Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose and L-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.

Cortese, R., Sifontes Herrera, V.A., Duca, D., Murzin, D. (2012). l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study. JOURNAL OF PHYSICAL CHEMISTRY. C, 116(116 (28)), 14908-14916 [10.1021/jp3026336].

l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study

CORTESE, Remedios;DUCA, Dario;
2012-01-01

Abstract

Adsorption of 5 L-arabinose tautomers – one acyclic and four cyclic (α and β, pyranose and furanose) species – on a ruthenium surface was studied as a precursor-process of the, nowadays more and more, industrially important sugar catalytic hydrogenation on metal surfaces in water medium. The study was mostly referred to a 37-atom metal catalyst fragment, even though border-effects on the adsorption processes were also checked employing a 61-atom metal fragment. In order to figure out conformational effects on the title process the tautomer flexibility was, at first, investigated by the genetic-algorithm based code Balloon, considering the conformational spaces of the different aquo tautomers. On the whole, 30 L-arabinose conformers, representing the complete conformational set (of a “realistic” water solution), were isolated by the genetic-algorithm based code Balloon. These were further refined at DFT level and then analyzed when interacting with a ruthenium surface, always at DFT level, by SIESTA. It was found that i) cyclic L-arabinose tautomers give rise to less strong adsorption than the acyclic tautomeric form; ii) L-arabinose molecules preferentially adsorb perpendicularly to the metallic surface; iii) one among the α-pyranose and one among the β-furanose derivatives are largely the most abundant adsorbed species; iv) the dominant L-arabinopyranose and L-arabinofuranose surface configurations are clearly related to corresponding not-adsorbed species that preserve both conformations and intramolecular hydrogen bonds during their the adsorption. The consideration of the points above allowed us to pick out significant properties, characterizing L-arabinose adsorption on ruthenium.
Settore CHIM/03 - Chimica Generale E Inorganica
Cortese, R., Sifontes Herrera, V.A., Duca, D., Murzin, D. (2012). l-Arabinose Conformers Adsorption on Ruthenium Surfaces: A DFT Study. JOURNAL OF PHYSICAL CHEMISTRY. C, 116(116 (28)), 14908-14916 [10.1021/jp3026336].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/64709
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