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Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering

Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively stud...

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Autores principales: Zubi, Yasmine S., Liu, Bingqing, Gu, Yifan, Sahoo, Dipankar, Lewis, Jared C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8809394/
https://www.ncbi.nlm.nih.gov/pubmed/35222930
http://dx.doi.org/10.1039/d1sc05792h
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author Zubi, Yasmine S.
Liu, Bingqing
Gu, Yifan
Sahoo, Dipankar
Lewis, Jared C.
author_facet Zubi, Yasmine S.
Liu, Bingqing
Gu, Yifan
Sahoo, Dipankar
Lewis, Jared C.
author_sort Zubi, Yasmine S.
collection PubMed
description Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)(3)(2+) for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.
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spelling pubmed-88093942022-02-24 Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering Zubi, Yasmine S. Liu, Bingqing Gu, Yifan Sahoo, Dipankar Lewis, Jared C. Chem Sci Chemistry Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)(3)(2+) for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts. The Royal Society of Chemistry 2022-01-10 /pmc/articles/PMC8809394/ /pubmed/35222930 http://dx.doi.org/10.1039/d1sc05792h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Zubi, Yasmine S.
Liu, Bingqing
Gu, Yifan
Sahoo, Dipankar
Lewis, Jared C.
Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title_full Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title_fullStr Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title_full_unstemmed Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title_short Controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
title_sort controlling the optical and catalytic properties of artificial metalloenzyme photocatalysts using chemogenetic engineering
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8809394/
https://www.ncbi.nlm.nih.gov/pubmed/35222930
http://dx.doi.org/10.1039/d1sc05792h
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