Water concentration dependent photochemistry of ketoprofen in aqueous solutions

Abstract

Ketoprofen is an important photosensitive drug molecule that has received much attention for the study of its photochemistry in different solvents. In this paper, nanosecond time-resolved resonance Raman spectroscopy was utilized to investigate the photochemistry of ketoprofen in aqueous solutions with varying water concentrations. The rate constants and reaction mechanism of ketoprofen are strongly dependent on the concentration of the solvent. In neat acetonitrile and solvents with low concentrations of water (like water–acetonitrile ≤ 1 : 1, v/v), ketoprofen exhibits mostly benzophenone-like photochemistry to generate a triplet state which in turn produces a ketyl radical-like species by a hydrogen abstraction reaction. However, in solvents with very high concentrations of water (such as water–acetonitrile ≥ 9 : 1, v/v), the triplet state ketoprofen is observed first and then undergoes a prompt decarboxylation process to form a triplet protonated biradical carbanion species. For solvents with moderate higher water concentrations (such as between 50% and 90% water by volume), the hydrogen abstraction and decarboxylation processes are two competitive pathways with different rate constants. The triplet state of ketoprofen will simultaneously produce a ketyl radical species and a triplet protonated biradical carbanion species with the amount of each species dependent on the water concentration.