Del Vigo, E.A.; Marino, C.; Stortz, C.A."Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose" (2017) Carbohydrate Research. 448:136-147
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An exhaustive search approach was used to establish all possible rotamers of α- and β-D-galactopyranose using DFT at the B3LYP/6-311+G** and M06-2X/6-311+G** levels, both in vacuum calculations, and including two variants of continuum solvent models as PCM and SMD to simulate water solutions. Free energies were also calculated. MM3 was used as the starting point for calculations, using a dielectric constant of 1.5 for vacuum modeling, and 80 for water solution modeling. For the vacuum calculations, out of the theoretically possible 729 rotamers, only about a hundred rendered stable minima, highly stabilized by hydrogen bonding and scattered in a ca. 14 kcal/mol span. The rotamer with a clockwise arrangement of hydrogen bonds was the most stable for the α-anomer, whereas that with a counterclockwise arrangement was the most stable for the β-anomer. Free energy calculations, and especially solvent modeling, tend to flatten the potential energy surface. With PCM, the total range of energies was reduced to 9–10 kcal/mol (α-anomer) or 7–8 kcal/mol (β-anomer). These figures fall to 4.5–6 kcal/mol using SMD. At the same time, the total number of possible rotamers increases dramatically to about 300 with PCM, and to 400 with SMD. Both models show a divergent behavior: PCM tends to underestimate the effect of solvent, thus rendering as the most stable many common rotamers with vacuum calculations, and giving underestimations of populations of β-anomers and gt rotamers in the equilibrium. On the other hand, SMD gives a better estimation of the solvent effect, yielding correct populations of gt rotamers, but more β-anomers than expected by the experimental values. The best agreement is observed when the functional M06-2X is combined with SMD. Both DFT models show minimal geometrical differences between the optimized conformers. © 2017 Elsevier Ltd


Documento: Artículo
Título:Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose
Autor:Del Vigo, E.A.; Marino, C.; Stortz, C.A.
Filiación:Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Consejo Nacional de Investigaciones Científicas y Técnicas, Centro de Investigaciones en Hidratos de Carbono (CIHIDECAR), Departamento de Química Orgánica, Pab. 2, Ciudad Universitaria, Buenos Aires, 1428, Argentina
Palabras clave:Conformation; Density functional theory; Exhaustive search; Galactose; Rotamer; Solvent model; Chemical bonds; Conformations; Density functional theory; Free energy; Quantum chemistry; Solvents; Divergent behaviors; Exhaustive search; Experimental values; Free-energy calculations; Galactose; Geometrical differences; Rotamers; Solvent model; Hydrogen bonds; galactopyranose; galactose; unclassified drug; galactose; solvent; Article; calculation; chemical structure; conformation; density functional theory; dielectric constant; energy; hydrogen bond; priority journal; rotamer; solvation; solvent effect; vacuum; X ray diffraction; chemistry; conformation; molecular model; quantum theory; stereoisomerism; Carbohydrate Conformation; Galactose; Models, Molecular; Quantum Theory; Solvents; Stereoisomerism
Página de inicio:136
Página de fin:147
Título revista:Carbohydrate Research
Título revista abreviado:Carbohydr. Res.
CAS:galactose, 26566-61-0, 50855-33-9, 59-23-4; Galactose; Solvents


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---------- APA ----------
Del Vigo, E.A., Marino, C. & Stortz, C.A. (2017) . Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose. Carbohydrate Research, 448, 136-147.
---------- CHICAGO ----------
Del Vigo, E.A., Marino, C., Stortz, C.A. "Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose" . Carbohydrate Research 448 (2017) : 136-147.
---------- MLA ----------
Del Vigo, E.A., Marino, C., Stortz, C.A. "Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose" . Carbohydrate Research, vol. 448, 2017, pp. 136-147.
---------- VANCOUVER ----------
Del Vigo, E.A., Marino, C., Stortz, C.A. Exhaustive rotamer search of the 4C1 conformation of α- and β-D-galactopyranose. Carbohydr. Res. 2017;448:136-147.