Reactivity Tuning of Metal-Free Artificial Photoenzymes through Binding Site Specific Bioconjugation
Reactivity Tuning of Metal-Free Artificial Photoenzymes through Binding Site Specific Bioconjugation
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DOI：
10.1002/ejoc.202201412
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发表时间：
2023-03-10
影响因子：
2.8
通讯作者：
Jarvis, Amanda G.
中科院分区：
文献类型：
--
作者：
Kuckhoff, Thomas;Brewster, Richard C.;Jarvis, Amanda G.
人工无金属光酶的设计和开发旨在结合酶反应的选择性和现代合成光催化剂的优点。消除了对稀土金属的需求，并允许更温和的反应条件，从而产生更可持续的催化系统。在这里，我们提出了一种新型的人工光酶的设计，将基于供体-受体设计的有机光催化部分整合到类固醇载体蛋白(SCP-2L)中。SCP-2L具有疏水隧道，便于底物在水介质中结合。光催化剂被选择性地结合到三个SCP-2L突变体上，拥有一个非天然的半胱氨酸残基，策略性地放置在蛋白质的疏水隧道周围。这三种修饰的光酶对有机硫化物的氧化具有选择性，最高可达192个转化率。
The design and development of artificial metal-free photoenzymes aims to combine the selectivity of enzymatic reactions with the benefits of modern synthetic photocatalysts. Removing the need for rare earth metals and allowing for milder reaction conditions, leading to a more sustainable catalytic system. Here, we present the design of a novel artificial photoenzyme by integrating an organophotocatalytic moiety based on a donor-acceptor design into a steroid carrier protein (SCP-2L). SCP-2L possesses a hydrophobic tunnel facilitating substrate binding in aqueous media. The photocatalyst was site-selectively bound to three SCP-2L variants, possessing a non-native cysteine residue strategically placed around the hydrophobic tunnel of the protein. The three modified photoenzymes were shown to be selective for the oxidation of organic sulfides giving up to 192 turnovers.