The effect of urea on the structure of water: a molecular dynamics simulation.

This paper reports an analysis using molecular dynamics simulations of the effect of urea on the structure of water. Two definitions of the tetrahedral distributions are used to quantify this effect. The first one is sensitive to the mutual orientation between a reference water molecule and the water molecules forming the tetrahedron, and the second is sensitive to their radial distribution. The analysis shows that increasing urea mole fraction results in a reduction of the structured tetrahedral arrangement contribution in favor of an unstructured one. In order to understand this behavior, we used the nearest neighbor approach which allows us to get unambiguous information on the radial and orientation distributions of the water molecules around a probe one. The results indicate that the decrease of the tetrahedral arrangement of the nearest neighbors around a probe water molecule is associated with both the increase of the fluctuation in their radial distances as well as with the loss of their mutual orientations with respect to those observed in pure water. The tetrahedral distribution of water in the hydration shell of urea as well as that around its carbonyl and amine groups is also discussed.

The SPASIBA force field for chondroitin sulfate: vibrational analysis of D-glucuronic and N-acetyl-D-galactosamine 4-sulfate sodium salts.

Normal-mode analyses were carried out on the two components of the chondroitin 4-sulfate linear glycosaminoglycan, a copolymer implying alternate D-glucuronate beta-(1-->3) and N-acetyl-D-galactosamine 4-sulfate beta-(1-->4) (hereafter named D-galactosamine 4-sulfate) residues. Scaled quantum mechanical calculations (SQM) using the density functional theory approach at different levels of theory (B3LYP/6-31G** and B3LYP/6-31++G**) were performed to obtain correct vibrational assignments. The SPASIBA empirical force field parameters were then obtained from both theoretical predictions and observed IR and Raman data. It is shown that calculations including diffuse functions at the B3LP/6-31++G** level and the introduction of the Na+ counterion are necessary to give correct assignments of the CO2- symmetric (nu(s)) and antisymmetric (nu(a)) stretching modes for the glucuronic carboxylate residue.

Density functional theory and empirical derived force fields for the delocalized polaron form of polyaniline. Application to properties determination of an isolated oligomer using molecular dynamics simulations.

Normal mode analyses obtained from quantum chemical calculations at the DFT level of theory have been performed for the repetitive unit of the delocalized bipolaron form of polyaniline (PANI). Empirical molecular mechanics force field parameters were consecutively refined using the SPASIBA software and applied to the molecular dynamics properties of an isolated dodeca oligomer model of the leucoemeraldine form of PANI. It is shown that effects of protonation of the emeraldine base spread over the four rings constituting the repeating unit. Molecular dynamics simulations reveal alternative bendings of the whole chain with a time period of 18-20 ps for the model of PANI under study.

The SPASIBA force field as an essential tool for studying the structure and dynamics of saccharides.

The SPASIBA force field has been applied to the determination of the structure and dynamical properties of various disaccharides. It has been shown that the experimental properties (structure, dipole moment, conformational relative energies) are satisfactorily predicted. The anomeric and exo-anomeric effects are confidently reproduced without specific terms for the alpha and beta anomers and the type of glycosidic linkages.

On the use of ultraviolet resonance Raman intensities to elaborate molecular force fields: application to nucleic acid bases and aromatic amino acid residues models.

Normal modes analyses for different molecules with biological interest have been performed and checked via the calculation of resonance Raman intensities. For this purpose, molecular orbital calculations were used to determine bond order changes in the lowest-lying electronic transitions. These bond order changes were used to calculate resonance Raman intensities in order to obtain correct vibrational assignments and reliable force fields.

Normal modes of vibration of a model peptide adopting the C7 C5 structure. Application toi angiotensin II.

A normal coordinate treatment was performed on the C7C5 conformation using a modified Urey-Bradley force field refined from previous studies on beta-turns. The predicted frequencies were compared with the experimental ones obtained on the peptide hormone human angiotensin II. The existence of both a beta-turn and a C7C5 conformation in solid and in aqueous solution is discussed.

Raman spectroscopy and normal vibrations of peptides. Characteristic normal modes of a type-II beta turn.

Raman and infrared spectra have been recorded on the peptide Gly-LPro-Gly-Gly in its zwitterionic form and on its protected homolog Z-Gly-LPro-Gly-Gly-OMe (Z = N-benzyloxycarbonyl and OMe = methyl ester). Both peptides adopt a type-II beta-turn conformation into appropriate solvents, that is in dimethylsulfoxide and chloroform respectively. A normal coordinate treatment has been performed on Gly-LPro-Gly-Gly using a modified Urey-Bradley force field and the characteristic normal modes of vibrations. Their corresponding frequencies have been extracted from experimental investigations.

Vibrational normal modes of folded prolyl-containing peptides. Application to beta turns.

Normal mode analysis of standard beta turns has been performed using the refined force field obtained from type-II beta-turn-like conformation frequencies. Effects of various potentials are discussed and theoretical predictions are compared to the experimental results of various authors.