State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, PR China.
Nanoscale. 2019 Mar 28;11(13):5960-5966. doi: 10.1039/c9nr01093a.
Nanozymes provide comparative advantages over natural enzymes and conventional artificial enzymes for catalytic reactions. However, nanozymes are only suitable for limited types of reactions, whose catalytic principles are not yet fully revealed. Herein, a new nanozyme based on a bionic zeolitic imidazolate framework is proposed. Zeolitic imidazolate framework-8 (ZIF-8) possesses a similar geometric structure to that of the active center of human carbonic anhydrase II (hCAII) and exhibits catalytic performance analogous to that of the hCAII. The less imidazolate coordinated zinc cations on the external surface of ZIF-8 can act as Lewis acid sites, lowering the pKa of Zn-bound H2O molecules from 14 to 8.4, which facilitates the deprotonation of H2O molecules and generation of zinc-bound hydroxide nucleophiles. The esterase-like ZIF-8 nanozyme shows a similar affinity to p-nitrophenyl acetate compared with hCAII. The ZIF-8 nanozyme also promotes CO2 hydration and acetylthiocholine hydrolysis reaction, and a series of ZIFs are also found with intrinsic enzyme-like activities due to similar compositions and spatial structures. These results imply that the bionic nanoparticles can be developed to fabricate a new generation of nanozymes by mimicking the active sites of natural enzymes.
纳米酶在催化反应方面提供了相对于天然酶和传统人工酶的比较优势。然而,纳米酶仅适用于有限类型的反应,其催化原理尚未完全揭示。在此,提出了一种基于仿生沸石咪唑酯骨架的新型纳米酶。沸石咪唑酯骨架-8(ZIF-8)具有与人碳酸酐酶 II(hCAII)活性中心相似的几何结构,并表现出类似于 hCAII 的催化性能。ZIF-8 外表面较少配位的咪唑锌离子可以充当路易斯酸位,将 Zn 结合的 H2O 分子的 pKa 从 14 降低至 8.4,这有利于 H2O 分子的去质子化和生成锌结合的氢氧根亲核试剂。类酯酶的 ZIF-8 纳米酶与 hCAII 相比,对对硝基苯乙酸酯具有相似的亲和力。ZIF-8 纳米酶还促进了 CO2 水合和乙酰硫代胆碱水解反应,并且由于类似的组成和空间结构,一系列 ZIF 也被发现具有内在的酶样活性。这些结果表明,仿生纳米颗粒可以通过模拟天然酶的活性位点来开发新一代的纳米酶。