Premium
Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues
Author(s) -
Verma Manju,
Deshpande Parag A.
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600649
Subject(s) - exergonic reaction , chemistry , catalysis , adsorption , deprotonation , intramolecular force , reaction mechanism , rate determining step , density functional theory , dissociation (chemistry) , photochemistry , medicinal chemistry , inorganic chemistry , computational chemistry , stereochemistry , organic chemistry , ion
The biomimetic CO 2 hydration activity of Ru/Rh‐doped fullerenes was revealed by using density functional theory calculations. The mechanism of CO 2 hydration on the proposed heterofullerenes followed the mechanistic action of α‐carbonic anhydrases, and consisted of the adsorption and deprotonation of H 2 O, CO 2 interaction with hydroxyl groups, CO 2 bending, and proton transfer to give the HCO -3product. Free‐energy landscapes for the reaction showed the catalysts to be active for the reaction. H 2 O adsorption over the catalysts was exergonic whereas CO 2 adsorption 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 C 56 N 3 M (M=Ru/Rh), whereas H 2 O dissociation was found to be the rate‐limiting step for the reaction on C 59 M (M=Ru/Rh). C 56 N 3 M catalysts were found to be superior to C 59 M catalysts for biomimetic CO 2 hydration, as indicated by the free‐energy landscapes and energy requirements.