Li Ke, Zou Houbing, Tong Xili, Yang Hengquan
Shanxi Key Laboratory of Coal-based Value-added Chemicals Green Catalysis Synthesis, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China.
Shanxi Research Institute of Huairou Laboratory, Taiyuan 030032, China.
J Am Chem Soc. 2024 Jun 26;146(25):17054-17065. doi: 10.1021/jacs.4c01834. Epub 2024 Jun 13.
Developing new methods to engineer photobiocatalytic reactions is of utmost significance for artificial photosynthesis, but it remains a grand challenge due to the intrinsic incompatibility of biocatalysts with photocatalysts. In this work, photocatalysts and enzymes were spatially colocalized at Pickering droplet interfaces, where the reaction microenvironment and the spatial distance between two distinct catalysts were exquisitely regulated to achieve unprecedented photobiocatalytic cascade reactions. As proof of the concept, ultrathin graphitic carbon nitride nanosheets loaded with Au nanoparticles were precisely positioned in the outer interfacial layer of Pickering oil droplets to produce HO under light irradiation, while enzymes were exactly placed in the inner interfacial layer to catalyze the subsequent biocatalytic oxidation reactions using in situ formed HO as an oxidant. In the alkene epoxidation and thioether oxidation, our interfacial photobiocatalytic cascades showed a 2.0-5.8-fold higher overall reaction efficiency than the photobiocatalytic cascades in the bulk water phase. It was demonstrated that spatial localization of the photocatalyst and the enzyme at Pickering oil droplet interfaces not only provided their respective preferable reaction environments and intimate proximity for rapid HO transport but also protected the enzyme from oxidative inactivation caused by the photogenerated species. These remarkable interfacial effects contributed to the significantly enhanced photobiocatalytic cascading efficiency. Our work presents an innovative photobiocatalytic reaction system with manifold benefits, providing a cutting-edge platform for solar-driven chemical transformations via photobiocatalysis.
开发用于设计光生物催化反应的新方法对人工光合作用至关重要，但由于生物催化剂与光催化剂之间固有的不相容性，这仍然是一个巨大的挑战。在这项工作中，光催化剂和酶在皮克林液滴界面处空间共定位，在那里反应微环境以及两种不同催化剂之间的空间距离被精确调控，以实现前所未有的光生物催化级联反应。作为概念验证，负载金纳米颗粒的超薄石墨氮化碳纳米片被精确地定位在皮克林油滴的外界面层，以便在光照下产生羟基自由基，而酶则被准确地放置在内界面层，以原位形成的羟基自由基作为氧化剂催化后续的生物催化氧化反应。在烯烃环氧化和硫醚氧化反应中，我们的界面光生物催化级联反应的总反应效率比本体水相中的光生物催化级联反应高2.0至5.8倍。结果表明，光催化剂和酶在皮克林油滴界面处的空间定位不仅为它们各自提供了优选的反应环境，并使它们紧密靠近以实现羟基自由基的快速传输，而且还保护酶免受光生物种引起的氧化失活。这些显著的界面效应有助于显著提高光生物催化级联反应效率。我们的工作提出了一种具有多种优势的创新光生物催化反应体系，为通过光生物催化进行太阳能驱动的化学转化提供了一个前沿平台。
