Simms Charlotte, Mullaliu Angelo, de de Azambuja Francisco, Aquilanti Giuliana, Parac-Vogt Tatjana N
Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, 3001, Belgium.
Elettra Sincrotrone, Trieste, Basovizza, 34149, Italy.
Small. 2024 Mar;20(13):e2307236. doi: 10.1002/smll.202307236. Epub 2023 Nov 16.
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.
双金属金属有机框架材料（MOFs）是很有前景的纳米材料，然而由于合成、稳定性、金属氧化态控制、相纯度以及原子水平表征等问题，其对生物分子的反应活性仍具有挑战性。在此，通过在水环境中开发混合金属Zr/Ce-MOFs的合成方法，合理地解决了这些缺点，克服了MOF纳米酶开发中的重大障碍，使其在生物相关条件下具有足够的稳定性。具体而言，报道了在水/乙酸混合物中绿色安全地合成Zr/Ce-MOF-808，该方法可提供具有可靠纳米酶活性的显著水稳定材料，包括先前报道在水中不稳定的高Ce含量的MOFs。这些新材料优于类似的双金属MOF纳米酶，表明合理的合成修饰可以带来显著的改进。此外，通过X射线吸收精细结构（XAFS）和X射线衍射（XRD）进行的原子水平表征证实，优异的纳米酶源于合成方法的差异，这导致了水稳定材料的产生，以及Ce的掺入，这扰乱了材料的配体交换动力学，并最终可用于微调MOF的固有反应活性。类似地，以协同方式利用金属的合理策略应能使其他水稳定的双金属MOF纳米酶超越现有纳米酶，为各种生物技术应用铺平道路。
