DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps

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...

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Autores principales:	Navarro, Diego Alberto, Stortz, Carlos Arturo
Publicado:	2008
Materias:	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
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v343_n13_p2292_Navarro http://hdl.handle.net/20.500.12110/paper_00086215_v343_n13_p2292_Navarro
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_00086215_v343_n13_p2292_Navarro
record_format	dspace
spelling	paper:paper_00086215_v343_n13_p2292_Navarro2023-06-08T14:32:55Z DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps Navarro, Diego Alberto Stortz, Carlos Arturo 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 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. Fil:Navarro, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Stortz, C.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2008 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v343_n13_p2292_Navarro http://hdl.handle.net/20.500.12110/paper_00086215_v343_n13_p2292_Navarro
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	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
spellingShingle	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 Navarro, Diego Alberto Stortz, Carlos Arturo DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
topic_facet	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
description	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.
author	Navarro, Diego Alberto Stortz, Carlos Arturo
author_facet	Navarro, Diego Alberto Stortz, Carlos Arturo
author_sort	Navarro, Diego Alberto
title	DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
title_short	DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
title_full	DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
title_fullStr	DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
title_full_unstemmed	DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
title_sort	dft/mm modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps
publishDate	2008
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v343_n13_p2292_Navarro http://hdl.handle.net/20.500.12110/paper_00086215_v343_n13_p2292_Navarro
work_keys_str_mv	AT navarrodiegoalberto dftmmmodelingofthefivememberedringin36anhydrogalactosederivativesanditsinfluenceondisaccharideadiabaticmaps AT stortzcarlosarturo dftmmmodelingofthefivememberedringin36anhydrogalactosederivativesanditsinfluenceondisaccharideadiabaticmaps
_version_	1768545400366563328

DFT/MM modeling of the five-membered ring in 3,6-anhydrogalactose derivatives and its influence on disaccharide adiabatic maps

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