TY - JOUR

T1 - Transmembrane Shuttling of Photosynthetically Produced Electrons to Propel Extracellular Biocatalytic Redox Reactions in a Modular Fashion

AU - Jurkaš, Valentina

AU - Weissensteiner, Florian

AU - De Santis, Piera

AU - Vrabl, Stephan

AU - Sorgenfrei, Frieda A.

AU - Bierbaumer, Sarah

AU - Kara, Selin

AU - Kourist, Robert

AU - Wangikar, Pramod P.

AU - Winkler, Christoph K.

AU - Kroutil, Wolfgang

N1 - Funding Information: This project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska‐Curie grant agreement No 764920. S.B. acknowledge the Austrian Science Fund (FWF) for funding within the project CATALOX (DOC 46‐B21). The COMET center: acib: Next Generation Bioproduction is funded by BMK, BMDW, SFG, Standortagentur Tirol, Government of Lower Austria und Vienna Business Agency in the framework of COMET—Competence Centers for Excellent Technologies. The COMET‐Funding Program is managed by the Austrian Research Promotion Agency FFG. The University of Graz and the Field of Excellence BioHealth are acknowledged for financial support. J. Schrittwieser is acknowledged for providing substrate. Funding Information: This project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 764920. S.B. acknowledge the Austrian Science Fund (FWF) for funding within the project CATALOX (DOC 46-B21). The COMET center: acib: Next Generation Bioproduction is funded by BMK, BMDW, SFG, Standortagentur Tirol, Government of Lower Austria und Vienna Business Agency in the framework of COMET—Competence Centers for Excellent Technologies. The COMET-Funding Program is managed by the Austrian Research Promotion Agency FFG. The University of Graz and the Field of Excellence BioHealth are acknowledged for financial support. J. Schrittwieser is acknowledged for providing substrate. Publisher Copyright: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2022/9/26

Y1 - 2022/9/26

N2 - Many biocatalytic redox reactions depend on the cofactor NAD(P)H, which may be provided by dedicated recycling systems. Exploiting light and water for NADPH-regeneration as it is performed, e.g. by cyanobacteria, is conceptually very appealing due to its high atom economy. However, the current use of cyanobacteria is limited, e.g. by challenging and time-consuming heterologous enzyme expression in cyanobacteria as well as limitations of substrate or product transport through the cell wall. Here we establish a transmembrane electron shuttling system propelled by the cyanobacterial photosynthesis to drive extracellular NAD(P)H-dependent redox reactions. The modular photo-electron shuttling (MPS) overcomes the need for cloning and problems associated with enzyme- or substrate-toxicity and substrate uptake. The MPS was demonstrated on four classes of enzymes with 19 enzymes and various types of substrates, reaching conversions of up to 99 % and giving products with >99 % optical purity.

AB - Many biocatalytic redox reactions depend on the cofactor NAD(P)H, which may be provided by dedicated recycling systems. Exploiting light and water for NADPH-regeneration as it is performed, e.g. by cyanobacteria, is conceptually very appealing due to its high atom economy. However, the current use of cyanobacteria is limited, e.g. by challenging and time-consuming heterologous enzyme expression in cyanobacteria as well as limitations of substrate or product transport through the cell wall. Here we establish a transmembrane electron shuttling system propelled by the cyanobacterial photosynthesis to drive extracellular NAD(P)H-dependent redox reactions. The modular photo-electron shuttling (MPS) overcomes the need for cloning and problems associated with enzyme- or substrate-toxicity and substrate uptake. The MPS was demonstrated on four classes of enzymes with 19 enzymes and various types of substrates, reaching conversions of up to 99 % and giving products with >99 % optical purity.

KW - Biocatalysis

KW - Photocatalysis

KW - Redox Chemistry

KW - Reductions

KW - Transmembrane Shuttling

UR - http://www.scopus.com/inward/record.url?scp=85137031837&partnerID=8YFLogxK

U2 - 10.1002/anie.202207971

DO - 10.1002/anie.202207971

M3 - Article

C2 - 35921249

AN - SCOPUS:85137031837

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 40

M1 - e202207971

ER -