HF/6-31G* Energy Surfaces for Disaccharide Analogs

Alfred D. French, Anne Marie Kelterer, Glenn P. Johnson, Michael K. Dowd, Christopher J. Cramer

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The HF/6-31G* level of theory was used to calculate relaxed potential energy surfaces for 12 analogs of disaccharides. The analogs were made by replacing glucose with tetrahydropyran and fructose with 2-methyltetrahydrofuran. Molecules had zero, one or two anomeric carbon atoms, and di-axial, axial-equatorial, and di-equatorial linkages. Despite the absence of hydroxyl groups, the surfaces account well for conformations that are observed in crystals of the parent disaccharides. Thus, torsional energy and the simple bulk of ring structures are major factors in determining disaccharide conformation. The contour shapes around the global minima depend on the number of anomeric carbons involved in the linkage, while the presence of alternative minima that have relative energies less than 4 kcal/mol mostly requires equatorial bonds. However, molecules with two adjacent anomeric centers gave exceptions to these rules. Flexibility values related to a partition function show that the di-axial trehalose analog is the most rigid. The di-equatorial pseudodisaccharide analog with no anomeric centers is most flexible. Reproduction of these surfaces is proposed as a simple test of force fields for modeling carbohydrates. Also, these surfaces can be used in a simple hybrid method for calculating disaccharide energy surfaces.

Original languageEnglish
Pages (from-to)65-78
Number of pages14
JournalJournal of Computational Chemistry
Volume22
Issue number1
DOIs
Publication statusPublished - 15 Jan 2001

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Disaccharides
Surface Energy
Interfacial energy
Analogue
Conformation
Linkage
Conformations
Carbon
Molecules
Potential Energy Surface
Potential energy surfaces
Trehalose
Fructose
Carbohydrates
Force Field
Global Minimum
Hybrid Method
Energy
Glucose
Partition Function

ASJC Scopus subject areas

  • Chemistry(all)
  • Safety, Risk, Reliability and Quality

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HF/6-31G* Energy Surfaces for Disaccharide Analogs. / French, Alfred D.; Kelterer, Anne Marie; Johnson, Glenn P.; Dowd, Michael K.; Cramer, Christopher J.

In: Journal of Computational Chemistry, Vol. 22, No. 1, 15.01.2001, p. 65-78.

Research output: Contribution to journalArticleResearchpeer-review

French, Alfred D. ; Kelterer, Anne Marie ; Johnson, Glenn P. ; Dowd, Michael K. ; Cramer, Christopher J. / HF/6-31G* Energy Surfaces for Disaccharide Analogs. In: Journal of Computational Chemistry. 2001 ; Vol. 22, No. 1. pp. 65-78.
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