title: Computational Design of New Heterofullerene-Based Biomimetic α-Carbonic Anhydrase Analogues.
abstract: The biomimetic CO2hydration activity of Ru/Rh-doped fullerenes was revealed by using density functional theory calculations. The mechanism of CO2hydration on the proposed heterofullerenes followed the mechanistic action of α-carbonic anhydrases, and consisted of the adsorption and deprotonation of H2O, CO2interaction with hydroxyl groups, CO2bending, and proton transfer to give the HCO-3 product. Free-energy landscapes for the reaction showed the catalysts to be active for the reaction. H2O adsorption over the catalysts was exergonic whereas CO2adsorption over the catalyst-OH complex was observed to be an endergonic process. Intramolecular proton transfer resulting in the final product, HCO-3 , was found to be the rate-limiting step for the reaction on C56N3M (M=Ru/Rh), whereas H2O dissociation was found to be the rate-limiting step for the reaction on C59M (M=Ru/Rh). C56N3M catalysts were found to be superior to C59M catalysts for biomimetic CO2hydration, as indicated by the free-energy landscapes and energy requirements.
authors.affiliation: Quantum and Molecular Engineering Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur, 721302, India), Tel: (+91) 3222-283916.
authors.forename: Manju
authors.initials: M
authors.lastname: Verma
authors.affiliation: Quantum and Molecular Engineering Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur, 721302, India), Tel: (+91) 3222-283916. parag@che.iitkgp.ernet.in.
authors.forename: Parag A
authors.initials: PA
authors.lastname: Deshpande
mesh_terms: D055162:Biocatalysis; D040761:Biomimetic Materials / Q000737:chemistry* / Q000378:metabolism; D002245:Carbon Dioxide / Q000737:chemistry* / Q000378:metabolism; D002256:Carbonic Anhydrases / Q000737:chemistry* / Q000378:metabolism; D037741:Fullerenes / Q000737:chemistry* / Q000378:metabolism; D011789:Quantum Theory; D012238:Rhodium / Q000737:chemistry / Q000378:metabolism; D012428:Ruthenium / Q000737:chemistry / Q000378:metabolism; D014867:Water / Q000737:chemistry / Q000378:metabolism
chemical_list: D037741:Fullerenes; D014867:Water; D002245:Carbon Dioxide; D012428:Ruthenium; D012238:Rhodium; D002256:Carbonic Anhydrases
keywords: biomimetic catalysis; carbon dioxide fixation; density functional calculations; electronic structure; free-energy landscape