Trace determination of 10 beta-lactam antibiotics in environmental and food samples by capillary liquid chromatography.

A sensitive and reliable method using capillary HPLC with UV-diode array detection (DAD) has been developed and validated for the trace determination of residues of 10 beta-lactam antibiotics of human and veterinary use, in milk, chicken meat and environmental water samples. The analytes included ampicillin, amoxicillin, penicillin V, penicillin G, cloxacillin, oxacillin, dicloxacillin, nafcillin, piperacillin and clavulanic acid. Legal levels are regulated by the EU Council regulation 2377/90 in animal edible tissues for these compounds. For food analysis, a solid-phase extraction (SPE) procedure consisting in a tandem of Oasis HLB and Alumina N cartridges was applied for off-line preconcentration and cleanup. For water analysis, the first step was only necessary. The limits of detection for the studied compounds were between 0.04-0.06 microg l(-1) for water samples and 0.80-1.40 microg l(-1) (or microg kg(-1)) in the case of foods derived from animals. Average recoveries for fortified samples at different concentration levels ranged between 82.9% and 98.2%, with relative standard deviations (RSDs) lower than 9%. The method showed the advantages of capillary HPLC for the detection of these widely applied antibiotics in different samples at very low concentration levels.

Capillary zone electrophoresis with diode-array detection for analysis of local anaesthetics and opium alkaloids in urine samples.

The present study describes the simultaneous determination of four drugs, two local anaesthetics (lidocaine and bupivacaine) and two opium alkaloids (noscapine and papaverine) by capillary zone electrophoresis (CZE) with solid-phase extraction (SPE) procedure using Oasis HLB cartridges. Their recoveries ranged from 81 to 107% at the target concentrations of 2.0, 5.0 and 8.0 microgmL(-1) in spiked urine samples. Coefficients of variation of the recoveries ranged from 2.1 to 11.3% at these concentrations. The quantitation limits of the method were approximately 300 ngmL(-1) for the different compounds studied. The assay is very specific for these compounds and requires a short sample preparation procedure prior to the electrophoretic analysis.

Trace determination of beta-lactam antibiotics in environmental aqueous samples using off-line and on-line preconcentration in capillary electrophoresis.

A sensitive and reliable method using capillary zone electrophoresis with UV-diode array detection (CZE-DAD) has been developed and validated for trace determination of beta-lactam antibiotics in waste, well and river water matrices. Due to the lack of sensitivity of the UV-vis detection, a solvent extraction/solid-phase extraction (SPE) method applied for off-line preconcentration and cleanup of water samples, in combination with an on-line preconcentration methodology named large volume sample stacking (LVSS) have been applied. The analytes included nafcillin, dicloxacillin, cloxacillin, oxacillin, ampicillin, penicillin G and amoxicillin. Average recoveries for water samples fortified with the studied beta-lactams at different concentration levels (1.0, 2.0 and 4.0 microg/L) were ranging between 94 and 99%, with relative standard deviations (RSDs) lower than 10%. The precision, calculated as intra-day and inter-day standard deviations fell within acceptable ranges (3.3-7.2%). The limits of detection were estimated to range between 0.08 and 0.80 microgL(-1) for the studied compounds. All the samples analyzed were negative for all the analytes at these levels of concentration and the method showed its usefulness for the detection of these widely applied beta-lactam antibiotics in different kinds of waters.

Analysis of different beta-lactams antibiotics in pharmaceutical preparations using micellar electrokinetic capillary chromatography.

The potential of micellar electrokinetic capillary chromatography (MEKC) for analyzing nine beta-lactams antibiotics (cloxacillin, dicloxacillin, oxacillin, penicillin G, penicillin V, ampicillin, nafcillin, piperacillin, amoxicillin) in different pharmaceutical preparations, have been demonstrated. An experimental design strategy has been applied to optimize the main variables: pH and buffer concentration, concentration of the micellar medium, separation voltage and capillary temperature. Borate buffer (26mM) at pH 8.5 containing 100mM sodium dodecyl sulphate (SDS) was used as the background electrolyte. The method was validated. Linearity, limit of detection and quantitation and precision were established for each compound. The analysis of some of the beta-lactams in Orbenin capsules, Britapen tables and in Veterin-Micipen injectable, all used in human and veterinary medicine, have demonstrated the applicability of these technique for quality control in the pharmaceutical industry.

Determination of phytohormones of environmental impact by capillary zone electrophoresis.

A test mixture of five phytohormones [naphthaleneacetic acid (NAA), naphthoxyacetic acid (NOA), indoleacetic acid (IAA), indolebutyric acid (IBA), and indolepropionic acid (IPA)] was investigated. These compounds were cleanly separated with good resolution by capillary zone electrophoresis with a UV diode array detector using 20 mM sodium phosphate buffer (pH 7.25). The lowest detection limit was obtained for IPA (0.45 mg L(-)(1) or 0.005 mg kg(-)(1)) and the highest for NAA (1.04 mg L(-)(1) or 0.014 mg kg(-)(1)). The method has been applied for tomato samples fortified with the five phytohormones using a liquid-liquid extraction procedure, obtaining recovery percentages ranging from 91 to 109.0%.

Simultaneous determination of the pesticides carbaryl and thiabendazole in environmental samples by a three-dimensional derivative variable-angle and a synchronous room-temperature phosphorescence spectroscopy.

A three-dimensional derivative variable-angle synchronous scanning (DVASS) and a synchronous scanning (SS) heavy-atom room-temperature phosphorimetry (HAI-RTP) method are reported, for the first time, to identify and quantify the spectral overlapping phosphorescent pesticides thiabendazole (TBZ) and carbaryl (CBL). These pesticides are widely used in agriculture. The phosphorescence emission of the two compounds was obtained using sodium sulfite as the O2 scavenger and an external heavy atom salt. A careful selection of these experimental variables has been carried out. The increase of selectivity afforded by the DVASS and the SS methodology permitted the demonstration of its applicability to the simultaneous determination of phosphorescent signals of these two pesticides with overlapping spectral profiles. Limits of detection ranged between 1.4 ng/mL for TBZ and 1.7 ng/mL for CBL. The proposed method has been satisfactorily applied to the analysis of both pesticides in different types of water samples.

Determination of imidacloprid and its metabolite 6-chloronicotinic acid in greenhouse air by application of micellar electrokinetic capillary chromatography with solid-phase extraction.

A method is described for the analysis of the insecticide imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and its metabolite 6-chloronicotinic acid by micellar electrokinetic chromatography with diode-array detection at 270 and 227 nm, respectively. The best results were obtained using sodium dodecyl sulphate at a concentration of 60 mM and a running buffer of NH4Cl/NH3 at 15 mM (pH 8.5). The selection of instrumental parameters such as voltage at 30 kV with an injection time of 20 s gave the best resolution with an analysis time of less than 6 min. The method yields similar sensitivity for the parent compound and for the metabolite, with detection limits of 0.71 and 1.18 microg/ml for imidacloprid and 6-chloronicotinic acid, respectively. The sampling and analysis of these two pesticides in greenhouse air was carried out using personal samplers connected to XAD-2 cartridges as sampling media, investigating the dissipation of analytes in a 24-h period after their application.

Fluorescence optosensors based on different transducers for the determination of polycyclic aromatic hydrocarbons in water.

This paper presents the development of two optosensors for the determination of four polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene, fluoranthene and benzo[b]fluoranthene) using a photomultiplier device and an intensified coupled charge device (ICCD) as optical transducers, respectively. These optosensors are based on the on-line immobilization of the analytes onto a non-ionic resin solid support (Amberlite XAD-4) in a continuous flow system, followed by the measurement of their native fluorescence. The determinations were performed using 15 mM H(2)PO(4)(-)/HPO(4)(2-) buffer solution at pH 7 and 25% 1,4-dioxane. Detection limits were 6.4 and 9.3 for ANT, 3.3 and 2.5 for BbF, 1.4 and 13.2 for FLT, and 1.7 and 7.8 for BaP using optosensor 1 or 2, respectively. Relative standard deviations were 7.9 and 6.7 for ANT at 50 ng mL(-1), 3.5 and 7.4 for BbF at 60 ng mL(-1), 3.6 and 8.9 for FLT at 50 ng mL(-1), and 6.7 and 11.6 for BaP at 50 ng mL(-1) using optosensor 1 or 2, respectively. Finally, a critical comparison between the two configurations based on different transducers (photomultiplier and ICCD) for resolving and simultaneously determining mixtures of the polycyclic aromatic hydrocarbons under study in water samples (tap and mineral waters) were carried out.

A sensitive fluorescence optosensor for analysing propranolol in pharmaceutical preparations and a test for its control in urine in sport.

We describe a simple and selective method for analysing propranolol and a sensitive test for its control in urine. A flow-through fluorescence optosensor based on on-line immobilization in a non-ionic-exchanger (Amberlite XAD-7) solid support in a continuous flow was used in both cases. Determination was made in 5 mM H(2)PO(4)(-)/HPO(4)(2-) buffer solution at pH 6 at a working temperature of 20 degrees C. Fluorescence intensities were measured at lambda(ex/em) = 300/338 nm with a response time of 80 s, thus obtaining a linear concentration range of between 0 and 250.0 ng ml(-1) with a detection limit of 1.3 ng ml(-1), an analytical sensitivity of 6.0 ng ml(-1) and a standard deviation of 2.40% at a 150 ng ml(-1) concentration level for propranolol. We also propose a test to detect propranolol in urine with a linear concentration range between 0 and 100.0 ng ml(-1), a detection limit of 0.2 ng ml(-1), an analytical sensitivity of 1.0 ng ml(-1), and a standard deviation of 0.84% at a 75 ng ml(-1) concentration level. The effect of proteins presents in urine samples were evaluated. The two proposed methods were satisfactorily applied to commercial formulations and urine samples respectively.

Simple determination of propranolol in pharmaceutical preparations by heavy atom induced room temperature phosphorescence.

The applicability of heavy atom induced room temperature phosphorescence in real samples is demonstrated in this work. In this methodology only two reagents, potassium iodide as heavy atom salt and sodium sulphite as oxygen scavenger, were used to obtain phosphorescent signal of propranolol in solution. Thus a new simple, rapid and selective phosphorimetric method is proposed for propranolol determination in pharmaceutical preparations. The phosphorescence intensity was measured at 492 nm exciting at 294 nm. Phosphorescence was fully developed instantly, obtaining a linear concentration range between 0 and 500 ng ml(-1) with a detection limit of 14.4 ng ml(-1), an analytical sensitivity of 6.7 ng ml(-1) and a standard deviation of 1.4% at a 300 ng ml(-1) concentration level. The method has been successfully applied to the analysis of propranolol in an antidepressive pharmaceutical preparation and it was validated using standard addition methodology.

HAI-RTP determination of carbaryl pesticide in different irrigation water samples of south Spain.

In this work, a widely used pesticide named carbaryl, present in numerous water supplies, has been determined by the so-called heavy atom induced room-temperature phosphorescence (HAI-RTP) methodology. A detailed study of numerous instrumental variables such as sensitivity, slits, decay time, and gate time, and those of experimental type such as heavy atoms, oxygen scavenger, temperature, buffer solutions, and organic solvents, have been carried out. The detection limit was 2.8 ng mL(-)(1) with a relative standard deviation of 2.12% at the 150 ng mL(-)(1) level. Spiked irrigation water samples taken from different places near agricultural fields gave mean percentage recoveries of 95.7%. The results obtained in this study indicate that the proposed method is suitable for the determination of residues of carbaryl pesticide in water samples with good reproducibility and sensitivity for the analysis of this compound being rapid and very simple for routine analysis.

Facile and selective determination of the cerebral vasodilator nafronyl in a commercial formulation by heavy atom induced room temperature phosphorimetry.

This paper presents a facile and selective method for the determination of the pharmaceutical compound nafronyl using heavy atom induced room temperature phosphorimetry (HAI-RTP) as analytical technique. The determination was performed in potassium iodide 1.6 M and sodium sulphite 0.002 M at a measurement temperature of 20 degrees C. The phosphorescence intensity was then measured at lambda(exc) = 292 nm and lambda(em) = 524 nm. Phosphorescence was fully developed instantly, obtaining a linear concentration range between 2.7 and 250 ng ml(-1) with the detection limit of 2.7 ng ml(-1), an analytical sensitivity of 5.1 ng ml(-1) and a standard deviation of 2.17%, at a 150 ng ml (-1) concentration level. The proposed method has been satisfactorily applied to the unique Spanish commercial formulation containing nafronyl at a 100 mg level per capsule. The recovery was 108%, with a 1.7%, standard deviation of the analytical measurement. The method has been validated using standard addition methodology.

Application of partial least-squares calibration to phosphorimetric data for determination of polycyclic aromatic hydrocarbons in spiked environmental samples.

A partial least-squares calibration method is proposed, for the first time, for phosphorescence signals. The proposed method is based on the determination of phenanthrene, fluoranthene, and benz[a]anthracene by room temperature phosphorimetry, using microemulsion solutions. The emission and first-derivative emission spectra of the ternary mixtures were tested to perform the calibration matrix. Improved recoveries were found for the prior differentiation step in the analysis of ternary mixtures of these polycyclic aromatic hydrocarbons in road dust samples. The proposed method yielded recoveries ranging from 93.2 to 115.3%, with relative standard deviations of < 6.8%.

Fluorimetric determination of procaine in pharmaceutical preparations based on its reaction with fluorescamine.

A simple spectrofluorimetric analysis of a local anaesthetic named procaine using a specific labelling reagent for primary amino groups, has been developed. Because procaine shows very weak native fluorescence, the technique of spectrofluorimetry has been very much limited for its determination. A detail study of the variables affecting the derivatisation reaction (pH, fluorescamine (FC) concentration, temperature, reaction time), have minuciously been studied. The minimum detectable quantity is estimated as 7.7 ng ml(-1), with a relative standard deviation of 2.16% (ten determinations) for a procaine concentration of 100 ng ml(-1). The present method can be employed for the analysis of procaine by direct fluorescence measurements, without the interference from other compounds. The applicability of the present methodology have been demonstrated analysing three pharmaceutical preparations containing the analyte with satisfactory results.

Simple and rapid determination of the drug naproxen in pharmaceutical preparations by heavy atom-induced room temperature phosphorescence.

A simple, selective and sensitive heavy atom-induced room temperature phosphorimetric method (HAI-RTP) is described for the determination of naproxen (NAP) in pharmaceutical preparations. The phosphorescence signals are a consequence of intermolecular protection when analytes are, exclusively, in presence of a heavy atom salt and sodium sulfite as an oxygen scavenger to minimize RTP quenching. These variables selection constitute the basis of a HAI-RTP method for the determination of naproxen (detection limit 17.6 ng ml(-1); 1.71% relative standard deviation at 250 ng ml(-1)). The method has been applied satisfactorily to the analysis of pharmaceutical preparations.

The use of dansyl chloride in the spectrofluorimetric determination of the synthetic antioxidant butylated hydroxyanisole in foodstuffs.

A sensitive method is presented for the determination of the synthetic antioxidant butylated hydroxyanisole (BHA) based on the dansylation process of the phenolic hydroxy group. The fluorescence developed can be measured directly without previous extraction or chromatographic separation of the labelled fluorescent compound. It is shown the effect of numerous experimental variables affecting the fluorescence intensity and the signal-to-noise ratio of the dansyl derivative. The compound was determined over the range 0.05-5 mug ml(-1), with a relative S.D. of 3.8% (300 ng ml(-1)) and a detection limit of 52 ng ml(-1). The selectivity conferred by the dansylation reaction has permitted to avoid the interference of normally accompanying antioxidants, such as butylated hydroxytoluene (BHT), due to steric impediment. The stability of the DNS-derivative is well suited for the analysis of different foodstuffs.

Room-temperature phosphorimetric method for the determination of the drug naphazoline in pharmaceutical preparations.

A selective and sensitive micelle-stabilized room-temperature phosphorimetric (MS-RTP) method for the determination of naphazoline in pharmaceutical preparations is described. The method is based on obtaining a phosphorescence signal from naphazoline using a micellar agent (sodium dodecyl sulfate), a heavy atom salt (TINO3) and a deoxygenation agent (Na2SO3). Optimization of the various conditions permitted the establishment of an MS-RTP method for naphazoline determination with a detection limit of 64.2 ng ml-1 and a relative standard deviation of 3.74% at the 500 ng ml-1 level. The method was applied to the analysis of pharmaceutical preparations.

Method for the Quantitative Determination of 1-Naphthaleneacetic Acid in Spiked Canned Pineapple Samples by Micelle-Stabilized Room Temperature Phosphorescence.

This paper presents a convenient method for the determination of 1-naphthaleneacetic acid (NAA) plant growth regulator in spiked canned pineapple samples by micellar-stabilized room temperature phosphorescence with sodium dodecyl sulfate as a micellar medium, thallium nitrate as an external heavy atom, and sodium sulfite as an oxygen scavenger. A multivariate optimization approach using the type of central composite blocked cube-star design was carried out. The analytical curve of NAA gives a linear dynamic range of 70-500 ng mL(-)(1) with a detection limit of 21 ng mL(-)(1) and precision of 2.37% (n = 7). A mean recovery value of 98.6% was obtained for 250 ng mL(-)(1) NAA in the pineapple samples.

Determination of the plant growth regulator beta-naphthoxyacetic acid by micellar-stabilized room temperature phosphorescence.

This paper presents a method for the determination of the plant growth regulator beta-naphthoxyacetic acid (NOA) by micellar-stabilized room temperature phosphorescence with the surfactant Triton X-100 (TX-100) as the micellar medium, thallium nitrate as the heavy atom and sodium sulphite as the oxygen scavenger. A multivariate optimization approach using the blocked cube star design of central composite was carried out. The analytical curve of NOA gives a linear dynamic range of 0.4-3.0 mug ml(-1) and a detection limit of 0.13 mug ml(-1). A recovery of 93.6% was obtained for 1 mug ml(-1) NOA in spiked apple samples.

Derivative spectrophotometric resolution of mixtures of the food colourants Tartrazine, Amaranth and Curcumin in a micellar medium.

A study of the absorption spectra of the food colourants Tartrazine (E-102), Amaranth (E-123) and Curcumin (E-100) in various organic solvents and pH media, have been carried out. In addition, the spectral behaviour in aqueous micellar systems of anionic, cationic and non-ionic surfactants, as well as beta-cyclodextrin, was investigated. Analytical methods are proposed for the determination of the three dyes in mixtures without any prior separation step, by the application of the derivative technique to the normal absorption spectra, based on the use of cetyltrimethylammonium bromide (CTAB) in 0.1 M NaOH, over the concentration range 2-50 mug ml(-1). The methods are applied for determining the three dyes in commercial food products.