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Theoretical study of structure and properties of hexuronic acid and d-glucosamine structural units of glycosaminoglycans


The Becke3LYP functional of DFT theory was used to investigate molecular structure and sodium affinity of the systems CH3CO2Na (1), CH3–O–SO3Na (2), CH3–NH–SO3Na (3), saccharide_1Na2 (4), saccharide_2Na (5), saccharide_3Na3 (6), saccharide_4Na2 (7), and saccharide_5Na2 (8), respectively, which are models of N- and O-sulfate glycosaminoglycans. Interaction enthalpies, entropies and Gibbs energies of the sodium-coordinated systems in the gas phase were determined with the B3LYP/6-311+G(d,p) and B3LYP/6-31+G(d) methods. The computed Gibbs energies, ΔG o, of model systems 13 are negative and span a rather broad energy interval (from −500 to −1,500 kJ mol−1). Gibbs interaction energies for sodium acetate, sodium sulfate and sodium sulfamate functions of the five saccharides, systems 48 are always lower than those values found for the model compounds 13. The ionization of sodium salts of saccharides studied in gas phase is in most cases connected with considerable conformational rearrangement of the ionic species. This rearrangement causes an additional energetic stabilization of anionic species and is connected with the substantial release of entropy.

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This research was supported by the grant from the APVV Granting Agency (Grant No. 51-034504).

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Correspondence to Milan Remko.

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Remko, M., Hricovíni, M. Theoretical study of structure and properties of hexuronic acid and d-glucosamine structural units of glycosaminoglycans. Struct Chem 18, 537–547 (2007).

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  • Hexuronic Acid
  • d-Glucosamine
  • Glycosaminoglycans
  • DFT method