Infrared spectra of solid and aqueous solutions of N-acetyl-alpha-D-glucosamine and beta-D-glucuronic acid have been investigated by means of Fourier transform infrared (FT-IR) spectroscopy and quantum chemical density functional theory (DFT) calculations. The errors of the computed harmonic force field were corrected according to the scaled quantum mechanical (SQM) method of Pulay, with scale factors partly from the literature and partly developed here. Scale factors for the hydrogen-bonded OH groups were determined by SQM treatment of ethylene glycol. The IR spectra and test computations revealed that beta-D-glucuronic acid is present as a dimer, formed by hydrogen-bonding between the COOH groups, in the solid phase. On the basis of the calculated results, 64 and 56 bands in the 4000-50 cm(-1) range of the FT-IR spectra have been assigned for N-acetyl-alpha-D-glucosamine and beta-D-glucuronic acid, respectively.

The conformational space of (4)C(1) alpha- and beta-d-glucuronic acid was scanned by HF/3-21G(p) calculations followed by optimization of the 15 most stable structures for each, using the B3LYP density functional theory method in conjunction with a diffuse polarized valence triple-zeta basis set. We found a general preference of the alpha anomers in the isolated molecules in agreement with the large endo-anomeric hyperconjugation effects in these structures. From the other intramolecular interactions (exo-anomeric hyperconjugation, hydrogen-bonding, dipole-dipole, and steric interactions), the effect of the hydrogen bonding is the most pronounced and plays a major role in determining the stability order within the alpha and beta series. The most stable conformer of both alpha and beta (4)C(1) d-glucuronic acid is the structure with the maximum number (5) of intramolecular hydrogen bonds. Introduction of solvent (water) effects by the SCI-PCM model resulted in two characteristic changes of the energetic properties: the gas-phase stability order changed considerably, and the energy range of the 15 most stable conformers decreased from 30 to 15 kJ/mol. The geometrical parameters reflect well the superimposed effects of hyperconjugation and hydrogen-bonding interactions. Most characteristics are the variations of the C-O bond distances (within a range of 0.04 A) upon the combined intramolecular effects.