A time-resolved spectroscopy and density functional theory study of the solvent dependent photochemistry of fenofibric acid

Phys Chem Chem Phys. 2013 Feb 7;15(5):1557-68. doi: 10.1039/c2cp41739a.

Abstract

The solvent dependent photochemistry of fenofibric acid (FA) was studied by femtosecond transient absorption and nanosecond time-resolved resonance Raman experiments and density functional theory calculations. In acetonitrile-rich solution, a typical nπ* triplet state FA ((3)FA) is formed through a highly efficient intersystem crossing and then the (3)FA species undergoes some reaction with water to generate a ketyl radical intermediate at low water concentrations. In contrast, nπ* (3)FA changes from a reaction with water to generate a ketyl radical intermediate at lower water concentrations to a decarboxylation reaction with the assistance of water molecules to produce a biradical intermediate at higher water concentrations in water-rich solutions. The decarboxylation reaction leads to the formation of the FA carbanion in 50% phosphate buffer solution and the FA carbanion is observed on the picosecond to nanosecond time scale and the cleavage of the FA carbanion gives rise to the enolate 3(-) anion at later nanosecond delay times. As regards fenofibrate (FB), it only exhibits a benzophenone-like photochemistry, which consists of some reaction with water to generate a ketyl radical intermediate, being observed in the different aqueous solutions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Absorption
  • Acetonitriles / chemistry
  • Fenofibrate / analogs & derivatives*
  • Fenofibrate / chemistry
  • Solvents / chemistry*
  • Spectrum Analysis, Raman
  • Time Factors
  • Water / chemistry

Substances

  • Acetonitriles
  • Solvents
  • Water
  • fenofibric acid
  • Fenofibrate
  • acetonitrile