TY - JOUR
T1 - Light-Driven NADPH Cofactor Recycling by Photosystem I for Biocatalytic Reactions
AU - Medipally, Hitesh
AU - Guarneri, Alice
AU - Pospisil, Lars
AU - Franssen, Maurice C.R.
AU - van Berkel, Willem J.H.
AU - Paul, Caroline E.
AU - Nowaczyk, Marc M.
PY - 2023
Y1 - 2023
N2 - Biocatalytic asymmetric reduction of C=C and C=O bonds is highly attractive to produce valuable (chiral) chemicals for the fine and pharmaceutical industry, yet occurs at the expense of reduced nicotinamide adenine dinucleotide coenzyme NADPH that requires recycling. Established methods each have their challenges. Here we developed a light-driven approach based on photosystem I (PSI) by mimicking the natural electron transfer from PSI via ferredoxin (Fd) towards ferredoxin NADP+ reductase (FNR) in vitro. Illumination with red light led to reduction of NADP+ to NADPH with a turnover frequency of 2.55 s−1 (>9000 h−1) at pH 7.5. Light-driven NADPH regeneration by PSI-Fd-FNR was coupled with three oxidoreductases for asymmetric reduction of C=C and C=O bonds, reaching up to 99 % conversion with a turnover number of 3035, and retaining enantioselectivity. This study demonstrates the capacity of a PSI system to drive continuous NADPH-dependent biocatalytic conversions with light.
AB - Biocatalytic asymmetric reduction of C=C and C=O bonds is highly attractive to produce valuable (chiral) chemicals for the fine and pharmaceutical industry, yet occurs at the expense of reduced nicotinamide adenine dinucleotide coenzyme NADPH that requires recycling. Established methods each have their challenges. Here we developed a light-driven approach based on photosystem I (PSI) by mimicking the natural electron transfer from PSI via ferredoxin (Fd) towards ferredoxin NADP+ reductase (FNR) in vitro. Illumination with red light led to reduction of NADP+ to NADPH with a turnover frequency of 2.55 s−1 (>9000 h−1) at pH 7.5. Light-driven NADPH regeneration by PSI-Fd-FNR was coupled with three oxidoreductases for asymmetric reduction of C=C and C=O bonds, reaching up to 99 % conversion with a turnover number of 3035, and retaining enantioselectivity. This study demonstrates the capacity of a PSI system to drive continuous NADPH-dependent biocatalytic conversions with light.
KW - biocascades
KW - enzymatic reduction
KW - ferredoxin NADP oxidoreductase
KW - NADPH cofactor regeneration
KW - photobiocatalysis
UR - http://www.scopus.com/inward/record.url?scp=85166981564&partnerID=8YFLogxK
U2 - 10.1002/cctc.202300821
DO - 10.1002/cctc.202300821
M3 - Article
AN - SCOPUS:85166981564
SN - 1867-3880
VL - 15
JO - ChemCatChem
JF - ChemCatChem
IS - 18
M1 - e202300821
ER -