College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
Molecules. 2023 Jan 17;28(3):922. doi: 10.3390/molecules28030922.
Chiral amines are essential components for many pharmaceuticals and agrochemicals. However, the difficulty in obtaining enantiomerically pure amines limits their application. In this study, hollow amorphous ZIF-90 (HamZIF-90) materials were prepared by template engraving, and chemical-enzyme coupling catalysts (HamZIF-90@Pd@CALB) were constructed for the chiral resolution of 1-phenylethylamine. Different from conventional materials, HamZIF-90 had tunable hollow structures by altering its central node zinc ion concentrations, and the embedded hydrogel template gave it more pore structures, which facilitated the loading of enzyme molecules and Pd nanoparticles (NPs). The establishment of the coupling catalysts shortened the mass transfer distance of the reactant molecules between the metal nanoparticles and the enzyme catalyst in the dynamic kinetic resolution (DKR) reaction, resulting in 98% conversion of 1-phenylethylamine and 93% selectivity of Sel.R-amide. The proposal of this idea provided a good idea for future tailor-made MOFs loaded with chemical and enzyme coupled catalyst.
手性胺是许多药物和农用化学品的重要组成部分。然而,获得对映体纯胺的难度限制了它们的应用。在这项研究中,通过模板刻蚀制备了空心无定形 ZIF-90(HamZIF-90)材料,并构建了化学-酶偶联催化剂(HamZIF-90@Pd@CALB),用于 1-苯乙胺的对映体拆分。与传统材料不同,通过改变其中心节点锌离子浓度,HamZIF-90 具有可调谐的空心结构,嵌入的水凝胶模板赋予其更多的孔结构,有利于酶分子和钯纳米颗粒(NPs)的负载。偶联催化剂的建立缩短了动态动力学拆分(DKR)反应中金属纳米粒子和酶催化剂之间反应物分子的传质距离,导致 1-苯乙胺转化率达到 98%,Sel.R-酰胺选择性达到 93%。该理念的提出为未来定制负载化学和酶偶联催化剂的 MOFs 提供了一个很好的思路。