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Designed imidazole-based supramolecular catalysts for accelerating oxidation/hydrolysis cascade reactions

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An Erratum to this article was published on 29 February 2024

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Abstract

Reconstructing enzymatic active sites presents a significant challenge due to the intricacies involved in achieving enzyme-like scaffold folding and spatial arrangement of essential functional groups. There is also a growing interest in building biocatalytic networks, wherein multiple enzymatic active sites are localized within a single artificial system, allowing for cascaded transformations. In this work, we report the self-assembly of imidazole or its derivatives with fluorenylmethyloxycarbonyl-modified histidine and Cu2+ to fabricate a supramolecular catalyst, which possesses catechol oxidase-like dicopper center with multiple imidazole as the coordination sphere. Transmission electron microscopy, low-temperature X-band continuous-wave electron paramagnetic resonance, K-edge X-ray absorption spectra/the extended X-ray absorption fine structure analysis, and density functional theory modeling were used for the structural characterization of the catalyst. The phenol derivatives and the dissolved oxygen were used as the substrates, with the addition of 4-aminoantipyrine to generate a red adduct with a maximum absorbance at 510 nm, for obtaining time-dependent absorbance change curves and estimating the activities. The results reveal that the addition of imidazole synergistically accelerates the oxidative activity about 10-fold and the hydrolysis activity about 14-fold than fluorenylmethyloxycarbonyl modified-histidine/Cu2+. The supramolecular nanoassembly also exhibits the ability to catalyze oxidation/hydrolysis cascade reactions, converting 2′,7′-dichlorofluorescin diacetate into 2′,7′-dichlorofluorescein. This process can be regulated through the methylation of the imidazole component at various positions. This work may contribute to the design of advanced biomimetic catalysts, and shed light on early structural models of the active sites of the primitive copper-dependent enzymes.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 52173194), Beijing Natural Science Foundation (No. 2232017), and Fundamental Research Funds for the Central Universities (No. buctrc201902). The theoretical simulations are supported by Hefei advanced computing center and high performance computing platform of BUCT.

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  1. State Key Laboratory of Organic-Inorganic Composites, Key Lab of Biomedical Materials of Natural Macromolecules (Ministry of Education), Beijing Laboratory of Biomedical Materials, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Yuanxi Liu, Shichao Xu, Haifeng Wu, Baoli Zhang & Zhen-Gang Wang

  2. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, 230029, China

    Wenjie Xu & Li Song

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  1. Yuanxi Liu
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  2. Wenjie Xu
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Liu, Y., Xu, W., Xu, S. et al. Designed imidazole-based supramolecular catalysts for accelerating oxidation/hydrolysis cascade reactions. Nano Res. (2024). https://doi.org/10.1007/s12274-024-6489-5

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