B3LYP/6-31G*, RHF/6-31G* and MM3 heats of formation of disaccharide analogs

A. D. French, A. M. Kelterer, G. P. Johnson, M. K. Dowd

Research output: Contribution to journalArticleResearchpeer-review

Abstract

ΔHf values were calculated with the bond- and group-enthalpy method for analogs of 13 disaccharides to learn the relative stabilities for various configurations about the carbon atoms connected to the linkage oxygen atom. The analogs were based on tetrahydropyran and, in the case of the sucrose analogs, tetrahydrofuran. The molecular mechanics program MM3 calculates these values as an option. The method was also used with RHF/6-31G* and B3LYP/6-31G* quantum mechanics (QM) theory. ΔHf values had ranges of 15-17 kcal (all energies herein are molar) by the different methods, with the analogs of the three trehaloses and sucrose having the lowest values. ΔHf values for the isomeric analogs of non-reducing sugars with two anomeric centers are about - 150 kcal, about 8 kcal lower than for the analogs of the reducing dimers (nigerose, maltose, laminarabiose, cellobiose and galabiose (α-D-galactosyl-D-galactose)) by all three types of calculation. The analogs of the di-axial, axial-equatorial and di-equatorial, non-glycosidic pseudo-disaccharides had ΔHf values within 1.0 kcal by each of the three methods. They were about 8 kcal higher than for the molecules that contain one glycosidic sequence. The relative ΔHf values by QM were within 1.0 kcal of their corresponding relative electronic energies, except for the methylated sucrose analog, for which the discrepancy was about 1.85 kcal at both QM levels. Compared to our B3LYP results, the RHF-based calculations overestimated the stability of all molecules by about 2.85 kcal. The MM3 values were close to the B3LYP numbers, with the largest discrepancy for the cellobiose analog, 1.76 kcal. The stabilization embodied in the group enthalpy increment for anomeric centers is another manifestation of the anomeric effect.

Original languageEnglish
Pages (from-to)303-313
Number of pages11
JournalJournal of molecular structure
Volume556
Issue number1-3
DOIs
Publication statusPublished - 12 Dec 2000

Fingerprint

Disaccharides
Quantum theory
heat of formation
Mechanics
Sucrose
Cellobiose
Hot Temperature
analogs
Enthalpy
Atoms
Trehalose
Molecular mechanics
Molecules
Maltose
Quantum Theory
sucrose
Galactose
Sugars
Dimers
quantum mechanics

Keywords

  • Carbohydrates
  • Cellobiose
  • Exo-anomeric effect
  • Galabiose
  • Laminarabiose
  • Maltose
  • Nigerose
  • Sucrose
  • Tetra hydrofuran
  • Tetrahydropyran
  • Trehalose

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

B3LYP/6-31G*, RHF/6-31G* and MM3 heats of formation of disaccharide analogs. / French, A. D.; Kelterer, A. M.; Johnson, G. P.; Dowd, M. K.

In: Journal of molecular structure, Vol. 556, No. 1-3, 12.12.2000, p. 303-313.

Research output: Contribution to journalArticleResearchpeer-review

French, A. D. ; Kelterer, A. M. ; Johnson, G. P. ; Dowd, M. K. / B3LYP/6-31G*, RHF/6-31G* and MM3 heats of formation of disaccharide analogs. In: Journal of molecular structure. 2000 ; Vol. 556, No. 1-3. pp. 303-313.
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AU - Dowd, M. K.

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AB - ΔHf values were calculated with the bond- and group-enthalpy method for analogs of 13 disaccharides to learn the relative stabilities for various configurations about the carbon atoms connected to the linkage oxygen atom. The analogs were based on tetrahydropyran and, in the case of the sucrose analogs, tetrahydrofuran. The molecular mechanics program MM3 calculates these values as an option. The method was also used with RHF/6-31G* and B3LYP/6-31G* quantum mechanics (QM) theory. ΔHf values had ranges of 15-17 kcal (all energies herein are molar) by the different methods, with the analogs of the three trehaloses and sucrose having the lowest values. ΔHf values for the isomeric analogs of non-reducing sugars with two anomeric centers are about - 150 kcal, about 8 kcal lower than for the analogs of the reducing dimers (nigerose, maltose, laminarabiose, cellobiose and galabiose (α-D-galactosyl-D-galactose)) by all three types of calculation. The analogs of the di-axial, axial-equatorial and di-equatorial, non-glycosidic pseudo-disaccharides had ΔHf values within 1.0 kcal by each of the three methods. They were about 8 kcal higher than for the molecules that contain one glycosidic sequence. The relative ΔHf values by QM were within 1.0 kcal of their corresponding relative electronic energies, except for the methylated sucrose analog, for which the discrepancy was about 1.85 kcal at both QM levels. Compared to our B3LYP results, the RHF-based calculations overestimated the stability of all molecules by about 2.85 kcal. The MM3 values were close to the B3LYP numbers, with the largest discrepancy for the cellobiose analog, 1.76 kcal. The stabilization embodied in the group enthalpy increment for anomeric centers is another manifestation of the anomeric effect.

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