用于太阳能

大连理工大学段春迎团队开发了用于太阳能-化学转化的酶接枝的辅助因子修饰金属有机胶囊。相关研究成果发表在2023年3月14日出版的《美国化学会杂志》。

太阳能到化学转化的半人工方法可以实现超出天然酶能力的化学转化，但由于它们不可避免地需要辅因子穿梭和再生，因此在促进体内级联方面面临显著挑战。

该文中，研究人员报告了一种酶接枝策略，以构建金属-有机胶囊对接人工酶（金属有机酶，MOE），该策略包括辅因子修饰的胶囊的自组装以及酶支架和胶囊之间的超分子酶识别特征，以绕过辅因子穿梭和再生。金属有机胶囊内的NADH模拟物与由胺的缩合和醇底物在微环境中的脱氢形成的亚胺中间体相互作用，在胶囊内形成复合物，随后用作原位生成的光响应辅因子。

在光照下，光响应辅因子促进胶囊的内部空间（超分子氢化）和外部空间（酶脱氢）之间的有效质子/电子传输，以分别使醇脱氢和亚胺中间体氢化，从而避免传统复杂的多步骤辅因子穿梭和再生。半人工酶使水/有机溶液和大肠杆菌中不同类型的醇高效转化为胺产品，为商品和精细化学品的可持续和环保生物制造提供了广泛的机会。

附：英文原文

Title: Enzyme Grafting with a Cofactor-Decorated Metal-Organic Capsule for Solar-to-Chemical Conversion

Author: Jianwei Wei, Liang Zhao, Yu Zhang, Gang Han, Cheng He, Chong Wang, Chunying Duan

Issue&Volume: March 14, 2023

Abstract: Semi-artificial approaches to solar-to-chemical conversion can achieve chemical transformations that are beyond the capability of natural enzymes, but face marked challenges to facilitate in vivo cascades, due to their inevitable need for cofactor shuttling and regeneration. Here, we report on an enzyme grafting strategy to build a metal-organic capsule-docking artificial enzyme (metal-organic-enzyme, MOE) that comprised the self-assembly of a cofactor-decorated capsule and the supramolecular enzyme-recognition features between the enzyme scaffold and the capsule to bypass cofactor shuttling and regeneration. The incorporated NADH mimics within the metal-organic capsule interacted with the imine intermediate that formed from the condensation of the amines and the dehydrogenation of alcohol substrates in the microenvironment to form complexes within the capsule and subsequently served as an in situ-generated photoresponsive cofactor. Upon illumination, the photoresponsive cofactor facilitates efficient proton/electron transport between the inner space (supramolecular hydrogenation) and outer space (enzymatic dehydrogenation) of the capsule to dehydrogenize the alcohols and hydrogenize the imine intermediates, respectively, circumventing the conventionally complex multistep cofactor shuttling and regeneration. The semi-artificial enzyme endows the conversion of diverse types of alcohol to amine products in both aqueous/organic solutions and Escherichia coli with high efficiency, offering a wide range of opportunities for sustainable and environmentally friendly biomanufacturing of commodity and fine chemicals.

DOI: 10.1021/jacs.2c12636

Source: https://pubs.acs.org/doi/10.1021/jacs.2c12636

JACS：《美国化学会志》，创刊于1879年。隶属于美国化学会，最新IF：16.383 官方网址：https://pubs.acs.org/journal/jacsat 投稿链接：https://acsparagonplus.acs.org/psweb/loginForm?code=1000