Second-order multivariate calibration procedures applied to high-performance liquid chromatography coupled to fast-scanning fluorescence detection for the determination of fluoroquinolones.

Different second-order multivariate calibration algorithms, namely parallel factor analysis (PARAFAC), N-dimensional partial least-squares (N-PLS) and multivariate curve resolution-alternating least-squares (MCR-ALS) have been compared for the analysis of four fluoroquinolones in aqueous solutions, including some human urine samples (additional four fluoroquinolones were simultaneously determined by univariate calibration). Data were measured in a short time with a chromatographic system operating in the isocratic mode. The detection system consisted of a fast-scanning spectrofluorimeter, which allows one to obtain second-order data matrices containing the fluorescence intensity as a function of retention time and emission wavelength. The developed approach enabled us to determine eight analytes, some of them with overlapped profiles, without the necessity of applying an elution gradient, and thus significantly reducing both the experimental time and complexity. The study was employed for the discussion of the scopes of the applied second-order chemometric tools. The quality of the proposed technique coupled to each of the evaluated algorithms was assessed on the basis of the figures of merit for the determination of fluoroquinolones in the analyzed water and urine samples. Univariate calibration of four analytes led to limits of detection in the range 20-40 ng mL(-1) and root mean square errors for the validation samples in the range 30-60 ng mL(-1) (corresponding to relative prediction errors of 3-8%). The ranges for second-order multivariate calibration (using PARAFAC and N-PLS) of the remaining four analytes were: limit of detection, 2-8 ng mL(-1), root mean square errors, 3-50 ng mL(-1) and relative prediction errors, 1-5%.

Combined liquid and solid-surface room temperature fluorimetric determination of naproxen and salicylate in serum.

A rapid and sensitive method for the determination of naproxen and salicylate in serum is presented. The employed strategy combines solid-phase extraction on a reverse-phase membrane with spectrofluorimetry. Solid-phase extraction under optimum pH conditions makes NX to be retained over the solid surface (where it is directly determined by a fluorimetric technique). Salicylate passes through the disk and is also fluorimetrically determined, but in solution. The linear calibration ranges for NX in the membrane and salicylate in solution were 0.014-0.250 and 0.010-0.250 microg ml(-1), respectively. The lowest value, in each case, is the corresponding limit of quantitation. The performance of the method is demonstrated with the successful determination of both drugs in spiked and real human serum samples.