Determination of testosterone propionate in cosmetics using excitation-emission matrix fluorescence based on oxidation derivatization with the aid of second-order calibration methods

Abstract A sensitive excitation-emission fluorescence method was proposed to determine testosterone propionate (TP) in several cosmetics with the aid of second-order calibration methods based on the self-weighted alternating trilinear decomposition (SWATLD) and parallel factor analysis (PARAFAC) algorithms. TP can be transformed into a highly fluorescent derivative through oxidation reaction with concentrated sulfuric acid (H 2 SO 4 ). Both algorithms have been recommended to enhance the selectivity and attain TP concentration in cosmetics free from interference from potential interfering matrix contaminants introduced during simple cosmetic pretreatment procedure, even in the presence of other homogeneous drugs. Satisfactory results have been achieved for TP in complicated cosmetics, fully exploiting “second-order advantage”. The correlation coefficients of TP obtained by using both SWATLD and PARAFAC with N  = 3 are 0.9968 and 0.9974, and the average recoveries, 99.3 ± 4.7% and 101.3 ± 5.9%, respectively. Furthermore, in order to investigate the performance of the proposed methods, some statistical parameters and figures of merit of SWATLD and PARAFAC, i.e., sensitivity (SEN), selectivity (SEL) and limit of detection (LOD) were evaluated, and the accuracy of both algorithms was also validated by the elliptical joint confidence region (EJCR) test.

[1]  U. Rohr.  The impact of testosterone imbalance on depression and women's health. , 2002, Maturitas.

[2]  Rasmus Bro,et al.  Real-time monitoring and chemical profiling of a cultivation process , 2006 .

[3]  W. Ying,et al.  Determination of Sexual Hormones in Liquid Cosmetics by Polymer Monolith Microextraction Coupled with High Performance Liquid Chromatography , 2007 .

[4]  R. Gonzalo-Lumbreras,et al.  HPLC method development for testosterone propionate and cipionate in oil-based injectables. , 2005, Journal of pharmaceutical and biomedical analysis.

[5]  O. Andersen,et al.  Characterization and matching of oil samples using fluorescence spectroscopy and parallel factor analysis. , 2005, Analytical chemistry.

[6]  Hideki Shirakawa,et al.  Blind spectral decomposition of single-cell fluorescence by parallel factor analysis. , 2004, Biophysical journal.

[7]  B. Le Bizec,et al.  Novel analytical methods for the determination of steroid hormones in edible matrices. , 2008, Analytica chimica acta.

[8]  L. Lucentini,et al.  Quantitation of anabolic hormones and their metabolites in bovine serum and urine by liquid chromatography-tandem mass spectrometry. , 2000, Journal of chromatography. A.

[9]  Ronei J. Poppi,et al.  Second- and third-order multivariate calibration: data, algorithms and applications , 2007 .

[10]  Hai-Long Wu,et al.  Simultaneous determination of 6-methylcoumarin and 7-methoxycoumarin in cosmetics using three-dimensional excitation-emission matrix fluorescence coupled with second-order calibration methods. , 2008, Talanta.

[11]  Xing-Fang Li,et al.  Determination of testosterone and its metabolites using liquid chromatography with elevated column temperature and flow-rate gradient , 2002 .

[12]  Lisbeth Olsson,et al.  On-line cell mass monitoring of Saccharomyces cerevisiae cultivations by multi-wavelength fluorescence. , 2004, Journal of biotechnology.

[13]  Alejandro García-Reiriz,et al.  Multiway partial least-squares coupled to residual trilinearization: a genuine multidimensional tool for the study of third-order data. Simultaneous analysis of procaine and its metabolite p-aminobenzoic acid in equine serum. , 2007, Analytical chemistry.

[14]  Yang Li,et al.  A novel trilinear decomposition algorithm for second-order linear calibration , 2000 .

[15]  R. Fitzgerald,et al.  Serum total testosterone: immunoassay compared with negative chemical ionization gas chromatography-mass spectrometry. , 1996, Clinical chemistry.

[16]  B. Le Bizec,et al.  Enzymatic hydrolysis of conjugated steroid metabolites: search for optimum conditions using response surface methodology. , 2000, The Analyst.

[17]  G. M. Escandar,et al.  Determination of carbamazepine in serum and pharmaceutical preparations using immobilization on a nylon support and fluorescence detection , 2004 .

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

[19]  Yoon-Chang Kim,et al.  Three- and four-way parallel factor (PARAFAC) analysis of photochemically induced excitation-emission kinetic fluorescence spectra. , 2005, The Analyst.

[20]  Alejandro C. Olivieri,et al.  Standard error of prediction in parallel factor analysis of three-way data , 2004 .

[21]  T. Higashi,et al.  Studies on neurosteroids XVIII LC–MS analysis of changes in rat brain and serum testosterone levels induced by immobilization stress and ethanol administration , 2006, Steroids.

[22]  Hai-Long Wu,et al.  An alternating trilinear decomposition algorithm with application to calibration of HPLC–DAD for simultaneous determination of overlapped chlorinated aromatic hydrocarbons , 1998 .

[23]  M. Blokland,et al.  Metabolism of methyltestosterone, norethandrolone and methylboldenone in a heifer , 2005 .

[24]  R. Yu,et al.  Fluorescence determination of metoprolol in human plasma by trilinear decomposition-based calibration techniques , 2006, Analytical and bioanalytical chemistry.

[25]  J. A. Arancibia,et al.  Second-order advantage achieved with four-way fluorescence excitation-emission-kinetic data processed by parallel factor analysis and trilinear least-squares. Determination of methotrexate and leucovorin in human urine. , 2004, Analytical chemistry.

[26]  Avraham Lorber,et al.  Net analyte signal calculation in multivariate calibration , 1997 .

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

[28]  G. M. Escandar,et al.  Two different strategies for the fluorimetric determination of piroxicam in serum. , 2003, Talanta.

[29]  Ru-Qin Yu,et al.  Efficient way to estimate the optimum number of factors for trilinear decomposition , 2001 .

[30]  J. Segura,et al.  Electrospray mass spectrometry of testosterone esters: Potential for use in doping control , 1997, Steroids.

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

[32]  A. Olivieri,et al.  A test field for the second-order advantage in bilinear least-squares and parallel factor analyses: fluorescence determination of ciprofloxacin in human urine. , 2004, Analytical chemistry.

[33]  T. Grizzard,et al.  Characterizing natural organic material from the Occoquan Watershed (Northern Virginia, US) using fluorescence spectroscopy and PARAFAC. , 2006, The Science of the total environment.