Flow-Batch Method with a Sequential Injection System for Spectrophotometric Determination of Selenium(IV) in Selenium-Enriched Yeast Using o-Phenylenediamine

A precise, accurate, and reliable flow-batch spectrophotometric method for the determination of selenium (IV) was developed using o-phenylenediamine as a reagent with a sequential injection monosegmented flow system incorporating a simple heating unit. The reaction zones of selenium(IV) and o-phenylenediamine were mixed and heated in a chamber at 62°C for 5 minutes. The piaselanol complexes were then detected at a maximum absorption wavelength of 335 nm. In-line single standard calibration and standard addition procedures were developed employing the monosegmented flow technique. Under the optimized conditions, a linear calibration graph in a range of 0.1–4.0 mg L^?1 selenium (IV) was obtained with limits of detection and quantitation of 0.01 and 0.1 mg L^?1, respectively. Relative standard deviations were 2% [for both 0.1 and 0.5 mg L^?1 selenium (IV) (n = 11)]. A sample throughput of 2 h^?1 using four standard addition levels was achieved. The developed system was successfully applied to raw selenium-enriched yeast samples. The analyses performed by the developed method agreed well with those obtained from a standard inductively coupled plasma mass spectrometry method.     

Determination of Propylene Glycol in Low Volume Plasma and Urine Samples of Neonates by LC with Photodiode Array Detection

In order to enhance the sensitivity and to develop a method suitable for quantification of propylene glycol (PG) in low volume neonate plasma and urine samples, several steps in earlier described high performance liquid chromatographic methods were optimised. Chromatographic separation on a reversed-phase column and ultraviolet detection resulted in cleaner chromatograms without interfering compounds. Linearity of the standard curves was validated in the concentration range 0.25?C50 mg L^?1. The lower limit of quantification was 20 times lower than in earlier described methods. Presented method was suitable for quantification of PG concentrations in low volume neonate plasma (15?C46 mg L^?1) and urine samples (20?C175 mg L^?1) enabling us to document very low renal versus non-renal contribution of PG clearance in neonates.     

Fast Determination of Phenolic Compounds in Brazilian Wines from Vale do São Francisco Region by CE

Six phenolic compounds were separated and determined by capillary zone electrophoresis in red wine from Brazil’s region Vale do São Francisco with total analysis time of 12 min. The limit of detections varied from 1.59 to 2.24 mg L^?1. The relative standard deviations (for n = 6) varied from 0.28 to 3.50 %. The red wine samples analyzed were bought in the local market and the phenolic compound recoveries were in the range of 98–101 %. The concentrations of gallic acid in the samples of wines varied from 16.0 to 42.0 mg L^?1, caffeic acid (3.16–5.18 mg L^?1), syringic acid (5.73–13.0 mg L^?1), kaempferol (2.32–4.33 mg L^?1), quercetin (1.68–4.03 mg L^?1), myricetin (7.52–25.1 mg L^?1). The concentrations found agree with data reported in the literature.     

Determination of Trenbolone Acetate in Cattle Feeds by a Flow Injection Chemiluminescence Method

A flow injection chemiluminescence (CL) method is described for the determination of trenbolone acetate based on the CL generated during its reaction with KMnO₄ in acidic medium. The CL intensity is greatly enhanced by alizarin yellow R. The CL intensity is linear with trenbolone acetate concentration in the range 0.1–100.0 mg L^?1 with a detection limit of 0.05 mg L^?1. The sample throughout is about 90 h^?1 and the relative standard deviation for 2.0 mg L^?1 trenbolone acetate solution is 1.5% (n = 11). The proposed method was applied to the determination of trenbolone acetate in cattle feeds.     

Determination of Vitamins A and E Exploiting Cloud Point Extraction and Micellar Liquid Chromatography

Cloud point extraction and micellar chromatographic methods were developed for determination of vitamins A and E. The stationary phase was C18 and the mobile phase was 3.00% (w/v) SDS, 15.0% (v/v) butyl alcohol and 0.02 mol L^?1 phosphate buffer solution at pH 7.0. The retention times for vitamins A and E were 9.6 and 13.0, respectively. The extraction solution was 100 mmol L^?1 Triton X-100, 650 mg NaCl and 1.0% ascorbic acid at 70°C for 30 min. The method is precise (r.s.d. < 7%), the linear range was from 5.0 up to 360.0 mg L^?1 for both vitamins. Recovery test showed recuperation between 90.2 and 99.2%, and LOD and LOQ of 0.234 and 0.108 mg L^?1, 0.780 and 0.360 mg L^?1 to vitamins A and E were found.     

Magnetic Nanoparticle-Based Micro-Solid Phase Extraction and GC�CMS Determination of Oxadiargyl in Aqueous Samples

A new facile, rapid, inexpensive, and sensitive method based on magnetic micro-solid phase extraction (M-??-SPE) coupled to gas chromatography?Cmass spectrometry (GC?CMS) was developed for determination of the herbicide oxadiargyl in environmental water samples. The feasibility of employing non-modified magnetic nanoparticles (MNPs) as sorbent was examined and applied to perform the extraction process. Influential parameters affecting the extraction efficiency along with desorption conditions were investigated and optimized. The limit of detection (LOD, S/N = 3) and limit of quantification (LOQ, S/N = 10) of the method under optimized conditions were 0.005 and 0.030 ng mL^?1, respectively. The relative standard deviations (RSD) (n = 3) at a concentration of 0.10 ng mL^?1 was 11%. The calibration curve of oxadiargyl showed linearity in the range of 0.050?C0.50 ng mL^?1. The developed method was successfully applied to the extraction of oxadiargyl from spiked tap water and Zayande-Rood River water samples and the relative recoveries of 98 and 94% were obtained, respectively.     

Determination of Chlorophenoxy Acid Herbicides in Water Samples by Suspended Liquid-Phase Microextraction�CLiquid Chromatography

In this study, directly suspended liquid-phase microextraction was investigated for the extraction and determination of five chlorophenoxy acid herbicides in water samples. The optimized parameters for extraction of chlorophenoxy acid herbicides were 1 M HCl concentration in sample solution, solution temperature 20 °C, 45-min extraction time, 1,000 rpm stirring rate, 25 ??L extracting solvent volume and without NaCl addition. Under the optimum conditions, the enrichment factor ranged from 192 to 390. Calibration curves yielded good linearity (R ² > 0.999) and the linear range was 5.0?C500.0 ??g L^?1, limit of detection was 0.3?C0.4 ??g L^?1 and limit of quantification was 1?C2 ??g L^?1 for analytes and the relative standard deviations were in the range of 3?C10% (n = 3). Finally, the proposed method was successfully applied to the quantification of five chlorophenoxy acid herbicides in water samples and recovery was in the range of 74?C110%.     

Extraction of Azole Antifungal Drugs from Milk and Biological Fluids Using a New Hollow Fiber Liquid-Phase Microextraction and Analysis by GC-FID

A simple, rapid and sensitive high-performance liquid chromatography LC (HPLC) method of determining the concentration of the novel betulinic acid derivative DRF-4012 (5??-chloro-2,3-didehydroindolo[2??,3??:2,3]betulinic acid) in rat plasma for pharmacokinetic and toxicokinetic purposes has been developed and validated. A simple and fast protein precipitation was performed, and then an extraction using an ethyl acetate:methanol (75:25 v/v) mixture was used to extract DRF-4012 and an internal standard (IS, DRF-4015) from rat plasma. Chromatographic separation was achieved using a Zorbax Eclipse XDB-C8 reversed-phase column with UV detection at 235 nm. The isocratic mobile phase, phosphate buffer (water adjusted to pH 3 with 20% o-phosphoric acid) and acetonitrile (15:85, v/v), was run at a flow rate of 1.2 mL min^?1. The assay was linear (r ² > 0.99) over the concentration range 0.040?C75.0 ??g mL^?1, and presented limits of detection and quantification of 0.020 and 0.040 ??g mL^?1, respectively, in rat plasma. The absolute recovery of both the analyte and the IS was >85% from rat plasma. The intraday accuracy ranged from 99.25 to 102.67% with a precision of 2.62?C4.48%, and the interday accuracy ranged from 98.48 to 104.56% with a precision of 3.87?C5.68%. This developed and validated method was successfully used to determine the DRF-4012 concentration in rat plasma for a pharmacokinetic and toxicokinetic study after the intravenous administration of a 1 mg mL^?1 DRF-4012 nanoparticle formulation at doses of 2?C10 mg kg^?1 in Wistar rats.     

Simultaneous CE Determination of Captopril and Indapamide in Pharmaceuticals and Human Plasma

Capillary electrophoresis with UV photo diode-array detection was utilized to adopt a new method for the assay of captopril and indapamide in pharmaceuticals and human plasma. Electrophoretic conditions controlling the analysis were optimized to develop separation, sensitivity and rapidity. The optimum conditions obtained were 100 mM borate at pH 9.0, injection time 10.0 s, voltage 25 kV and column temperature 25 °C with detection at 220 nm. Relatively, wide dynamic ranges for captopril (1–100 mg L^?1) and indapamide (0.1–40 mg L^?1) were obtained. Also, the method recorded acceptable intra- and inter-day accuracy (89.8–97.9%) and precision (0.77–3.50%) in pharmaceutical formulations and human plasma. The sensitivity of the method was developed by the optimization and the preconcentration conducted for human plasma sample using liquid–liquid extraction. The limit of detection gained (0.075 and 0.045 mg L^?1 for captopril and indapamide, respectively) reached the level of both drugs possibly found in human plasma. The method is suitable to be applied in pharmaceutical industries for quality control and in clinical laboratories for therapeutic drug monitoring purposes.     

Uncertainty Analysis of Chlormequat Residue in Fruits by LC�CMS�CMS

A method for determination of chlormequat (CCC) residue in fruits by liquid chromatography?Ctandem mass spectrometry (LC?CMS?CMS) was developed. Residue of CCC was extracted from samples with methanol?Cwater (v/v, 1:1) containing 1.0% acetic acid, cleaned up by strong cationic exchange (SCX) cartridge, and then determined by LC?CMS?CMS. The method showed good linearity over the concentration range 0.002?C5.0 mg kg^?1 with correlation coefficient above 0.997. The limit of detection (LOD) and limit of quantitation (LOQ) for CCC were 5 × 10^?4 mg kg^?1 (S/N = 3) and 0.002 mg kg^?1 (S/N = 10), respectively. Recoveries for CCC at three spiked levels (0.025, 0.050, and 0.20 mg kg^?1) were in the range 80?C102%. Estimation of measurement uncertainty was calculated for CCC at the level of 0.025 mg kg^?1 in fruits. The results demonstrated that the uncertainty of recovery was the main contribution to the combined standard uncertainty. The relative combined standard uncertainties associated with the method ranged from 11 to 13%, depending on the sample matrices.     

Cyclic voltammetry as a screening tool for the fungal degradation of 2,4,6-trinitrotoluene in aqueous media

The use of an electrochemical technique based on cyclic voltammetry (CV) that can be implemented to monitor the degradation of the important nitroaromatic explosive 2,4,6-trinitrotoluene (TNT) in aqueous media when in contact with a microorganism is presented. The microorganism used in this study was an isolated fungus belonging to the Aspergillus genus. In the degradation experiments, during the first 21 days of exposure of the fungal growth to a 68 mg L^?1 TNT aqueous stock solution, the analyte concentration decreased by 44% to 38 mg L^?1 before plateauing through the 58th day of the study. Statistical figures of merit of the technique included linearity in the 1–92 mg L^?1 range and correlation coefficients above 98% for the three reduction peaks of TNT, a limit of detection (LOD) of 3 mg L^?1, a limit of quantification of 10 mg L^?1 and a method precision of 3.8% relative standard deviation (%RSD). Day-to-day and week-to-week repeatability were low at 5.1%RSD and 5.8%RSD, respectively. The results herein exhibit first-order kinetics for the ‘ortho’ nitro group. A clear to yellow colour transition in the control solution and fungi samples suggests the appearance of a TNT metabolite. UV-Vis spectrophotometry supports the presence of a possible derivative of TNT in the fungi samples.     

In-Capillary Derivatization and Preconcentration for CE of Metal Ions as Their Phenanthroline Complexes

A simple and automated method involving in-capillary derivatization and in-capillary preconcentration was developed for the simultaneous determination of metal ions by capillary zone electrophoresis. Fe(II), Zn(II), Cu(II) and Cd(II) were derivatized using 1,10-phenanthroline as the derivatizing agent. The in-capillary derivatization and in-capillary preconcentration via large volume injection were performed sequentially as follows: 60 mmol L^?1 1,10-phenanthroline was first hydrodynamically injected (0.2 psi) for 2 s; metal ions were introduced by hydrodynamic injection (0.5 psi) for 60 s; 0.2 mol L^?1 acetate pH 5.5 containing 20 % methanol was used as the running buffer. Four metal ions can be determined within 8 min using 16 kV. The resulting preconcentration factors were in the range 12–21. Good linearity was obtained for concentrations of 0.1–8.0 mg L^?1 (r ² > 0.990). The mean recoveries of the metal ions evaluated by fortification of wine samples were in the range 90–102 %. The limits of detection ranged from 0.05 to 0.2 mg L^?1. The proposed method can be applied for directly determining metal ions in wine samples.     

Ciprofloxacin and Norfloxacin Spectrophotometric Determination in a Fully Automated Multi-Pumping Flow System

A flow-based methodology for the spectrophotometric determination of ciprofloxacin and norfloxacin, based on the oxidation with N-bromosuccinimide in acidic medium, was developed. The proposed procedure was implemented in a multi-pumping flow system, which provided excellent mixing conditions due to the pulsed flow produced by solenoid micro-pumps actuation, resulting on a sensitive, simple, fast, and versatile analytical method. Linear calibration plots were obtained for ciprofloxacin and norfloxacin concentrations ranging from 5 to 70 mg L^?1 with an R.S.D < 2.2% (n = 10). Detection limits (3σ) were 0.27 mg L^?1 and 0.99 mg L^?1 for norfloxacin and ciprofloxacin, respectively.     

Determination of tetracyclines in milk samples by magnetic solid phase extraction flow injection analysis

A method is presented for magnetic solid phase extraction (MSPE) of tetracyclines in milk samples. The method involves the extraction and clean-up by silica based magnetic support dispersion on non-pretreated milk samples, followed by the magnetic isolation and desorption of the analytes by acidified methanol. The tetracyclines eluted from the magnetic support were determined simultaneously by flow injection analysis with spectrophotometric detection. Under optimal conditions, the linear range of the calibration curve ranges from 0.03 to 0.60 mg L^?1, with a limit of detection of 10 μg L^?1. Recoveries were determined for milk spiked at levels from 0.15 to 0.60 mg L^?1. Average recoveries ranged from 91.0 to 97.0%, with a precision of <5.0% in all cases. The method was validated by comparing the results with those obtained by MSPE-HPLC and SPE-HPLC. No significant differences were observed (p?<?0.05)     

RP-LC Determination of Residual Monomers in Polycarboxylate Superplasticizers

A procedure was developed for the determination of residual monomers in polycarboxylate superplasticizer by reversed-phase high performance liquid chromatography. Seven kinds of residual monomers were quantitatively determined on a SinoChrom ODS-BP (C18) column and UV detector at 205 nm. The mobile phases which were used to determine micromolecular monomers were composed of acetonitrile and phosphate buffer solution (0.05 mol L^?1, pH = 3) in the ratio of 8:92 (v/v). While the mobile phases for long side-chain monomers testing were composed of acetonitrile and phosphate buffer solution (0.05 mol L^?1, pH = 6.5) in the ratio of 40:60 (v/v). The linear response ranged from 4.0 × 10^?6?C2.0 × 10^?3 mol L^?1. The detection limit was 0.12 × 10^?5?C0.8 × 10^?5 mol L^?1. Determination of real samples showed that relative standard deviation of high conversion rate samples was 3.1?C8.7% and standard addition recovery ratio was 91.5?C102.8%. While the relative standard deviation of low conversion rate samples was less than or close to 1% and the standard addition recovery ratio was 96.3?C103.1%.     

The role of counter-anions in photocatalytic reduction of Ni(II) with a trace amount of titania nanoparticles

The reduction of Ni(II) ion, originated from nitrate or sulfate salts, was investigated based on photo-generated electrons in UV-irradiated TiO₂ aqueous suspensions. Design of experiments, modeling, and process optimization were performed using central composite design of response surface methodology. Influence of pH, temperature, and nickel concentration was investigated based on percentage of reduction efficiency (RE). Under operating conditions of pH = 9.3, T = 40 °C, [Ni(II)]_o = 5 mg L^?1, [TiO₂] = 100 mg L^?1 and after 90 min treatments, 64.8 and 76.1 % RE were achieved for nitrate and sulfate counter-anions, respectively. The higher efficiency obtained with sulfate anion was attributed to the more ionic strength and its interaction with titania nanoparticles. Rate of Ni(II) ions reduction, originated from both of the nickel salts, obeys pseudo-first-order kinetic model. As a relevant criterion, the electrical energy consumption and other criteria were evaluated and were compared with other previously reported processes.     

A Simple Method for Determination of Homologue Imidazolium Cations in Ionic Liquids Using IC with Direct Conductivity Detection

An investigation was carried out into the fast determination of five homologue imidazolium cations in ionic liquids by ion chromatography using a cation-exchange column and direct conductivity detection. Ethylenediamine, complex organic acid (citric acid, oxalic acid and tartaric acid) and organic modifiers (acetonitrile) were used as mobile phase. The influences of the eluent types, eluent concentration, eluent pH and column temperature on separation of the cations were discussed. Simultaneous separation and determination of the five homologue imidazolium cations in ionic liquids were achieved under an optimum condition. The optimized mobile phase was consisted of 0.25 mmol L^?1 ethylenediamine + 0.5 mmol L^?1 citric acid + 3% acetonitrile (v/v) (pH 4.1), set at a flow rate of 1.0 mL min^?1. The column temperature was 40 °C and detection limits were obtained in the range of 1.1–45.6 mg L^?1. The relative standard deviations of the chromatographic peak areas for the cations were <3.0% (n = 5). This method was successfully applied to separate imidazolium cations in ionic liquids produced by organic synthesis. The recoveries of spiked components were 92.5–101.9%.     

Synthesis and characterisation of novel chelating resin for selective preconcentration and trace determination of Pb(II) ions in aqueous samples by innovative microsample injection system coupled flame atomic absorption spectrometry

Expanded polystyrene (EPS) foam waste (white pollutant) was utilised for the synthesis of novel chelating resin i.e. EPS-N = N-α-Benzoin oxime (EPS-N = N-Box). The synthesised resin was characterised by FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis. A selective method for the preconcentration of Pb(II) ions on EPS-N = N-Box resin packed in mini-column was developed. The sorbed Pb(II) ions were eluted with 5.0 mL of 2.0 mol L^?1 HCl and determined by microsample injection system coupled flame atomic absorption spectrometry (MIS-FAAS). The average recovery of Pb(II) ions was achieved 95.5% at optimum parameters such as pH 7, resin amount 400 mg, flow rates 1.0 mL min^?1 (of eluent) and3.0 mL min^?1 (of sample solution). The total saturation capacity of the resin, limit of detection (LOD) and limit of quantification (LOQ) of Pb(II) ions were found to be 30 mg g^?1, 0.033 μg L^?1 and 0.107 μg L^?1, respectively with preconcentration factor of 300. The accuracy, selectivity and validation of the method was checked by analysis of sea water (BCR-403), wastewater (BCR-715) and Tibet soil (NCS DC-78302) as certified reference materials (CRMs). The proposed method was applied successfully for the trace determination of Pb(II) ions in aqueous samples.     

Electrooxidation of trifloxystrobin at the boron-doped diamond electrode: electrochemical mechanism,quantitative determination and degradation studies

The boron-doped diamond (BDD) presents attractive electrochemical sensing characteristics that are useful in analytical applications based on voltammetry and amperometry. It has a wide potential window in aqueous solutions enabling the quantification of the fungicide trifloxystrobin, measured at +1744 mV (versus Ag/AgCl), by square-wave anodic voltammetry in a Britton–Robinson (BR) buffer (0.04 mol L^?1; pH 4.00)/acetonitrile 70/30% v/v. The activation of the electrode was made using galvanostatic chronopotentiometry and cyclic voltammetry (CV). The linear analyte addition curve, I_p (µA) = (1.0 × 10^–1 ± 4.8 × 10^–6) C (mol L^?1) + (8.8 × 10^–2 ± 1.1 × 10^–3); R² = 0.997, was obtained using amplitude of 40 mV, frequency of 30 Hz, step potential of 20 mV. The instrumental limit of detection (LOD) was 1.4 × 10^–7 mol L^?1 (0.058 mg L^?1) and the dynamic linear range covered three decades (up to 1 × 10^–5 mol L^?1 or 4.1 mg L^?1). The samples were analysed with recoveries about 80% in orange juice samples and from 92.4% to 104.0% in water samples. A study to evaluate potential interferences was made in the presence of other fungicides. Diagnostic studies indicated that oxidation of trifloxystrobin in aqueous medium at the surface of the BDD is irreversible, involving two steps, each one with two electrons. The UV degradation of trifloxystrobin was evaluated using the proposed electrochemical method and the kinetics of degradation established with half-life of 1.07 min.     

Quantitative Analysis of Genistein in Human Plasma by Online Concentration CE with UV Detection

A rapid capillary electrophoresis method based on online acid barrage stacking has been successfully established for analysis of trace amounts of genistein in human plasma. Genistein was analyzed within 8 min, with 200 mmol L^?1 citric acid (pH 1.7) as acid barrage, and injection times of 180 and 30 s for sample and acid, respectively. Good linearity was obtained in the range 0.05–5 mg L^?1 and the limit of detection was 0.03 mg L^?1. Compared with normal sample injection, this method resulted in more than a fiftyfold improvement in detection sensitivity. The technique has potential for use in studies of genistein metabolism and of exposure levels in humans.