Determination of selenomethionine by high performance liquid chromatography-direct hydride generation-atomic absorption spectrometry

A simple, reliable, trace determination of selenomethionine (Semet) based on a direct hydride generation atomic absorption spectrometric method was developed using sodium tetrahydroborate (0.3% in 0.2% NaOH) and hydrochloric acid (3 M). The method excluded any chemical pretreatment prior to hydride generation (HG). The optimized HG system was successfully coupled with the HPLC system. The detection limit (3σ of blank; n=5), reproducibility (R.S.D. of three successive analyses/day, performed on three different days), and repeatability (R.S.D. of three successive analyses) of the method were 1.08 ng ml⁻¹, 9.8% for 9.04 ng ml⁻¹ and 2.1–9.5% for 30.0–1.27 ng ml⁻¹ Semet as Se (standards prepared in Milli-Q water). Calibration graph was linear up to 30 ng ml⁻¹. This HPLC-HG-AAS method is very promising and successfully determined Semet (spiked) in human urine.     

Simultaneous Determination of Cefepime and the Quinolones Garenoxacin, Moxifloxacin and Levofloxacin in Human Urine by HPLC-UV

A liquid chromatographic method with a C₁₈ column and acetonitrile/0.1 M phosphoric acid/ sodium hydroxide buffer (pH 3.0)/0.01 M n-octylamine (pH 3.0) as mobile phase in gradient mode has been developed and optimised for the simultaneous determination of the cephalosporin cefepime and the quinolones garenoxacin, levofloxacin and moxifloxacin. Identification and quantification was carried out with a diode-array UV detector, with working wavelengths of 256 nm for cefepime, 292 nm for levofloxacin, 294 nm for moxifloxacin and 282 nm for garenoxacin. The mobile flow-rate and sample volume injected were 1 mL min⁻¹ and 20 µL, respectively. The retention times and detection limits for each antibiotic were 4.9 min and 1.9 µg mL⁻¹ for cefepime, 7.5 min and 2.2 µg mL⁻¹ for levofloxacin, 8.9 min and 2.7 µg mL⁻¹ for moxifloxacin and 10.7 min and 1.8 µg mL⁻¹ for garenoxacin, respectively. The method was applied to the determination of the four molecules in spiked samples of human urine.     

Square-wave cathodic adsorptive stripping voltammetric determination of trace amounts of 2-mercaptobenzimidazole in water samples

A sensitive, simple and reproducible square-wave cathodic adsorptive stripping voltammetric method is developed for the determination of 2-mercaptobenzimidazole (MBIM) in different water samples using a static mercury drop electrode (SMDE) as a working electrode. The solution conditions and instrumental parameters were optimized for the determination of MBIM by square-wave cathodic adsorptive stripping voltammetry. This method is based on a sensitive adsorptive reduction peak of the MBIM at ?0.532 V vs. Ag/AgCl reference electrode in a Britton-Robinson buffer at pH 10.0. The linear concentration range was 20–600 ng ml^?1 when using 0.0 V as the accumulation potential. The detection limit of the method was calculated to be 8.41 ng ml^?1. The precision was excellent with relative standard deviations (n = 20) of 2.30%, 1.71%, 2.25% and 1.33% at MBIM concentrations of 40, 90, 200 and 500 ng ml^?1, respectively. The proposed voltammetric method is used for the determination of MBIM in different spiked water samples.     

Occurrence of ochratoxin A in Turkish wines

A total of 95 wine samples including 34 white, 10 rosé and 51 red wines originating from four different Turkish areas were analysed for ochratoxin A (OTA). An analytical method based on immunoaffinity column (IAC) for clean-up and high performance liquid chromatography with fluorescence detection (HPLC-FD) was used to determine OTA in wines. The limit of detection (LOD) was estimated as 0.006 ng ml^− 1 for white wine and 0.010 ng ml^− 1 for rosé and red wines. The limit of quantification (LOQ) was estimated as 0.020 ng ml^− 1 in white wine and 0.030 ng ml^− 1 in rosé and red wines. Recovery experiments were carried out with spiked samples in the range 0.1–1 ng ml^− 1 of OTA. The average OTA recoveries from spiked white wine samples varied from 79.43% to 85.07%; while the mean recoveries for rosé and red wine samples were in the range of 77.48–83.96% and 76.61–83.55%, respectively. OTA was detected in 82 (86%) wine samples at levels of < 0.006–0.815 ng ml^− 1, which were below the maximum allowable limit established by the European Community. The mean OTA concentration in red wines was slightly higher than in white and rosé wines. Furthermore, our data indicate that the geographic region of origin has strong influence on OTA level for white, rosé and red wines: wines originating from Thrace (n = 44, mean = 0.158 ng ml^− 1) and Aegean (n = 28, mean = 0.060 ng ml^− 1) regions of Turkey were more contaminated with OTA compared with wines originating from central (n = 15, mean = 0.027 ng ml⁻¹) and east Anatolia (n = 8, mean = 0.027 ng ml^− 1) areas. This study showed that the occurrence of OTA in Turkish wines is high, but at levels that probably leads to a non-significant human exposure to OTA by consumption of wines.     

Determination of B in body fluids by isotope dilution inductively coupled mass spectrometry with direct injection nebulization

The determination of B in small volumes of undigested blood plasma and urine by isotope dilution and high efficiency direct injection nebulization (DIN) inductively coupled plasma mass spectrometry (ICP-MS) is proposed. The C interference over ¹¹B was removed by precipitating the samples proteins. Samples aliquots of 1 ml were spiked with an enriched ¹⁰B solution and shaken during 1 h to attain the isotopic equilibrium. Thereafter, the sample proteins were denaturated with nitric acid and the supernatant was analyzed. This procedure was effective to reduce C concentrations in approximately 94%. Sample volumes of 50 μl were introduced into the ICP by the direct injection nebulizer producing transient signals lasting 30 s for B isotopes measurements. Precision of ¹⁰B/¹¹B measurements was characterized by relative standard deviation (RSD) lower than 1%. The instrumental mass discrimination factor was lower than 5%. Total B concentrations from 100 to 135 μg L⁻¹ in plasma and 0.499 to 3.021 mg L⁻¹ in urine samples were found. Reproducibility of triplicate samples was characterized by RSD<2.0% for plasma and lower than 1.3% for urine samples. Limit of detection (3σ) of 0.6 ng ml⁻¹ was calculated from synthetic blood plasma blank. Results of the denatured supernatant and digested plasma and urine samples were comparable at the 95% confidence level.     

Differential Pulse Polarographic Determination of Moxifloxacin Hydrochloride in Pharmaceuticals and Biological Fluids

Abstract

A simple, fast, sensitive and fully validated differential pulse polarographic (DPP) method for the determination of trace amounts of moxifloxacin in pharmaceutics, serum and urine is reported. Moxifloxacin exhibited irreversible cathodic peak over the pH 5.00–11.00 in Britton–Robinson (B–R) buffer. At pH 10.00 (the analytical pH), a well‐defined peak at ?1.61 V versus saturated calomel electrode was obtained. The current has been characterized as being diffusion‐controlled process. The diffusion current constant (i_d) was 1.48±0.12 and the current–concentration plot was rectilinear over the range from 5×10^?7 to 1×10^?4 M with correlation coefficient (n=10) of 0.995.

The proposed method was applied to commercial tablets and average percentage recovery was in agreement with that obtained by spectrophotometric comparison method. The method was extended to the in vitro determination of moxifloxacin in spiked human serum and urine.     

Speciation of mercury by continuous flow liquid-liquid extraction and inductively coupled plasma atomic emission spectrometry detection

An accurate, precise, sensitive and automated non-chromatographic method for methylmercury speciation based on a selective continuous liquid-liquid extraction of methylmercury, into xylene, as bromide and cold mercury vapour generation directly from the organic phase and final ICP-AES mercury detection is proposed. Both separation steps, liquid-liquid and gas-liquid are accomplished in a continuous mode and on line with ICP-AES as detector. The detection limit attained for methylmercury was 4ng·ml^–1 (as mercury). The precision of the determination at a concentration level around 20 times the detection limit was +-5%. The proposed methodology has been applied successfully to the speciation of methylmercury and inorganic mercury in spiked sea water and spiked urine samples.     

Assay of femtogram level nitrite in human urine using luminol–myoglobin chemiluminescence

In this paper, a sensitive flow injection chemiluminescence system luminol–myoglobin was described for determining femtogram nitrite. Nitrite bound myoglobin producing the ferric heme nitrite complexes, which catalyzed the electron transfer of luminol to myoglobin leading to fast chemiluminescence. The chemiluminescence intensity in the presence of nitrite was remarkably enhanced compared with that in the absence of it. Under the optimum reaction conditions the chemiluminescence increment produced was proportional to the concentration of nitrite in the range of 0.05 pg ml^− 1–1.0 ng ml^− 1 (R² = 0.9991), with a detection limit (3σ) of 20.0 fg ml^− 1. At the flow rate of 2.0 ml min^− 1, the whole process including sampling and washing could be completed in 0.5 min offering the sampling efficiency of 120 h^− 1 accordingly, and the relative standard deviation (RSD) was less than 2.60% (n = 5). It was satisfactory for the application to determine nitrite in human urine samples, and the possible mechanism was proposed.     

Determination of medecamycin by adsorptive stripping voltammetry with an activated electrode

The adsorptive and electrochemical behaviors of medecamycin were investigated on a glassy carbon electrode (GCE) pretreated by anodic oxidation at +1.8 V for 5 min in 0.025 mol l^–1 NH₃-NH₄Cl (pH 8.6) solution. An adsorptive stripping voltammetric method for the determination of medecamycin at the pretreated glassy carbon electrode has been developed. Medecamycin was accumulated in NH₃-NH₄Cl buffer (pH 9.0) at a potential of –0.7 V (vs. saturated calomel electrode (SCE)) for a certain time, and then determined by second-order differential anodic stripping voltammetry. The second-order differential anodic stripping peak current at +0.72 V was proportional to the concentration of medecamycin in the range 2.0 g ml^–1 to 50.0 g ml^–1. The detection limit (three times the signal-to-noise) was 1.0 g ml^–1 and the relative standard deviation of the results was 3.28% for eight successive determinations of 10.0 g ml^–1 medecamycin. This method has been applied to the direct determination of medecamycin in commercial tablets and spiked urine samples with satisfactory results.     

Determination of some selected polycyclic aromatic hydrocarbons in environmental samples by high-performance liquid chromatography with fluorescence detection

Summary Analytical methods for the determination in environmental samples, of some selected Polycyclic Aromatic Hydrocarbons (PAH's), which are included on the EPA Priority Pollutant list, have been developed and evaluated. The methodology involves the extraction of PAH's from water samples by solvent extraction with dichloromethane. Solid samples were ultrasonically extracted with acetone/hexane and the extract was cleaned up on a silica gel/alumina column. The concentrated and cleaned up extracts were analysed by HPLC on a polymeric C₁₈ column using a gradient of acetonitrile/water as the mobile phase and fluorescence detection. Typical detection limits lie in the range of 1–30 ng ml^–1 of the analytes, but after sample pretreatment detection limits of 10–300 ng l^–1 were obtained. The extraction, clean-up and HPLC methodology was applied to the determination of selected PAH's in coal washings samples and the method was validated by the quantification of PAH's in a natural contaminated and a spiked sediment.     

Electrochemical Behavior and Determination of Uric Acid at Single-Walled Carbon Nanotube Modified Gold Electrodes

The voltammetric behavior of uric acid was studied at a single-walled carbon nanotube (SWNT) modified gold electrode. Uric acid can effectively accumulate at this electrode and produce an anodic peak at about 0.45 V (vs. SCE) in pH 5.0 sodium acetate buffer solutions (HAc-NaAc). The experimental parameters, such as solution pH, accumulation time, and amount of SWNT, were optimized for determination. Under the optimum conditions, the anodic peak current is linear to the uric acid concentration over the range of 1.0×10⁻⁷ M to 2.5×10⁻⁵ M with a correlation coefficient of 0.998. The detection limit was 5.0×10⁻⁸ M for 60 s accumulation. The electrode could be easily regenerated and exhibited good stability. A 5.0×10⁻⁶ M uric acid solution was measured ten times using the same electrode, and the relative standard deviation of the peak current was 1.3%. This method was successfully applied to the determination of uric acid in human urine samples, and the recovery was 97–99%. The feasibility for simultaneous determination of xanthine, ascorbic acid and uric acid was discussed. These species did not interfere with each other in a certain concentration range. The influence of some surfactants on the anodic peak was also examined.     

Adsorptive stripping voltammetric determination of netilmicin in the presence of formaldehyde

A linear sweep adsorptive stripping voltammetric method for the determination of netilmicin in the presence of formaldehyde has been proposed for the first time. In the presence of 3.0×10⁻³ g ml⁻¹ formaldehyde, netilmicin exhibits a sensitive cathodic peak at −1.30 V (vs. the saturated calomel electrode, SCE) in a medium of Britton–Robinson buffer (pH 8.7) with a scan rate of 100 mV s⁻¹ after a preconcentration period of 120 s at −1.10 V (vs. SCE). The peak current showed a linear dependence on the netilmicin concentration over the range 4.2×10⁻⁹–1.0×10⁻⁷ g ml⁻¹. The achieved limits of detection and quantitation were 1.0×10⁻¹⁰ and 3.3×10⁻¹⁰ g ml⁻¹ netilmicin, respectively. It was deduced from the experiments that the amine–aldehyde condensation product formed between netilmicin and formaldehyde is mainly responsible for the appearance of the peak. The electrochemical behavior of netilmicin in the presence of formaldehyde has been studied. The method was applied to the direct determination of netilmicin in injectable formulations and spiked human urine and serum samples.      

Atomization Characteristic of Chromium on a Molybdenum Tube Atomizer by Electrothermal Atomic Absorption Spectrometry and Determination of Chromium in Biological Materials

Atomization characteristics of chromium have been studied by electrothermal atomic absorption spectrometry with a molybdenum tube atomizer. The appearance temperature (T_app) of chromium nitrate was 1300°C. TheT_appwas independent of the heating rate of atomizer, but the temperature at the peak of the Cr AA signal increased with the heating rate. A sensitive absorption chromium signal was obtained in pure argon purge gas. The chromium signal decreased as the ratio of hydrogen in the purge gas increased. The optimal gas flow rate was Ar 480 ml min⁻¹+ H₂20 ml min⁻¹because of the avoidance of oxidation of the atomizer. The absolute characteristic mass (the mass of element giving 0.0044 abs.) of chromium by the atomizer was 0.35 pg and the detection limit was 23 pg ml⁻¹(3S/N). The interferences caused by large amounts of interferents were evaluated. The addition of thiourea served to eliminate the severe interferences. The accuracies of the recommended method were considered almost satisfactory for the determination of chromium in biological materials, compared with the certified values of NIST materials. The recovery of spiked chromium in biological materials was in the range from 93.5 to 102%.     

Determination of 4-methylbenzilidene camphor in sunscreen by square wave voltammetry in media of cationic surfactant

The voltammetric behavior of 4-methylbenzelidene camphor (MBC) was studied by square wave voltammetry (SWV) using mercury electrode. The experimental condition that provided the highest peak current with the best reduction signal definition of MBC was found in Britton-Robinson buffer and cationic surfactants, cetyltrimethylammoniun bromide (CTABr). A single peak of MBC reduction was observed at − 1.21 V versus Ag/AgCl. The developed methodology was applied for determination of MBC in commercial sunscreen SPF 15, 20 and 30 and for the simultaneous determination when other protection agents were associated, such as benzophenone-3 (BENZO) and octyl methoxycinammate (OMC). Both methodologies had shown good determination values for the analyzed samples. The calculated detection limit was 2.99 × 10^− 9 mol L^− 1 and the quantification limit was 9.98 × 10^− 9 mol L^− 1.     

Absorptiometric determination of micro- and submicroamounts of iron using an extractive method with pyridine-2-acetaldehyde salicyloylhydrazone

The formation and extraction into chloroform of iron complex with PASH (λ_max = 640 nm) was studied. Beer's law is obeyed between 2.7 and 16.0 μg · ml⁻¹ of iron, in organic phase (10 ml). The method can be applied to volume ratios V_aq.:V_org. from 1:1 to 20:1. The minimum concentration determinable in aqueous phase is 135 ng ml⁻¹ of iron. The interferences of 73 species were evaluated and eliminated when it was possible. The extraction method of the green complex was applied for the spectrophotometric determination of iron(II) in several standard, geochemical, and bromatological samples. A procedure based on the standard addition method was applied satisfactorily to the determination of as little as 25 ng of iron(II) per milliliter.     

Speciation of silicon and phosphorous using liquid chromatography coupled with sector field high resolution ICP-MS

Sector-field high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) has been used, at R=3000, to resolve spectral interferences caused by N₂⁺ and CO⁺ on ²⁸Si⁺, and NOH⁺ and NO⁺ on ³¹P⁺, thereby facilitating the speciation of these elements. Polydimethylsiloxanes (PDMS), ranging from 162 g mol⁻¹ to 16 500 g mol⁻¹, and their silanol breakdown products, have been separated by size exclusion and reverse phase chromatography, respectively, and detected using HR-ICP-MS. Detection limits (as Si) of between 12–30 ng ml⁻¹ and 0.1–4 ng ml⁻¹ were obtained for the PDMS and silanol compounds, respectively. Quantitative and reproducible methods have been developed for the analysis of four common organophosphorous pesticides in blood plasma, and inorganic phosphates in food, with detection limits of between 0.9–2 ng ml⁻¹ and 1–39 ng ml^−1, respectively.     

Ethylisobutrazine hydrochloride as a selective and sensitive reagent for the spectrophotometric determination of vanadium(V) and its application to vanadium-bearing minerals and alloys

Ethylisobutrazine hydrochloride is proposed as a selective and sensitive reagent for the spectrophotometric determination of vanadium(V). It forms a red-colored species with vanadium(V) in 3.5–6.5 M phosphoric acid medium. An eight-fold molar excess of reagent is necessary for the full development of the color. The red species exhibits an absorption maximum at 518 nm with a molar absorptivity of 9.75 × 10³ liters mol⁻¹ cm⁻¹. Sandell's sensitivity is 5.2 ng cm⁻². Beer's law is obeyed over the range 0.1–6.2 ppm of vanadium(V) with an optimum concentration range of 0.4–6.0 ppm. The effects of acidity, time, temperature, order of addition of reagents, reagent concentration, and the interferences from various ions, are reported. The method has been used successfully for the determination of vanadium in ilmenite and vanadium steels that contain chromium, molybdenum, manganese, nickel, copper, tungsten, and titanium.     

Differential pulse cathodic stripping adsorption voltammetric determination of trace amounts of lead using factorial design for optimization

A sensitive cathodic stripping voltammetric method is developed for determination of lead(II), with adsorptive collection of complexes with Pyrogallol red (PGR) on to a hanging mercury drop electrode. After accumulation of the complex at −0.80 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from −0.20 to −0.50 V with differential pulse method. Then the reduction peak current for the lead(II)-PGR complex is measured at −0.39 V. The influence of reagent and instrumental variables was completely studied by factorial design analysis. The optimum analytical conditions for the determination of lead(II) were established. Under optimum conditions, lead(II) determined in the range of 0.1-30.0 ng ml⁻¹ with a limit of detection of 0.06 ng ml⁻¹. The method is successfully applied to determination of lead(II) in water sample.     

Preconcentration of metal ions using an immobilized dialkyldithiocarbamate in a flow system

Flow injection analysis with on-line preconcentration using a minicolumn loaded with dialkyldithiocarbamate immobilized on controlled pore glass is described for the determination of Rh(III), Co²⁺, Cu²⁺, Hg²⁺, and Hg₂²⁺. The detection limits range from 0.05 ng ml⁻¹ for Cu²⁺ to 50 ng ml⁻¹ for Hg²⁺ for 5- or 10-ml samples, improvement of 2–3 orders of magnitude compared with direct injection. The operating conditions are optimized and the effects of interferents are studied. The capacity of the collector varied from 0.9 mmol g⁻¹ for Rh(III) to ca 4 mmol g⁻¹ (Co²⁺, Cu²⁺, Hg²⁺).     

Determination of furazolidone in urine by square-wave voltammetric method

A fast, simple and sensitive square-wave voltammetric (SWV) method for the determination of trace amounts of furazolidone (FZ) in urine is reported. A three-electrode system containing stationary mercury dropping (SMDE) working electrode, Pt auxiliary electrode and Ag/AgCl reference electrode was used throughout. Briton-Rabinson buffer solution is used as both pH adjusting agent and supporting electrolyte. The calibration graph showed good linearity in the concentration range of 20–900 ng ml^?1 of furazolidone with a regression coefficient of 0.9996. The equation Δ(i) = 0.0095C_FZ + 0.234 was used for calculation of furazolidone concentration in the sample solution, where C_FZ is the concentration of furazolidone in ng ml^?1 and Δ(i) is the difference between voltammogram peak currents of sample and blank solution. The RSD for 8 replicate measurements of a 60 ng ml^?1 solution and LOD of the proposed method were found to be 2.2% and 5.2 ng ml^?1, respectively. The procedure was successfully applied to the determination of furazolidone in urine samples.