Green, Safe, and Reliable Synthesis of Bimetallic MOF‐808 Nanozymes With Enhanced Aqueous Stability and Reactivity for Biological Applications

SmallEarly View 2307236 Research Article Green, Safe, and Reliable Synthesis of Bimetallic MOF-808 Nanozymes With Enhanced Aqueous Stability and Reactivity for Biological Applications Charlotte Simms, Charlotte Simms orcid.org/0000-0002-9334-9476 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 BelgiumSearch for more papers by this authorAngelo Mullaliu, Angelo Mullaliu orcid.org/0000-0003-2800-2836 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 BelgiumSearch for more papers by this authorFrancisco de de Azambuja, Corresponding Author Francisco de de Azambuja [email protected] orcid.org/0000-0002-5537-5411 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 Belgium E-mail: [email protected]Search for more papers by this authorGiuliana Aquilanti, Giuliana Aquilanti orcid.org/0000-0001-6683-2668 Elettra Sincrotrone, Trieste, Basovizza, 34149 ItalySearch for more papers by this authorTatjana N. Parac-Vogt, Corresponding Author Tatjana N. Parac-Vogt [email protected] orcid.org/0000-0002-6188-3957 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 Belgium E-mail: [email protected]Search for more papers by this author Charlotte Simms, Charlotte Simms orcid.org/0000-0002-9334-9476 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 BelgiumSearch for more papers by this authorAngelo Mullaliu, Angelo Mullaliu orcid.org/0000-0003-2800-2836 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 BelgiumSearch for more papers by this authorFrancisco de de Azambuja, Corresponding Author Francisco de de Azambuja [email protected] orcid.org/0000-0002-5537-5411 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 Belgium E-mail: [email protected]Search for more papers by this authorGiuliana Aquilanti, Giuliana Aquilanti orcid.org/0000-0001-6683-2668 Elettra Sincrotrone, Trieste, Basovizza, 34149 ItalySearch for more papers by this authorTatjana N. Parac-Vogt, Corresponding Author Tatjana N. Parac-Vogt [email protected] orcid.org/0000-0002-6188-3957 Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001 Belgium E-mail: [email protected]Search for more papers by this author First published: 16 November 2023 https://doi.org/10.1002/smll.202307236Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Bimetallic metal-organic frameworks (MOFs) are promising nanomaterials whose reactivity towards biomolecules remains challenging due to issues related to synthesis, stability, control over metal oxidation state, phase purity, and atomic level characterization. Here, these shortcomings are rationally addressed through development of a synthesis of mixed metal Zr/Ce-MOFs in aqueous environment, overcoming significant hurdles in the development of MOF nanozymes, sufficiently stable on biologically relevant conditions. Specifically, a green and safe synthesis of Zr/Ce-MOF-808 is reported in water/acetic acid mixture which affords remarkably water-stable materials with reliable nanozymatic reactivity, including MOFs with a high Ce content previously reported to be unstable in water. The new materials outperform analogous bimetallic MOF nanozymes, showcasing that rational synthesis modifications could impart outstanding improvements. Further, atomic-level characterization by X-ray Absorption Fine Structure (XAFS) and X-ray Diffraction (XRD) confirmed superior nanozymes arise from differences in the synthetic method, which results in aqueous stable materials, and Ce incorporation, which perturbs the ligand exchange dynamics of the material, and could ultimately be used to fine tune the intrinsic MOF reactivity. Similar rational strategies which leverage metals in a synergistic manner should enable other water-stable bimetallic MOF nanozymes able to surpass existing ones, laying the path for varied biotechnological applications. Conflict of Interest The authors declare no conflict of interest. Open Research Data Availability Statement The data that support the findings of this study are available from the corresponding author upon reasonable request. Supporting Information Filename Description smll202307236-sup-0001-SuppMat.pdf2.5 MB Supporting Information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1L. Lauková, B. Konecná, L. Janovicová, B. Vlková, P. Celec, Biomolecules 2020, 10, 2. 10.3390/biom10071036 Google Scholar 2Á. Bódi, G. Kaslik, I. Venekei, L. Gráf, Eur. J. Biochem. 2001, 268, 6238. 10.1046/j.0014-2956.2001.02578.x CASPubMedWeb of Science®Google Scholar 3E. Vandermarliere, M. Mueller, L. Martens, Mass Spectromet. Rev. 2013, 32, 453. 10.1002/mas.21376 CASPubMedWeb of Science®Google Scholar 4K. Saeki, K. Ozaki, T. Kobayashi, S. Ito, J. Biosci. Bioeng. 2007, 103, 501. 10.1263/jbb.103.501 CASPubMedWeb of Science®Google Scholar 5A. Zaks, Curr. Opin. Chem. 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