Different strategies for the direct determination of amoxicillin in human urine by second-order multivariate analysis of kinetic-spectrophotometric data.

The kinetic evolution of UV-visible absorption spectra of amoxicillin in the presence of copper(II) ions has been processed by the second-order multivariate methods parallel factor analysis (PARAFAC) and also by a novel approach based on partial least-squares with residual bilinearization (PLS/RBL). The latter one is employed for the first time to evaluate kinetic-spectral information. The mechanism of the analyte metal-catalyzed hydrolysis involves a reaction intermediate and a final reaction product, both with spectra which may allow for the determination of amoxicillin in human urine, even in the presence of unsuspected sample components. This is possible thanks to the second-order advantage exploited by the employed chemometric algorithms, among which PARAFAC and PLS/RBL gave the best results. Amoxicillin was determined in a series of spiked and real urine samples, which allowed to perform, respectively, a recovery study and a comparison with the reference high-performance liquid chromatographic technique. The best figures of merit were obtained with PLS/RBL, namely sensitivity, 0.5AUL mg(-1) (AU=absorbance units), analytical sensitivity, 500L mg(-1) and limit of detection, 6mg L(-1). Relative advantages and disadvantages of the employed algorithms are discussed.

[1]  S. R. Crouch,et al.  Evaluation of classical and three-way multivariate calibration procedures in kinetic-spectrophotometric analysis , 2000 .

[2]  Luis Cuadros Rodríguez,et al.  Estimation of Performance Characteristics of an Analytical Method Using the Data Set Of The Calibration Experiment , 1993 .

[3]  N. Sidiropoulos,et al.  Least squares algorithms under unimodality and non‐negativity constraints , 1998 .

[4]  N. Teshima,et al.  Reverse flow injection analysis of complexing agents and its application to estimation of complexing capacity. , 1993, Talanta.

[5]  Facundo M. Fernández,et al.  Novel application and comparison of multivariate calibration for the simultaneous determination of Cu, Zn and Mn at trace levels using flow injection diode array spectrophotometry , 1999 .

[6]  Avraham Lorber,et al.  Analytical figures of merit for tensorial calibration , 1997 .

[7]  Rasmus Bro,et al.  Multi-way Analysis with Applications in the Chemical Sciences , 2004 .

[8]  C. Ang,et al.  Determination of amoxicillin residues in animal tissues by solid-phase extraction and liquid chromatography with fluorescence detection. , 2000, Journal of AOAC International.

[9]  P. G. Navarro,et al.  Spectrofluorimetric study of the degradation of α-amino β-lactam antibiotics catalysed by metal ions in methanol† , 1998 .

[10]  A. Olivieri,et al.  Two Multivariate Strategies Applied to Three-Way Kinetic Spectrophotometric Data for the Determination of Mixtures of the Pesticides Carbaryl and Chlorpyrifos , 2004, Applied spectroscopy.

[11]  Alejandro C Olivieri,et al.  Interference-free analysis using three-way fluorescence data and the parallel factor model. Determination of fluoroquinolone antibiotics in human serum. , 2003, Analytical chemistry.

[12]  N. M. Faber,et al.  Uncertainty estimation and figures of merit for multivariate calibration (IUPAC Technical Report) , 2006 .

[13]  R. Bro.  PARAFAC. Tutorial and applications , 1997 .

[14]  D. Barrett,et al.  Measurement of amoxicillin in plasma and gastric samples using high-performance liquid chromatography with fluorimetric detection. , 2002, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[15]  A. Lorber.  Error propagation and figures of merit for quantification by solving matrix equations , 1986 .

[16]  R. Tauler.  Multivariate curve resolution applied to second order data , 1995 .

[17]  H. Mascher,et al.  Determination of amoxicillin in plasma by high-performance liquid chromatography with fluorescence detection after online oxidation. , 1990, Journal of chromatography.

[18]  Alejandro C Olivieri,et al.  Computing sensitivity and selectivity in parallel factor analysis and related multiway techniques: the need for further developments in net analyte signal theory. , 2005, Analytical chemistry.

[19]  M. A. Herrador,et al.  Intra-laboratory testing of method accuracy from recovery assays. , 1999, Talanta.

[20]  E. V. Thomas,et al.  Partial least-squares methods for spectral analyses. 1. Relation to other quantitative calibration methods and the extraction of qualitative information , 1988 .

[21]  W. A. Moats.  Determination of AmpiciUin and Amoxicillin in Milk with an Automated Liquid Chromatographic Cleanup , 1994 .

[22]  J. Haginaka,et al.  High-performance liquid chromatographic assay of ampicillin, amoxicillin and ciclacillin in serum and urine using a pre-column reaction with 1,2,4-triazole and mercury(II) chloride. , 1985, The Analyst.

[23]  M. E. Díaz-García,et al.  Insights into the reaction of beta-lactam antibiotics with copper(II) ions in aqueous and micellar media: kinetic and spectrometric studies. , 2005, Analytical biochemistry.

[24]  Alejandro C. Olivieri,et al.  MVC1: an integrated MatLab toolbox for first-order multivariate calibration , 2004 .

[25]  R. Bro,et al.  A new efficient method for determining the number of components in PARAFAC models , 2003 .

[26]  I. S. Scarminio,et al.  Three-way chemometric method study and UV-Vis absorbance for the study of simultaneous degradation of anthocyanins in flowers of the Hibiscus rosa-sinensys species. , 2004, Talanta.

[27]  L. Goodman,et al.  The Pharmacological Basis of Therapeutics , 1941 .

[28]  A. Olivieri.  On a versatile second‐order multivariate calibration method based on partial least‐squares and residual bilinearization: Second‐order advantage and precision properties , 2005 .