当前位置:科学网首页 > 小柯机器人 >详情
自适应配位分子胶囊模拟光氧化酶
作者:小柯机器人 发布时间:2021/9/25 19:08:55

中科院福建物质结构研究所孙庆福团队开发出了利用自适应配位分子胶囊模拟光氧化酶的策略。相关研究成果发表在2021年9月23日出版的国际知名学术期刊《美国化学会杂志》。

酶催化的一个重要特征是在与底物结合后诱导契合构象的变化。

该文中,研究人员报道了一种仿生水溶性分子胶囊,其具有向底物结合的适应性结构变化,为高效光催化提供了理想的平台。分子胶囊由三个蒽桥联双TPT[TPT=2,4,6-三(4-吡啶基)-1,3,5-三嗪]配体和六个(bpy)Pd(NO3)2(bpy=2,2′-联吡啶)配位组装而成。一旦基质结合到其疏水腔,该胶囊将经历定量的胶囊到碗的转化。蒽单元产生的可见光吸收和后期形成的五重π-π堆积主客体络合物上的电荷转移吸收,在温和条件下有效地促进了硫化物客体在可见光照射下的好氧光氧化。

通过催化剂的可转化性质和亚砜产品的亲水性,实现了预期的周转数和产品选择性(亚砜对砜)。由适应性配位胶囊和变构效应物等基质实现的光催化过程,为构建模拟酶催化的人工系统铺平了道路。

附:英文原文

Title: Photooxidase Mimicking with Adaptive Coordination Molecular Capsules

Author: Dan-Ni Yan, Li-Xuan Cai, Pei-Ming Cheng, Shao-Jun Hu, Li-Peng Zhou, Qing-Fu Sun

Issue&Volume: September 23, 2021

Abstract: One important feature of enzyme catalysis is the induced-fit conformational change after binding substrates. Herein, we report a biomimetic water-soluble molecular capsule featuring adaptive structural change toward substrate binding, which offers an ideal platform for efficient photocatalysis. The molecular capsule was coordination-assembled from three anthracene-bridged bis-TPT [TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] ligands and six (bpy)Pd(NO3)2 (bpy = 2,2′-bipyridine). Once substrates bind to its hydrophobic cavity, this capsule would undergo quantitative capsule-to-bowl transformation. Visible-light absorption brought about by both the anthracene units and the charge-transfer absorption on the late-formed quintuple π–π stacked host–guest complex efficiently facilitates aerobic photooxidation for the sulfide guests by visible-light irradiation under mild conditions. Desired turnover numbers and product selectivity (sulfoxide over sulfone) have been achieved by the transformable nature of the catalyst and the hydrophilicity of the sulfoxide product. Such a photocatalytic process enabled by an adaptive coordination capsule and substrates as the allosteric effector paves the way for constructing artificial systems to mimic enzyme catalysis.

DOI: 10.1021/jacs.1c06390

Source: https://pubs.acs.org/doi/10.1021/jacs.1c06390

 

期刊信息

JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000