Print Email Facebook Twitter Piezobiocatalysis Title Piezobiocatalysis: Ultrasound-Driven Enzymatic Oxyfunctionalization of C-H Bonds Author Yoon, Jaeho (Korea Advanced Institute of Science and Technology) Kim, Jinhyun (Korea Advanced Institute of Science and Technology) Tieves, F. (TU Delft BT/Biocatalysis) Zhang, W. (TU Delft BT/Biocatalysis) Alcalde, Miguel (C/) Hollmann, F. (TU Delft BT/Biocatalysis) Park, Chan Beum (Korea Advanced Institute of Science and Technology) Date 2020 Abstract Peroxygenases have long inspired the selective oxyfunctionalization of various aliphatic and aromatic compounds, because of their broad substrate spectrum and simplicity of catalytic mechanism. This study provides a proof-of-concept of piezobiocatalysis by demonstrating peroxygenase-catalyzed oxyfunctionalization reactions fueled by piezocatalytically generated H2O2. Bismuth oxychloride (BiOCl) generated H2O2 in situ via an oxygen reduction reaction under ultrasonic wave conditions. Through the simple combination of water, ultrasound, recombinant, evolved unspecific peroxygenase from Agrocybe aegerita (rAaeUPO), and BiOCl, the piezobiocatalytic platform accelerated selective hydroxylation of ethylbenzene to enantiopure (R)-1-phenylethanol [total turnover number of rAaeUPO (TTNrAaeUPO), 2002; turnover frequency, 77.7 min-1 >99% enantiomeric excess (ee)]. The BiOCl-rAaeUPO couple also catalyzed other representative substrates (e.g., propylbenzene, 1-chloro-4-ethylbenzene, cyclohexane, and cis-β-methylstyrene) with high turnover frequency and selectivity. We alleviated the oxidative stress of piezocatalytically generated OH- on rAaeUPO by spatial separation of rAaeUPO and BiOCl, which resulted in greatly enhanced TTNrAaeUPO of >3900 and the notable prolongation of reaction time. Overall, the BiOCl-rAaeUPO couple serves as a mechanical-to-chemical energy conversion platform for driving peroxygenase-catalyzed reactions under ultrasonic conditions. Subject oxidationoxyfunctionalizationperoxygenasepiezobiocatalysispiezocatalysis To reference this document use: http://resolver.tudelft.nl/uuid:4e41f63a-019e-4348-b0f9-235ba40dc0e5 DOI https://doi.org/10.1021/acscatal.0c00188 Embargo date 2020-09-18 ISSN 2155-5435 Source ACS Catalysis, 10 (9), 5236-5242 Bibliographical note Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public. Part of collection Institutional Repository Document type journal article Rights © 2020 Jaeho Yoon, Jinhyun Kim, F. Tieves, W. Zhang, Miguel Alcalde, F. Hollmann, Chan Beum Park Files PDF acscatal.0c00188.pdf 4.61 MB Close viewer /islandora/object/uuid:4e41f63a-019e-4348-b0f9-235ba40dc0e5/datastream/OBJ/view