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Multi-nanozyme cascade system for boosting colorimetric sensing by selective etching bimetallic MOFs.

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Title: Multi-nanozyme cascade system for boosting colorimetric sensing by selective etching bimetallic MOFs.
Authors: Lin, Yuhang1 (AUTHOR), Wang, Tianshuo1 (AUTHOR), Liu, Yuanhao1 (AUTHOR), Pu, Lianxi1 (AUTHOR), Jia, Mingxuan1 (AUTHOR), Zhou, Xilong1 (AUTHOR), Ding, Lijun1 (AUTHOR) ljding@ujs.edu.cn, Zhu, Weiran1,2 (AUTHOR) keweiranzhu@ust.hk, Wang, Kun1 (AUTHOR) wangkun@ujs.edu.cn
Source: Analytica Chimica Acta. Jun2025, Vol. 1353, pN.PAG-N.PAG. 1p.
Subjects: Multienzyme complexes, Oxidation-reduction reaction, Metal defects, Catalytic activity, Superoxide dismutase, Bimetallic catalysts
Abstract: Rational engineering of multienzyme system architecture is essential for achieving high-performance multi-enzyme cascade catalysis in sensing applications. In this context, the initiation step of the cascade reaction pathway plays a pivotal role in enhancing catalytic efficiency. CoFe Prussian blue analogue (CoFePBA), a dual-metal organic framework, is an ideal template for multi-enzyme design, leveraging its diverse dual-metal ion functionalities and synergistic effects. Defect engineering approaches enable the fine-tuning of catalytic properties, optimizing electron transfer and promoting reaction intermediates. Therefore, the rational design of the multienzyme system structure is critical for efficient cascade catalysis. In this study, we utilized deep eutectic solvents (DES) to selectively induce Co defects in CoFePBA (CoFePBA-DES) under mild conditions, providing more active sites and enhancing the Co2+/Co3+ ratio, significantly boosting the initial step of the cascade reaction. This then triggers the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD)—which facilitates the conversion of products from O 2 to O 2 •- to endogenous H 2 O 2 , achieving a two-fold increase in its yield and subsequently to OH• in a sequential reaction, demonstrating excellent multi-enzyme cascade catalytic activity. Utilizing the inhibitory effect of glutathione (GSH) on multi-enzyme cascade catalytic activity, we designed a highly efficient and rapid colorimetric sensor for the sensitive detection of GSH, with a detection range of 0.5–160 μM and a detection limit of 0.15 μM. Compared to traditional etching techniques, DES-based methods offer superior selectivity, lower toxicity, and better structural preservation of the MOF framework, making them a promising tool for controlled defect engineering. By selectively creating defects, the initial steps of the cascade reaction are activated, resulting in a significant enhancement of catalytic activity. This approach provides a viable pathway for the preparation of high-performance dual-metal catalysts for cascade reaction catalysts and sensing applications. We employ Deep Eutectic Solvents (DES) to selectively induce cobalt metal defects under mild conditions, which acted as an initiation step of the cascade reaction to activate the reaction process and significantly enhance catalytic efficiency, and then initiate the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD). This system facilitates the transformation of products from O 2 ·- to H 2 O 2 and ultimately to OH radicals. The metal vacancies with a higher Co2+/Co3+ ratio enhance the OXD-like and SOD-like activities. Additionally, these vacancies provide adsorption active sites during the reaction process, significantly boosting the catalytic activity of the nanocatalyst. As a result, the hydrogen peroxide generation in CoFePBA increases by 100 %, demonstrating outstanding cascade catalytic activity. [Display omitted] • Selective etching of bimetallic nanozymes was achieved by deep eutectic solvents. • Cascade reaction within the multi-nanozyme was realized. • Selective etching of Co can accerate the initial step of the cascade reaction. • A colorimetric sensor was designed for the sensitive detection of glutathione. • The sensor exhibits a detection range of 0.5–160 μM and a detection limit of 0.15 μM. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
Description
Abstract:Rational engineering of multienzyme system architecture is essential for achieving high-performance multi-enzyme cascade catalysis in sensing applications. In this context, the initiation step of the cascade reaction pathway plays a pivotal role in enhancing catalytic efficiency. CoFe Prussian blue analogue (CoFePBA), a dual-metal organic framework, is an ideal template for multi-enzyme design, leveraging its diverse dual-metal ion functionalities and synergistic effects. Defect engineering approaches enable the fine-tuning of catalytic properties, optimizing electron transfer and promoting reaction intermediates. Therefore, the rational design of the multienzyme system structure is critical for efficient cascade catalysis. In this study, we utilized deep eutectic solvents (DES) to selectively induce Co defects in CoFePBA (CoFePBA-DES) under mild conditions, providing more active sites and enhancing the Co2+/Co3+ ratio, significantly boosting the initial step of the cascade reaction. This then triggers the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD)—which facilitates the conversion of products from O 2 to O 2 •- to endogenous H 2 O 2 , achieving a two-fold increase in its yield and subsequently to OH• in a sequential reaction, demonstrating excellent multi-enzyme cascade catalytic activity. Utilizing the inhibitory effect of glutathione (GSH) on multi-enzyme cascade catalytic activity, we designed a highly efficient and rapid colorimetric sensor for the sensitive detection of GSH, with a detection range of 0.5–160 μM and a detection limit of 0.15 μM. Compared to traditional etching techniques, DES-based methods offer superior selectivity, lower toxicity, and better structural preservation of the MOF framework, making them a promising tool for controlled defect engineering. By selectively creating defects, the initial steps of the cascade reaction are activated, resulting in a significant enhancement of catalytic activity. This approach provides a viable pathway for the preparation of high-performance dual-metal catalysts for cascade reaction catalysts and sensing applications. We employ Deep Eutectic Solvents (DES) to selectively induce cobalt metal defects under mild conditions, which acted as an initiation step of the cascade reaction to activate the reaction process and significantly enhance catalytic efficiency, and then initiate the three-enzyme cascade reaction system—oxidase (OXD), superoxide dismutase (SOD), and peroxidase (POD). This system facilitates the transformation of products from O 2 ·- to H 2 O 2 and ultimately to OH radicals. The metal vacancies with a higher Co2+/Co3+ ratio enhance the OXD-like and SOD-like activities. Additionally, these vacancies provide adsorption active sites during the reaction process, significantly boosting the catalytic activity of the nanocatalyst. As a result, the hydrogen peroxide generation in CoFePBA increases by 100 %, demonstrating outstanding cascade catalytic activity. [Display omitted] • Selective etching of bimetallic nanozymes was achieved by deep eutectic solvents. • Cascade reaction within the multi-nanozyme was realized. • Selective etching of Co can accerate the initial step of the cascade reaction. • A colorimetric sensor was designed for the sensitive detection of glutathione. • The sensor exhibits a detection range of 0.5–160 μM and a detection limit of 0.15 μM. [ABSTRACT FROM AUTHOR]
ISSN:00032670
DOI:10.1016/j.aca.2025.343976