Simultaneous Determination of Mefenamic and Tolfenamic Acids in Real Samples by Terbium-Sensitized Luminescence

A simple luminescent methodology for the simultaneous determination of mefenamic and tolfenamic acids in pharmaceutical preparations and human urine is proposed. Since the native fluorescence of both analytes is not intense, the method takes advantage of the lanthanide-sensitized luminescence, which provides a higher sensitivity. Due to the strong overlapping between the luminescence spectra of both terbium complexes, the use of luminescence decay curves to resolve mixtures of the analytes is proposed, since these curves are more selective. A factorial design with three levels per factor coupled to a central composite design was selected to obtain a calibration matrix of thirteen standards plus eight blank samples that was processed using a partial least-squares (PLS) analysis. In order to assess the goodness of the proposed method, a prediction set of synthetic samples was analyzed, obtaining recovery percentages between 90 and 104?%. Limits of detection, calculated by means of a new criterion, were 14.85?μg L^?1 and 15.89?μg L^?1 for tolfenamic and mefenamic acids, respectively. The method was tested in a pharmaceutical preparation containing mefenamic acid, obtaining recovery percentages close to 100?%. Finally, the simultaneous determination of both fenamates in human urine samples was successfully carried out by means of a correction of the above-explained model. No extraction method neither prior separation of the analytes were needed.