Cu NCs)因其独特的物理化学性质而成为极具前景的纳米材料,使其成为催化、传感和环境修复的理想平台。本研究探索了超小的水溶性铜-谷胱甘肽(Cu-SG)纳米团簇的开发,重点关注其对硝基苯酚(-NP)降解的催化能力、类似辣根过氧化物酶(HRP)的活性以及过氧化氢(HO)检测。在合成过程中,采用了一锅法合成和酸蚀刻策略相结合的方法。酸蚀刻方法被专门用作精确调节团簇结构性质的关键方法。水溶性超小Cu-SG纳米团簇表现出优异的催化效率,在六分钟内实现了98%的-NP转化为对氨基苯酚(-AP)。该反应遵循一级动力学,速率常数为0.44 min,与朗缪尔-欣谢尔伍德模型一致。值得注意的是,Cu-SG在多个反应循环中保持催化效率,突出了它们的可回收性和长期稳定性。此外,由于具有很强的类似HRP的活性,Cu-SG对快速比色法检测HO表现出优异的灵敏度和选择性,实现了6.03 μM的检测限,对其他离子和化合物的干扰具有高抗性。热力学分析表明,Cu-SG对-NP的还原是一个由焓驱动的自发过程,其中范德华力和氢键相互作用占主导。相比之下,Cu-SG与HO的相互作用是一个由熵驱动的自发过程,主导的疏水作用力驱动了类似HRP的催化机制。本研究证明了Cu-SG作为一种高效、稳定且可回收的水溶性铜纳米催化剂用于污染物降解以及作为活性物种敏感传感器的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bbda/11931283/9a87b1c2f10d/d5ra00897b-f1.jpg

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