Competition between Wolff rearrangement and 1,2-hydrogen shift in beta-oxy-alpha-ketocarbenes: electrostatic and specific solvent effects

Article Abstract:

The solvent effects on the competition between the Wolff transposition and 1,2-H-shift in beta-hydroxy-ketocarbenes in aqueous solution was carried out at B3LYP/6-31G** level of theory and studied by quantum chemical investigation. The reproduction of the experimental yields was not done even with the inclusion of solvent effects by means of a continuum model. Preferential stabilization of the TS for the 1,2-H-shift process is by solvent due to a H-bond between one of the water molecules in the association complex and the migrating hydrogen.

Macrolide antibiotics, Macrolides, Solvents, Ketones

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Quantum chemical study on the coordination environment of the catalytic zinc ion in matrix metalloproteinases

Article Abstract:

The coordination sphere of the catalytic zinc ion in the active form of the catalytic domain of the gelatinase A or matrix metalloproteinase 2 (MMP-2) is investigated. Quantum mechanical (QM) and hybrid quantum mechanical/molecular mechanical (QM/MM) methodologies are used to investigate the effect of the whole catalytic domain and solvent.

Science & research, Spain, Proteases, Chemical properties

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Relative Gibbs energies in solution through continuum models: Effect of the loss of translational degrees of freedom in bimolecular reactions on Gibbs energy barriers

Article Abstract:

A model is proposed for explicitly evaluating the effect of loss of translational degrees of freedom in solution on the Gibbs energy of activation in bimolecular reactions. The difference in Gibbs energy in solution between the two species I and II is evaluated, within the framework of continuum models,

Analysis, Solvation, Gibbs' free energy, Continuum mechanics

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