ABSTRACT
A new chemiluminescence (CL) detection system combined with flow injection analysis (FIA) for the determination of Pefloxacin is proposed. The determination is based on an energy transfer from Pefloxacin to terbium (III). The metal ion enhances the weak CL signal produced by the KMnO4/H2SO3/Pefloxacin system. A modified simplex method was used to optimize chemical and instrumental variables. The influence of the interaction of the permanganate, Tb (III), sodium sulphite and sulphuric acid concentrations, flow rate and injected sample volume was thoroughly investigated by using a modified simplex optimization procedure. The results revealed a strong direct relationship between flow rate and CL intensity throughout the studied range that was confirmed by a gamma test. The response factor for the CL emission intensity was used to assess performance in order to identify the optimum conditions for maximization of the response. Under such conditions, the CL response was proportional to the Pefloxacin concentration over a wide range. The detection limit as calculated according to Clayton's criterion 13.7µgL-1. The analyte was successfully determined in milk samples with an average recovery of 100.6±9.8%.
Subject(s)
Flow Injection Analysis/methods , Luminescent Measurements/methods , Milk/metabolism , Pefloxacin/analysis , Potassium Permanganate/chemistry , Sulfites/chemistry , Terbium/chemistry , Animals , Cattle , Milk/chemistryABSTRACT
A simple luminescent methodology for the simultaneous determination of doxycycline and chlortetracycline in pharmaceutical preparations and human urine is proposed. Since the native fluorescence of both analytes is negligible, this method takes advantage of the lanthanide-sensitized luminescence, which provides increased sensitivity. Due to the strong overlapping between the luminescence spectra of both europium complexes, the use of luminescence decay curves to resolve mixtures of the analytes is proposed, particularly as these curves are more selective. A factorial design, with three levels per factor, coupled to a central composite design was selected to obtain a calibration matrix of 13 standards plus one blank sample, which were processed with a partial least-squares analysis. In order to assess the effectiveness of the proposed method, a prediction set of 10 synthetic samples was analyzed, and recovery percentages between 95 and 104% were obtained. Limits of detection, calculated by means of a new criterion, were 3.27 and 1.06 µg L(-1) for doxycycline and chlortetracycline, respectively. The method was tested in three different pharmaceutical preparations containing the analytes, with average recovery percentages of 99.4 ± 1.8 for doxycycline and 100.5 ± 2.1 for chlortetracycline. Moreover, a central composite design was also developed to obtain a calibration matrix that made feasible the simultaneous determination of both tetracyclines in human urine samples. In this case, average recovery percentages were 98.0 ± 4.4 and 97.8 ± 4.6 for doxycycline and chlortetracycline, respectively. No extraction method or prior separation of the analytes was needed.
Subject(s)
Chlortetracycline/urine , Doxycycline/urine , Europium/chemistry , Luminescent Measurements/methods , Cetrimonium , Cetrimonium Compounds/chemistry , Chlortetracycline/chemistry , Doxycycline/chemistry , Edetic Acid/chemistry , Humans , Hydrogen-Ion Concentration , Least-Squares Analysis , Limit of Detection , Reproducibility of ResultsABSTRACT
A simple fluorescent methodology for the simultaneous determination of nabumetone and its main metabolite, 6-methoxy-2-naphthylacetic acid (6-MNA), in pharmaceutical preparations and human urine is proposed. Due to the strong overlapping between the fluorescence spectra of both analytes, the use of fluorescence decay curves to resolve their mixture is proposed, since these curves are more selective. Values of dependent instrumental variables affecting the signal-to-noise ratio were fixed using a simplex optimization procedure. A factorial design with three levels per factor coupled to a central composite design was selected to obtain a calibration matrix of thirteen standards plus one blank sample that was processed using a partial least-squares (PLS) analysis. In order to assess the goodness of the proposed method, a prediction set of ten synthetic samples was analyzed, obtaining recovery percentages between 97 and 105%. Limits of detection, calculated by means of a new criterion, were 0.96 µg L(-1) and 0.88 µg L(-1) for nabumetone and 6-MNA, respectively. The method was also tested in the pharmaceutical preparation Relif, which contains nabumetone, obtaining recovery percentages close to 100%. Finally, the simultaneous determination of both analytes in human urine samples was successfully carried out by the PLS-analysis of a matrix of fifteen standards plus four analyte blanks and the use of the standard addition technique. Although urine shows native fluorescence, no extraction method or prior separation of the analytes was needed.
Subject(s)
Butanones/analysis , Butanones/metabolism , Naphthaleneacetic Acids/analysis , Naphthaleneacetic Acids/metabolism , Pharmaceutical Preparations/chemistry , Spectrometry, Fluorescence/methods , Urinalysis/methods , Butanones/urine , Calibration , Humans , Least-Squares Analysis , Limit of Detection , Nabumetone , Naphthaleneacetic Acids/urine , Reproducibility of Results , Time FactorsABSTRACT
A rapid, simple, and inexpensive spectrofluorimetric method has been proposed for the simultaneous quantification of diflunisal, salicylic acid, fenoprofen, and 6-methoxy-2-naphthylacetic acid (6MNA). First-derivative nonlinear variable-angle synchronous fluorescence spectrometry has been developed to improve the selectivity of fluorescence measurements without loss of sensitivity. It allows the simultaneous determination of different substances in a mixture from a single spectrum based on a single scan. The analyses were performed in an ethanol-water (70%) medium at a pH of 9.2, adjusted by using ammonium/ammonia (0.5 M) as a buffer solution. The linear concentration ranges are 30.0-100.0, 100.0-600.0, 50.0-150.0, and 30.0-100.0 ng/mL for salicylic acid, fenoprofen, diflunisal, and 6-methoxy-2-naphthylacetic acid, respectively, at lambda(ex)/lambda(em) = 281.1/423.6, 241.2/301.2, 284.1/403.8, and 268.7/339.6 nm, respectively. Analytical parameters of the proposed method were calculated according to the error propagation theory. The sensitivity, repeatability, reproducibility, and limits of detection achieved with the proposed method are adequate for the determination of these anti-inflammatory drugs.
