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.
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The authors gratefully acknowledge financial support from the “Consejería de Educación y Cultura, Junta de Comunidades de Castilla-La Mancha” (Project Nº PCI-08-0120).
Fernando Martínez Ferreras thanks the Spanish Ministerio de Educación for a FPU (Formación del Profesorado Universitario) fellowship.
Mikami E, Goto T, Ohno T, Matsumoto H, Inagaki K, Ishihara H, Nishida M (2000) Simultaneous analysis of anthranilic acid derivatives in pharmaceuticals and human urine by high-performance liquid chromatography with isocratic elution. J Chromatogr B 744:81–89CrossRefGoogle Scholar
Papadoyannis IN, Zotou AC, Samanidou VF (1992) Simultaneous reversed-phase gradient-HPLC analysis of anthranilic acid derivatives in anti-inflammatory drugs and samples of biological interest. J Liq Chromatogr 15:1923–1945CrossRefGoogle Scholar
Kim KR, Yoon HR (1996) Rapid screening for acidic non-steroidal anti-inflammatory drugs in urine by gas chromatography-mass spectrometry in the selected-ion monitoring mode. J Chromatogr B 682:55–66CrossRefGoogle Scholar
Maurer HH, Tauvel FX, Kraemer T (2001) Screening procedure for detection of non-steroidal anti-inflammatory drugs and their metabolites in urine as part of a systematic toxicological analysis procedure for acidic drugs and poisons by gas chromatographymass spectrometry after extractive methylation. J Anal Toxicol 25:237–244PubMedGoogle Scholar
Laakkonen UM, Leinonen A, Savonen L (1994) Screening of non-steroidal anti-inflammatory drugs, barbiturates and methyl xanthines in equine urine by gas chromatography-mass spectrometry. Analyst 119:2695–2696PubMedCrossRefGoogle Scholar
Shinozuka T, Takei S, Kuroda N, Kurihara K, Yanagida J (1991) Micro-determination of anthranilic acid derivatives of anti-inflammatory drugs by high performance liquid chromatography and its application to forensic chemistry. Eisei Kagaku 37:461–466CrossRefGoogle Scholar
Cárdenas S, Gallego M, Valcárcel M, Ventura R, Segura J (1996) A partially automated pretreatment module for routine analyses for seventeen non-steroid antiinflammatory drugs in race horses using gas chromatography/mass spectrometry. Anal Chem 68:118–123PubMedCrossRefGoogle Scholar
González G, Ventura R, Smith AK, De La Torre R, Segura J (1996) Detection of non-steroidal anti-inflammatory drugs in equine plasma and urine by gas chromatography-mass spectrometry. J Chromatogr A 719:251–264PubMedCrossRefGoogle Scholar
Suenami K, Lim LW, Takeuchi T, Sasajima Y, Sato K, Takekoshi Y, Kanno S (2006) Rapid and simultaneous determination of nonsteroidal anti-inflammatory drugs in human plasma by LC-MS with solid-phase extraction. Anal Bioanal Chem 384:1501–1505PubMedCrossRefGoogle Scholar
Suenami K, Lim LW, Takeuchi T, Sasajima Y, Sato K, Takekoshi Y, Kanno S (2007) On-line sample extraction and enrichment of non-steroidal anti-inflammatory drugs by pre-column in capillary liquid chromatography mass spectrometry. J Chromatogr B 846:176–183CrossRefGoogle Scholar
Gallo P, Fabbrocino S, Vinci F, Fiori M, Danese V, Nasi A, Serpe L (2006) Multi-residue determination of non-steroidal anti-inflammatory drug residues in animal serum and plasma by HPLC and photo-diode array detection. J Chromatogr Sci 44:585–590PubMedGoogle Scholar
Dubreil-Chéneau E, Pirotais Y, Bessiral M, Roudaut B, Verdon E (2011) Development and validation of a confirmatory method for the determination of 12 non steroidal anti-inflammatory drugs in milk using liquid chromatography-tandem mass spectrometry. J Chromatogr A 1218:6292–6301PubMedCrossRefGoogle Scholar
Polasek M, Pospisilova M, Urbanek M (2000) Capillary isotachophoretic determination of flufenamic, mefenamic, niflumic and tolfenamic acids in pharmaceuticals. J Pharm Biomed Anal 23:135–142PubMedCrossRefGoogle Scholar
Ioannou PC, Rusakova NV, Andrikopoulou DA, Glynou KM, Tzompanaki GM (1998) Spectrofluorimetric determination of anthranilic acid derivatives based on terbium sensitized fluorescence. Analyst 123:2839–2843PubMedCrossRefGoogle Scholar
Arnaud N, Georges J (2003) Investigation of the luminescent properties of terbium-anthranilate complexes and application to the determination of anthranilic acid derivatives in aqueous solutions. Anal Chim Acta 476:149–157CrossRefGoogle Scholar
Rodríguez-Díaz RC, Aguilar-Caballos MP, Gómez-Hens A (2003) Simultaneous determination of ciprofloxacin and tetracycline in biological fluids based on dual-lanthanide sensitised luminescence using dry reagent chemical technology. Anal Chim Acta 494:55–62CrossRefGoogle Scholar
Izquierdo P, Gómez-Hens A, Pérez-Bendito D (1994) Study of the Eu(III)-tetracycline-thenoyltrifluoroacetone system by using the stopped-flow mixing technique: Determination of tetracycline in serum. Anal Chim Acta 292:133–139CrossRefGoogle Scholar
Rieutord A, Prognon P, Brion F, Mahuzier G (1997) Liquid-chromatographic determination using lanthanides as time-resolved luminescence probes for drugs and xenobiotics: advantages and limitations. Analyst 122:59R–66RPubMedCrossRefGoogle Scholar
Ibáñez GA (2008) Partial least-squares analysis of time decay data for Eu(III)-tetracycline complexes. Simultaneous luminescent determination of tetracycline and oxytetracycline in bovine serum. Talanta 75:1028–1034PubMedCrossRefGoogle Scholar
Olivieri AC, Goicoechea HC, Iñón FA (2004) MVC1: an integrated MatLab toolbox for first-order multivariate calibration. Chemom Intell Lab Syst 73:189–197CrossRefGoogle Scholar
Marquardt DW (1963) An algorithm for least-squares estimation of nonlinear parameters. J App Math 11:431–441Google Scholar
Owen DB (1962) Handbook of statistical tables. Addison Wesley, ReadingGoogle Scholar
Leiner MJP, Hubmann MR, Wolfbeis OS (1987) The total fluorescence of human urine. Anal Chim Acta 198:13–23CrossRefGoogle Scholar
Thomas EV, Haaland DM (1990) Comparison of multivariate calibration methods for quantitative spectral analysis. Anal Chem 62:1091–1099CrossRefGoogle Scholar
Haaland DM, Thomas EV (1988) Partial least-squares methods for spectral analyses. 1. Relation to other quantitative calibration methods and the extraction of qualitative information. Anal Chem 60:1193–1202CrossRefGoogle Scholar
Mandel J, Linning FJ (1957) Study of Accuracy in Chemical Analysis Using Linear Calibration Curves. Anal Chem 29:743–749CrossRefGoogle Scholar
Murillo Pulgarín JA, Alañón Molina A, Sánchez Ferrer-Robles I (2011) Simultaneous determination of salicylic acid and salicylamide in biological fluids. Spectrochim Acta Part A 79:909–914CrossRefGoogle Scholar
Murillo Pulgarín JA, García Bermejo LF, Sánchez García MN (2007) Multivariate calibration applied to the time-resolved chemiluminescence for the simultaneous determination of morphine and its antagonist naloxone. Anal Chim Acta 602:66–74PubMedCrossRefGoogle Scholar
Alañón Molina A, Murillo Pulgarín JA, Martínez Ferreras F (1978) Nomenclature, symbols, units and their usage in spectrochemical analysis. 2. Data interpretation. Spectrochim Acta B 33:242–245Google Scholar