Li Yijia, Xia Chunlei, Tian Ruizhen, Zhao Linlu, Hou Jinxing, Wang Jieqiong, Luo Quan, Xu Jiayun, Wang Liang, Hou Chunxi, Yang Bai, Sun Hongcheng, Liu Junqiu
State Key laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China.
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Key Laboratory of Organosilicon Material Technology, Zhejiang Province, Hangzhou Normal University, Hangzhou 311121, China.
ACS Nano. 2022 May 24;16(5):8012-8021. doi: 10.1021/acsnano.2c00960. Epub 2022 May 5.
A controllable protein nanostructures-based "On/Off" switchable artificial light-harvesting system (LHS) with sequential multistep energy transfer and photocatalysis was reported herein for mimicking the natural LHS in both structure and function. Single-layered protein nanosheets were first constructed via a reversible covalent self-assembly strategy using cricoid stable protein one (SP1) as building blocks to realize an ordered arrangement of pigments. Fluorescent chromophores like carbon dots (CDs) can be precisely distributed on the protein nanosheets superficially via electrostatic interactions and make the ratio between donors and acceptors adjustable. After being anchored with a photocatalysis center (eosin-5-isothiocyanate, EY), the constructed LHS could sequentially transfer energy between two kinds of chromophores (CD1 and CD2), and further transfer to EY center with a high efficiency of 84%. Interestingly, the Förster resonance energy transfer (FRET) process of our LHS could be reversibly "On/Off" switched by the redox regulated assembly and disassembly of SP1 building blocks. Moreover, the LHS has been further proved to promote the yield of a model cross-coupling hydrogen evolution reaction and regulate the process of the reaction with the FRET process "On/Off" state.
本文报道了一种基于可控蛋白质纳米结构的“开/关”可切换人工光捕获系统（LHS），该系统具有顺序多步能量转移和光催化功能，旨在在结构和功能上模拟天然光捕获系统。首先，通过可逆共价自组装策略，以环状稳定蛋白一（SP1）为构建模块构建单层蛋白质纳米片，以实现色素的有序排列。荧光发色团如碳点（CDs）可以通过静电相互作用精确地分布在蛋白质纳米片表面，使供体和受体之间的比例可调。在锚定光催化中心（异硫氰酸 eosin-5，EY）后，构建的LHS可以在两种发色团（CD1和CD2）之间顺序转移能量，并进一步以84%的高效率转移到EY中心。有趣的是，我们的LHS的荧光共振能量转移（FRET）过程可以通过SP1构建模块的氧化还原调节组装和拆卸来可逆地“开/关”切换。此外，LHS已被进一步证明可以提高模型交叉偶联析氢反应的产率，并通过FRET过程的“开/关”状态调节反应过程。
