Determination of anticarcinogenic and rescue therapy drugs in urine by photoinduced spectrofluorimetry using multivariate calibration: comparison of several second-order methods.

This paper shows the potential of excitation-emission fluorescence spectroscopy and several second-order methods, such as parallel factor analysis (PARAFAC), multiway partial least-squares (N-PLS) or bilinear least-squares (BLLS), as a multicalibration technique for the analysis of leucovorin (LV) and irinotecan (CPT-11). Although CPT-11 presents native fluorescence, leucovorin has little native fluorescence; however, under irradiation with short-wavelength UV light in the presence of traces of hydrogen peroxide, leucovorin was converted into a highly fluorescent compound. This reaction has been used for the sensitive and selective determination of both compounds. The convenience of analysing the total luminescence spectrum information when using multivariate calibration methods on fluorescence data is demonstrated. Direct determination of mixtures of both drugs in urine was accomplished on the basis of excitation-emission matrices (EEMs) and the three-way multivariate methods.

An environmental friendly method for the automatic determination of hypochlorite in commercial products using multisyringe flow injection analysis.

A multisyringe flow injection analysis system was used for the determination of hypochlorite in cleaning agents, by measurement of the native absorbance of hypochlorite at 292 nm. The methodology was based on the selective decomposition of hypochlorite by a cobalt oxide catalyst giving chloride and oxygen. The difference of the absorbance of the sample before and after its pass through a cobalt oxide column was selected as analytical signal. As no further reagent was required this work can be considered as a contribution to environmental friendly analytical chemistry. The entire analytical procedure, including in-line sample dilution in three steps was automated by first, dilution in a stirred miniature vessel, second by dispersion and third by in-line addition of water using multisyringe flow injection technique. The dynamic concentration range was 0.04-0.78 gL(-1) (relative standard deviation lower than 3%), where the extension of the hypochlorite decomposition was of 90+/-4%. The proposed method was successfully applied to the analysis of commercial cleaning products. The accuracy of the method was established by iodometric titration.

Optical fiber reflectance sensor coupled to a multisyringe flow injection system for preconcentration and determination of 1-naphthylamine in water samples.

A novel optical fiber reflectance sensor is coupled to a multisyringe flow injection system (MSFIA) for the preconcentration and determination of 1-naphthylamine (NPA) in water samples using C18 disks (octadecyl groups). NPA, being a first-class carcinogen, is important from a toxicological point of view and, therefore, its quantification is of considerable interest. In this study, the Griess reaction is used for sensitive and selective spectrophotometric determination of NPA. The reaction involves conversion of nitrite into nitrous acid in acidic medium followed by diazotization of sulphanilic acid and formation of a diazonium salt. The diazonium salt is then combined with NPA to form 4-(sulphophenylazo)-1-naphthylamine, an azo dye. This compound is subsequently retained onto a C18 disk followed by spectrophotometric detection at 540 nm, and it is then eluted with methanol in water (80%, v/v), so that the C18 disk is regenerated for subsequent experiments. Under the established optimum conditions, a calibration graph for NPA was constructed. Good linearity was observed within a concentration range from 10 to 160 microg l(-1). The lineal regression equation is A=(0.0027+/-0.0001) [NPA]+(0.0296+/-0.0047), r=0.9991; relative standard deviation values obtained from the analysis of 10 samples of 10, 80 and 160 microg l(-1) are 4.7, 1.2 and 0.6%, respectively. The mean value relative errors for concentrations of 10, 80, 160 microg l(-1) are 3.4, 0.9 and 0.4%, respectively. The detection and quantification limits were 1.1 and 3.7 microg l(-1). A sampling throughput of 14 injections per hour is achieved. The repeatability calculated for five different C18 disks was E(rel)=2.8%. The proposed technique has been validated by replicate analysis (n=6) of several water samples with spiked NPA, giving satisfactory results.

Determination of miconazole in pharmaceutical creams using internal standard and second derivative spectrophotometry.

A simple method is proposed for miconazole determination in pharmaceutical creams, based on extraction and second derivative spectrophotometry. In the presence of sodium lauryl sulfate (0.5%) and sulphuric acid (0.4 mol l(-1)), the miconazole and internal standard (IS) (methylene blue) were extracted to 100 microl of methylene chloride. The organic phase was evaporated in the nitrogen stream and the dry residue was dissolved in methanol (1.5 ml). The analytical signal was obtained as the ratio between second derivative absorbances measured at 236.9 nm (miconazole) and at 663.2 nm (IS). The use of IS in such multi-stage procedure enabled quite good analytical performance in calibration range 50.0 400 mg l(-1): linear correlation coefficient 0.9995, precision (measured as CV for ten replicates) at 50.0 mg l(-1) and at 400 mg l(-1) of miconazole was 1.5 and 0.5% respectively. Four commercial pharmaceutical creams were analyzed and the results obtained were in good agreement with the results obtained by reversed-phase high performance liquid chromatography (HPLC).

Application of the bivariate spectrophotometric method for the determination of metronidazole, furazolidone and di-iodohydroxyquinoline in pharmaceutical formulations.

The bivariate calibration algorithm was applied to the spectrophotometric determination of metronidazole, furazolidone and di-iodohydroxyquinoline in pharmaceutical dosage forms. The results obtained were compared with the results of derivative spectrophotometry. The statistical evaluation of method bias was carried out, and it was shown that the proposed procedure may be competitive with commonly used first-derivative spectrophotometry. The advantage of the bivariate calibration is its simplicity, and the fact that there is no need to use the derivatization procedures.

Enhanced spectrophotometric determination of chromium (VI) with diphenylcarbazide using internal standard and derivative spectrophotometry.

In the present work, erioglaucine A was applied as internal standard to enhanced spectrophotometric determination of chromium (VI) with diphenylcarbazide. The following procedure was used: (1) addition of internal standard and formation of ion pairs of Cr (VI) with benzyltributylammonium bromide (BTAB) (sample volume 100 ml), (2) extraction to 10 ml of methylene chloride, (3) evaporation in nitrogen stream, and (4) redissolution in a micro-volume with addition of diphenylcarbazide for color development (final volume 200 mul). The preconcentration factor achieved was about 400 and it was shown that, using internal standard, the analytical errors due to sample treatment were reduced. The analytical signals for chromium and internal standard were obtained at 591.30 and 653.50 nm from first derivative spectra, normalized against (1)D(653.50nm). The analytical characteristics evaluated were: detection limit = 0.06 mug l(-1), quantification limit = 0.19 mug l(-1), precision for 1 mug l(-1) 14.2%, and for 10 mug l(-1) 3.2%, correlation coefficient of linear regression was 0.9985. The proposed procedure was applied to determination of chromium (VI) in tap water. Total chromium was determined by electrothermal atomic absorption spectrometry, the recovery of hexavalent chromium added was then evaluated and compared with the results of the proposed procedure. In this experiment, good agreement was obtained between results obtained by the two methods.