Photolysis of thiochrome in aqueous solution: A kinetic study.

The photolysis of thiochrome (THC), an oxidation product of thiamine (vitamin B1) (THE), used for its fluorimetric assay, has been studied in the pH range 7.0-12.0. THC undergoes photooxidation to oxodihydrothiochrome (ODTHC) which is oxidized to a non-fluorescent compound (OP1) on UV irradiation. The kinetics of the consecutive first-order reactions: THC→k1ODTHC→k2OP1, has been evaluated and the values of first-order rate constants, k1 (0.58-4.20 × 10-5, s-1) and k2 (0.05-2.03 × 10-5, s-1), at pH 7.0-12.0 have been determined. The rates of degradation of THC and ODTHC are enhanced with pH and the second-order rate constants k1' and k2' for the OH- ion-catalyzed reaction are in the range of 0.002-58.3 M-1 s-1. The quantum yields of the photolysis of THC and ODTHC in the pH range 7.0-12.0 have been determined. THC, ODTHC and OP1 have been identified by chromatographic, spectrometric and fluorimetric methods. THC and ODTHC have similar fluorescence characteristics and emit at 450 and 445 nm, respectively. THC, ODTHC and OP1 with distinct absorption maxima (370, 344 and 290 nm, respectively) have been determined by a newly developed and validated multicomponent spectrometric method during the photolysis reactions. The on-line formation of THC by the photooxidation of THE may lead to the degradation of THC and give erroneous results in the fluorimetric assay of THE. A scheme for the photolysis reactions of THC in aqueous solution is presented.

Validation of a UV Spectrometric Method for the Assay of Tolfenamic Acid in Organic Solvents.

The present study has been carried out to validate a UV spectrometric method for the assay of tolfenamic acid (TA) in organic solvents. TA is insoluble in water; therefore, a total of thirteen commonly used organic solvents have been selected in which the drug is soluble. Fresh stock solutions of TA in each solvent in a concentration of 1 × 10(-4 )M (2.62 mg%) were prepared for the assay. The method has been validated according to the guideline of International Conference on Harmonization and parameters like linearity, range, accuracy, precision, sensitivity, and robustness have been studied. Although the method was found to be efficient for the determination of TA in all solvents on the basis of statistical data 1-octanol, followed by ethanol and methanol, was found to be comparatively better than the other studied solvents. No change in the stock solution stability of TA has been observed in each solvent for 24 hours stored either at room (25 ± 1°C) or at refrigerated temperature (2-8°C). A shift in the absorption maxima has been observed for TA in various solvents indicating drug-solvent interactions. The studied method is simple, rapid, economical, accurate, and precise for the assay of TA in different organic solvents.