Comparison of the predictive ability of several second-order multivariate methods in the simultaneous determination of two therapeutic drugs in human urine

• Published in: Talanta (Oxford) 2012-01, Vol.88, p.609-616
• Main Authors: Hurtado-Sánchez, M.C., Durán-Merás, I., Rodríguez-Cáceres, M.I., Jiménez-Girón, A., Olivieri, A.C.
• Format: Article
• Language: English
• Subjects: Algorithms; Analytical chemistry; Antineoplastic Agents - urine; Calibration; Camptothecin - analogs & derivatives; Camptothecin - urine; Chemistry; Chloroform - chemistry; CTP-11; Exact sciences and technology; Factor Analysis, Statistical; Fluorescence; Humans; Least-Squares Analysis; Liquid-Liquid Extraction; Multivariate Analysis; N-PLS/RBL; PARAFAC; Second-order multivariate calibration; Spectrometric and optical methods; Spectrometry, Fluorescence; Thalidomide; Thalidomide - urine; U-PLS/RBL; Urine
• ISSN: 0039-9140; 1873-3573
• DOI: 10.1016/j.talanta.2011.11.045

► We test the ability of second-order multivariate methods to solve complex mixtures. ► We approach the resolution of two chemotherapies with different fluorescence. ► The strong urine background overlaps with the less fluorescence analyte. ► Three-way fluorescence data were processed with PARAFAC, N-PLS/RBL and U-PLS/RBL. ► Only PARAFAC allows a successful quantitation of both analytes. The aim of this paper is to study the applicability of second-order multivariate methods in the simultaneous determination of two therapeutic drugs in human urine samples. The studied drugs, irinotecan and thalidomide, are used in the treatment of malignant tumours. Irinotecan (CPT-11) is used to treat colon cancer; recent studies have shown the benefits of using thalidomide in combination with CPT-11 in the treatment of this disease. CPT-11 is highly fluorescent, but the native fluorescence of thalidomide is very weak. The second-order methods assayed were parallel factor analysis (PARAFAC), unfolded partial least-squares (U-PLS) and multidimensional partial least-squares (N-PLS), both combined with the residual bilinearization procedure (RBL). The excitation-emission matrices (EEMs) of the samples were recorded as analytical signal. The accuracy and precision of the algorithms were evaluated through the root mean square error of prediction (RMSEP) and the elliptical joint confidence region test (EJCR), obtaining better results with PARAFAC, which was successfully applied to the determination of thalidomide and CPT-11 in human urine samples, after a previous liquid–liquid extraction with chloroform.