Puellmann, Pascal and Homann, Dominik and Karl, Tobias A. and Koenig, Burkhard and Weissenborn, Martin J. (2023) Light-Controlled Biocatalysis by Unspecific Peroxygenases with Genetically Encoded Photosensitizers. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 62 (41). ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
Fungal unspecific peroxygenases (UPOs) have gained substantial attention for their versatile oxyfunctionalization chemistry paired with impressive catalytic capabilities. A major drawback, however, remains their sensitivity towards their co-substrate hydrogen peroxide, necessitating the use of smart in situ hydrogen peroxide generation methods to enable efficient catalysis setups. Herein, we introduce flavin-containing protein photosensitizers as a new general tool for light-controlled in situ hydrogen peroxide production. By genetically fusing flavin binding fluorescent proteins and UPOs, we have created two virtually self-sufficient photo-enzymes (PhotUPO). Subsequent testing of a versatile substrate panel with the two divergent PhotUPOs revealed two stereoselective conversions. The catalytic performance of the fusion protein was optimized through enzyme and substrate loading variation, enabling up to 24300 turnover numbers (TONs) for the sulfoxidation of methyl phenyl sulfide. The PhotUPO concept was upscaled to a 100 mg substrate preparative scale, enabling the extraction of enantiomerically pure alcohol products. Unspecific peroxygenases (UPOs) have recently gained attraction as versatile oxyfunctionalization catalysts. One shortcoming, however, is their susceptibility towards the co-substrate hydrogen peroxide. As a solution, the concept of light-dependent UPO biocatalysis with genetically encoded flavin-containing photosensitizer proteins for in situ hydrogen peroxide production is introduced.+image
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PROTEINS; Biocatalysis; oxyfunctionalization; unspecific peroxygenases; flavins; photocatalysis |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 26 Mar 2024 06:41 |
| Last Modified: | 26 Mar 2024 06:41 |
| URI: | https://pred.uni-regensburg.de/id/eprint/60528 |
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