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Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts

[Image: see text] Due to their unique coordination structure, dirhodium paddlewheel complexes are of interest in several research fields, like medicinal chemistry, catalysis, etc. Previously, these complexes were conjugated to proteins and peptides for developing artificial metalloenzymes as homogen...

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Autores principales: Loreto, Domenico, Maity, Basudev, Morita, Taiki, Nakamura, Hiroyuki, Merlino, Antonello, Ueno, Takafumi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10189731/
https://www.ncbi.nlm.nih.gov/pubmed/37144589
http://dx.doi.org/10.1021/acs.inorgchem.3c00852
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author Loreto, Domenico
Maity, Basudev
Morita, Taiki
Nakamura, Hiroyuki
Merlino, Antonello
Ueno, Takafumi
author_facet Loreto, Domenico
Maity, Basudev
Morita, Taiki
Nakamura, Hiroyuki
Merlino, Antonello
Ueno, Takafumi
author_sort Loreto, Domenico
collection PubMed
description [Image: see text] Due to their unique coordination structure, dirhodium paddlewheel complexes are of interest in several research fields, like medicinal chemistry, catalysis, etc. Previously, these complexes were conjugated to proteins and peptides for developing artificial metalloenzymes as homogeneous catalysts. Fixation of dirhodium complexes into protein crystals is interesting to develop heterogeneous catalysts. Porous solvent channels present in protein crystals can benefit the activity by increasing the probability of substrate collisions at the catalytic Rh binding sites. Toward this goal, the present work describes the use of bovine pancreatic ribonuclease (RNase A) crystals with a pore size of 4 nm (P3(2)21 space group) for fixing [Rh(2)(OAc)(4)] and developing a heterogeneous catalyst to perform reactions in an aqueous medium. The structure of the [Rh(2)(OAc)(4)]/RNase A adduct was investigated by X-ray crystallography: the metal complex structure remains unperturbed upon protein binding. Using a number of crystal structures, metal complex accumulation over time, within the RNase A crystals, and structures at variable temperatures were evaluated. We also report the large-scale preparation of microcrystals (∼10–20 μm) of the [Rh(2)(OAc)(4)]/RNase A adduct and cross-linking reaction with glutaraldehyde. The catalytic olefin cyclopropanation reaction and self-coupling of diazo compounds by these cross-linked [Rh(2)(OAc)(4)]/RNase A crystals were demonstrated. The results of this work reveal that these systems can be used as heterogeneous catalysts to promote reactions in aqueous solution. Overall, our findings demonstrate that the dirhodium paddlewheel complexes can be fixed in porous biomolecule crystals, like those of RNase A, to prepare biohybrid materials for catalytic applications.
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spelling pubmed-101897312023-05-18 Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts Loreto, Domenico Maity, Basudev Morita, Taiki Nakamura, Hiroyuki Merlino, Antonello Ueno, Takafumi Inorg Chem [Image: see text] Due to their unique coordination structure, dirhodium paddlewheel complexes are of interest in several research fields, like medicinal chemistry, catalysis, etc. Previously, these complexes were conjugated to proteins and peptides for developing artificial metalloenzymes as homogeneous catalysts. Fixation of dirhodium complexes into protein crystals is interesting to develop heterogeneous catalysts. Porous solvent channels present in protein crystals can benefit the activity by increasing the probability of substrate collisions at the catalytic Rh binding sites. Toward this goal, the present work describes the use of bovine pancreatic ribonuclease (RNase A) crystals with a pore size of 4 nm (P3(2)21 space group) for fixing [Rh(2)(OAc)(4)] and developing a heterogeneous catalyst to perform reactions in an aqueous medium. The structure of the [Rh(2)(OAc)(4)]/RNase A adduct was investigated by X-ray crystallography: the metal complex structure remains unperturbed upon protein binding. Using a number of crystal structures, metal complex accumulation over time, within the RNase A crystals, and structures at variable temperatures were evaluated. We also report the large-scale preparation of microcrystals (∼10–20 μm) of the [Rh(2)(OAc)(4)]/RNase A adduct and cross-linking reaction with glutaraldehyde. The catalytic olefin cyclopropanation reaction and self-coupling of diazo compounds by these cross-linked [Rh(2)(OAc)(4)]/RNase A crystals were demonstrated. The results of this work reveal that these systems can be used as heterogeneous catalysts to promote reactions in aqueous solution. Overall, our findings demonstrate that the dirhodium paddlewheel complexes can be fixed in porous biomolecule crystals, like those of RNase A, to prepare biohybrid materials for catalytic applications. American Chemical Society 2023-05-05 /pmc/articles/PMC10189731/ /pubmed/37144589 http://dx.doi.org/10.1021/acs.inorgchem.3c00852 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Loreto, Domenico
Maity, Basudev
Morita, Taiki
Nakamura, Hiroyuki
Merlino, Antonello
Ueno, Takafumi
Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title_full Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title_fullStr Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title_full_unstemmed Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title_short Cross-Linked Crystals of Dirhodium Tetraacetate/RNase A Adduct Can Be Used as Heterogeneous Catalysts
title_sort cross-linked crystals of dirhodium tetraacetate/rnase a adduct can be used as heterogeneous catalysts
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10189731/
https://www.ncbi.nlm.nih.gov/pubmed/37144589
http://dx.doi.org/10.1021/acs.inorgchem.3c00852
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