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Title: Light-driven carbon−carbon bond formation via CO 2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase

Abstract

Redox enzymes are capable of catalyzing a vast array of useful reactions, but they require redox partners that donate or accept electrons. Semiconductor nanocrystals provide a mechanism to convert absorbed photon energy into redox equivalents for enzyme catalysis. Here, we describe a system for photochemical carbon−carbon bond formation to make 2-oxoglutarate by coupling CO 2 with a succinyl group. Photoexcited electrons from cadmium sulfide nanorods (CdS NRs) transfer to 2-oxoglutarate:ferredoxin oxidoreductase from Magnetococcus marinus MC-1 (MmOGOR), which catalyzes a carbon−carbon bond formation reaction. We thereby decouple MmOGOR from its native role in the reductive tricarboxylic acid cycle and drive it directly with light. We examine the dependence of 2-oxoglutarate formation on a variety of factors and, using ultrafast transient absorption spectroscopy, elucidate the critical role of electron transfer (ET) from CdS NRs to MmOGOR. We find that the efficiency of this ET depends strongly on whether the succinyl CoA (SCoA) cosubstrate is bound at the MmOGOR active site. We hypothesize that the conformational changes due to SCoA binding impact the CdS NR−MmOGOR interaction in a manner that decreases ET efficiency compared to the enzyme with no cosubstrate bound. Our work reveals structural considerations for the nano−bio interfaces involved in light-drivenmore » enzyme catalysis and points to the competing factors of enzyme catalysis and ET efficiency that may arise when complex enzyme reactions are driven by artificial light absorbers.« less

Authors:
ORCiD logo; ; ; ; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1579964
Grant/Contract Number:  
SC0010334; SC0012598
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 1; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Hamby, Hayden, Li, Bin, Shinopoulos, Katherine E., Keller, Helena R., Elliott, Sean J., and Dukovic, Gordana. Light-driven carbon−carbon bond formation via CO 2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase. United States: N. p., 2019. Web. doi:10.1073/pnas.1903948116.
Hamby, Hayden, Li, Bin, Shinopoulos, Katherine E., Keller, Helena R., Elliott, Sean J., & Dukovic, Gordana. Light-driven carbon−carbon bond formation via CO 2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase. United States. doi:10.1073/pnas.1903948116.
Hamby, Hayden, Li, Bin, Shinopoulos, Katherine E., Keller, Helena R., Elliott, Sean J., and Dukovic, Gordana. Wed . "Light-driven carbon−carbon bond formation via CO 2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase". United States. doi:10.1073/pnas.1903948116.
@article{osti_1579964,
title = {Light-driven carbon−carbon bond formation via CO 2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase},
author = {Hamby, Hayden and Li, Bin and Shinopoulos, Katherine E. and Keller, Helena R. and Elliott, Sean J. and Dukovic, Gordana},
abstractNote = {Redox enzymes are capable of catalyzing a vast array of useful reactions, but they require redox partners that donate or accept electrons. Semiconductor nanocrystals provide a mechanism to convert absorbed photon energy into redox equivalents for enzyme catalysis. Here, we describe a system for photochemical carbon−carbon bond formation to make 2-oxoglutarate by coupling CO 2 with a succinyl group. Photoexcited electrons from cadmium sulfide nanorods (CdS NRs) transfer to 2-oxoglutarate:ferredoxin oxidoreductase from Magnetococcus marinus MC-1 (MmOGOR), which catalyzes a carbon−carbon bond formation reaction. We thereby decouple MmOGOR from its native role in the reductive tricarboxylic acid cycle and drive it directly with light. We examine the dependence of 2-oxoglutarate formation on a variety of factors and, using ultrafast transient absorption spectroscopy, elucidate the critical role of electron transfer (ET) from CdS NRs to MmOGOR. We find that the efficiency of this ET depends strongly on whether the succinyl CoA (SCoA) cosubstrate is bound at the MmOGOR active site. We hypothesize that the conformational changes due to SCoA binding impact the CdS NR−MmOGOR interaction in a manner that decreases ET efficiency compared to the enzyme with no cosubstrate bound. Our work reveals structural considerations for the nano−bio interfaces involved in light-driven enzyme catalysis and points to the competing factors of enzyme catalysis and ET efficiency that may arise when complex enzyme reactions are driven by artificial light absorbers.},
doi = {10.1073/pnas.1903948116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 1,
volume = 117,
place = {United States},
year = {2019},
month = {12}
}

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