Abstract:
Different conformations of methyl 3,6-anhydro-4-O-methyl-α-d-galactoside (1) and 3,6-anhydro-4-O-methylgalactitol (2) were studied by molecular mechanics (using the program mm3) and by quantum mechanical (QM) methods at the B3LYP/6-31+G** and MP2/6-311++G** levels, with and without solvent emulation. In 2, where the five-membered ring is free to move, two main stable conformations of this ring were found, identified as North (N) and South (S). The latter appears to be more stable, by either calculation, though the energy difference is reduced when emulating solution behavior. In order to find out the possible influence of a glycosidic bond over its shape, and to explain the marked NMR chemical shift displacements observed by opening of the ring, the adiabatic maps of two disaccharides carrying an analog of β-galactoside linked to O-4 of 1 and 2 were generated. It was shown that the characteristics of the 3,6-AnGal terminal influence the characteristics of the map, especially at lower dielectric constants. On the other hand, different glycosidic angles also promote distinct stable conformations of the five-membered ring, changing from N to S, or even variants. Comparison with experimental results leads to the idea of highly flexible disaccharides, with variable values for both the five-membered ring and the glycosidic angles. © 2008 Elsevier Ltd. All rights reserved.
Registro:
Documento: |
Artículo
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Título: | DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps |
Autor: | Navarro, D.A.; Stortz, C.A. |
Filiación: | Departamento de Química Orgánica-CIHIDECAR, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina
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Palabras clave: | 3,6-Anhydrogalactose; Adiabatic maps; Five-membered ring; mm3; Modeling; Puckering; Maps; Polysaccharides; Speed; Quantum mechanical (QM) methods; Molecular mechanics; 3,6 anhydro 4 O methyl alpha dextro galactoside; 3,6 anhydro 4 O methylgalactitol; disaccharide; galactoside; solvent; adiabaticity; article; dielectric constant; mathematical computing; molecular biology; nuclear magnetic resonance; priority journal; quantum mechanics; Carbohydrate Conformation; Crystallography, X-Ray; Disaccharides; Galactitol; Galactose; Glycosides; Magnetic Resonance Spectroscopy; Models, Chemical; Molecular Conformation; Molecular Structure; Quantum Theory; Reproducibility of Results; Software |
Año: | 2008
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Volumen: | 343
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Número: | 13
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Página de inicio: | 2292
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Página de fin: | 2298
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DOI: |
http://dx.doi.org/10.1016/j.carres.2008.04.037 |
Título revista: | Carbohydrate Research
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Título revista abreviado: | Carbohydr. Res.
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ISSN: | 00086215
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CODEN: | CRBRA
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CAS: | Disaccharides; Galactitol, 608-66-2; Galactose, 26566-61-0; Glycosides
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Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v343_n13_p2292_Navarro |
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Citas:
---------- APA ----------
Navarro, D.A. & Stortz, C.A.
(2008)
. DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps. Carbohydrate Research, 343(13), 2292-2298.
http://dx.doi.org/10.1016/j.carres.2008.04.037---------- CHICAGO ----------
Navarro, D.A., Stortz, C.A.
"DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps"
. Carbohydrate Research 343, no. 13
(2008) : 2292-2298.
http://dx.doi.org/10.1016/j.carres.2008.04.037---------- MLA ----------
Navarro, D.A., Stortz, C.A.
"DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps"
. Carbohydrate Research, vol. 343, no. 13, 2008, pp. 2292-2298.
http://dx.doi.org/10.1016/j.carres.2008.04.037---------- VANCOUVER ----------
Navarro, D.A., Stortz, C.A. DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps. Carbohydr. Res. 2008;343(13):2292-2298.
http://dx.doi.org/10.1016/j.carres.2008.04.037