Loosen Alexandra, de Azambuja Francisco, Smolders Simon, Moons Jens, Simms Charlotte, De Vos Dirk, Parac-Vogt Tatjana N
Department of Chemistry, KU Leuven Celestijnenlaan 200F Leuven Belgium
Department Microbial and Molecular Systems, KU Leuven Celestijnenlaan 200F Leuven Belgium.
Chem Sci. 2020 May 22;11(26):6662-6669. doi: 10.1039/d0sc02136a.
Structural parameters influencing the reactivity of metal-organic frameworks (MOF) are challenging to establish. However, understanding their effect is crucial to further develop their catalytic potential. Here, we uncovered a correlation between reaction kinetics and the morphological structure of MOF-nanozymes using the hydrolysis of a dipeptide under physiological pH as model reaction. Comparison of the activation parameters in the presence of NU-1000 with those observed with MOF-808 revealed the reaction outcome is largely governed by the Zr cluster. Additionally, its structural environment completely changes the energy profile of the hydrolysis step, resulting in a higher energy barrier Δ for NU-1000 due to a much larger Δ term. The reactivity of NU-1000 towards a hen egg white lysozyme protein under physiological pH was also evaluated, and the results pointed to a selective cleavage at only 3 peptide bonds. This showcases the potential of Zr-MOFs to be developed into heterogeneous catalysts for non-enzymatic but selective transformation of biomolecules, which are crucial for many modern applications in biotechnology and proteomics.
确定影响金属有机框架（MOF）反应活性的结构参数颇具挑战性。然而，了解它们的作用对于进一步开发其催化潜力至关重要。在此，我们以生理pH下二肽的水解为模型反应，揭示了MOF纳米酶的反应动力学与形态结构之间的关联。将存在NU-1000时的活化参数与MOF-808的观测值进行比较，结果表明反应结果在很大程度上由Zr簇决定。此外，其结构环境完全改变了水解步骤的能量分布，由于更大的Δ项，导致NU-1000具有更高的能垒Δ。我们还评估了NU-1000在生理pH下对鸡蛋清溶菌酶蛋白的反应活性，结果表明仅在3个肽键处发生选择性裂解。这展示了Zr-MOFs开发成为用于生物分子非酶促但选择性转化的多相催化剂的潜力，这对于生物技术和蛋白质组学中的许多现代应用至关重要。
