image: An artificial photoenzymatic cascade was built through combining the photocatalytic H2O2 production by COF-TfpBpy with the H2O2-dependent enzymatic activity of P450 peroxygenases, achieving efficient sacrificial reagent free synthesis of 1-alkenes and hydroxyl fatty acids from naturally abundant fatty acids with only water, air and visible light.
Credit: ©Science China Press
This study is led by Prof. Dr. Shengying Li (State Key Laboratory of Microbial Technology, Shandong University) and Ass. Prof. Dr. Biaobiao Zhang (School of Science, Westlake University). The team designed and built a photoenzymatic cascade by combining photochemical water oxidation/O2 reduction with P450 peroxygenase catalysis to achieve efficient visible-light-driven oxidation of a range of fatty acids (C12-C20), leading to production of α-alkenes and hydroxyl fatty acids.
Fuels and oleochemicals have been chemically produced from abundant biological oils or fatty acids for more than a century, and modern biotechnology is now accelerating the advances in fatty acid chemistry. In recent years, enzymatic synthesis has been emerging as an effective way to produce value-added chemicals from renewable fatty acids. However, it is challenging to build a holistic catalytic system that requires only light, water and dioxygen for efficient conversion of the naturally abundant fatty acids.
The photo-biocatalytic system they established no longer requires any conventional sacrificial reagent or stabilizer, and the transformation of naturally abundant fatty acids into value-added products can be conveniently achieved by using two catalysts, water, air and light. This “green” process gave a promising TON > 15,000 for both P450BSβ and P450BSβ-DC and achieved gram scale production of α-olefins. This represents the most efficient H2O2-supplying system to support the catalytic activity of P450 peroxygenases so far. Besides, their successful establishment of the COF-TfpBpy/P450 peroxygenase hybrid system presents a new example to utilize solar energy to drive enzymatic conversions, providing a new and promising application of COFs.
Considering the simplicity, productivity and reusability of the photocatalyst COF-TfpBpy and scalability of the established cascade, they envision a more catalytically efficient, environmentally friendly, sustainable, and cost-effective cascade reaction will be available upon more optimization and development for large scale bioproduction of 1-alkenes and hydroxyl fatty acids from abundant fatty acid substrates.
See the article:
Photoenzymatic synthesis of 1-alkenes and hydroxyl fatty acids by cascading a COF photocatalyst and P450 peroxygenases
Journal
Science Bulletin