Determination of the Pesticides MCPA, 2,4,5-T,and 2,4,5-T-Isopropyl Ester by Low Temperature Phosphorimetry

Abstract

Sensitive low temperature phosphorimetric methods for the determination of the pesticides MCPA, 2,4,5-T, and 2,4,5-T-isopropyl ester in EPA solvent have been developed. The minimum detectable amounts are 0.1 p.p.m. for both 2,4,5-T formulations and 0.2 p.p.m. for MCPA. The ranges in linearity of the analytical calibration graphs are 0.2–60, 0.5–60, and 0.5–50 p.p.m. for 2,4,5-T, 2,4,5-T-isopropyl ester, and MCPA respectively. The procedure for 2,4,5-T has been applied to the analysis of a solid commercial formulation.     

Determination of Alachlor in food products by a fluorescence polarization immunoassay

A procedure for the determination of Alachlor in liquid media using a fluorescence polarization immunoassay (FPIA) was developed. The effects of the structure and purification degree of a tracer (analyte with a fluorescent label) on the analytical signals, sensitivity, and selectivity in the determination of Alachlor were studied. The tracer-antibody binding constants (K _T) and antigen-antibody binding constants (affinity constants K _Af) were calculated, and optimum immunoreagent pairs for the determination of Alachlor were chosen. The calibration graph was linear over the Alachlor concentration range 0.01–1.0 μg/mL; the detection limit was 8 ng/mL. The procedure was tested in the analysis of model solutions and soy-containing food products (sausages). Original Russian Text ? Yu.V. Nartova, T.N. Ermolaeva, M.R. Fleisher, R. Abuknesha, S.A. Eremin, 2008, published in Zhurnal Analiticheskoi Khimii, 2008, Vol. 63, No. 5, pp. 546–552.     

Genetic Algorithm Applied to Selection of Wavelength in Partial Least Squares for Simultaneous Spectrophotometric Determination of Nitrophenol Isomers

Abstract

Ternary mixtures of nitrophenol isomers have been simultaneously determined in synthetic and real matrix by application of genetic algorithm and partial least squares model. All factors affecting the sensitivity were optimized and the linear dynamic range for determination of nitrophenol isomers found. The simultaneous determination of nitrophenol mixtures by using spectrophotometric methods is a difficult problem, due to spectral interferences. The partial least squares modeling was used for the multivariate calibration of the spectrophotometric data. A genetic algorithm is a suitable method for selecting wavelength for PLS calibration of mixtures with almost identical spectra without loss prediction capacity. The experimental calibration matrix was designed by measuring the absorbance over the range 300–520 nm for 21 samples of 1–20 µg mL^?1, 1–20 µg mL^?1, and 1–10 µg mL^?1 of m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol, respectively. The root mean square error of prediction for m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol with genetic algorithms and without genetic algorithms were 0.3732, 0.5997, 0.3181 and 0.7309, 0.9961, 1.0055, respectively. The proposed method was successfully applied for the determination of m‐nitrophenol, o‐nitrophenol, and p‐nitrophenol in synthetic and water samples.     

Determination of the pesticides Chlorpropham,Propham, Propoxur,and Terbucarb by low temperature phosphorimetry

Summary Simple, direct, and sensitive low temperature phosphorimetric methods for the determination of Chlorpropham, Propham, Propoxur, and Terbucarb in EPA solvent are described. The minimum detectable amounts are 0.01 p. p. m. for Chlorpropham and Propham and 0.02 and 0.3 p. p. m. for Propoxur and Terbucarb respectively. The ranges of linearity of the analytical calibration graphs are 0.05-7.5, 0.05–10, 0.5–50, and 1–50 p. p. m. for Chlorpropham, Propham, Propoxur, and Terbucarb respectively. The procedure for Chlorpropham has been applied to the analysis of a solid commercial formulation.

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Bestimmung der Pesticide Chlorpropham, Propham, Propoxur und Terbucarb bei Tief-Temperatur-Phosphorimetrie

Zusammenfassung Einfache, direkte und empfindliche Methoden für die Bestimmung der genannten Pesticide in dem Lösungsmittel Diethylether-i-Pentan-abs. Ethanol wurden beschrieben. Die geringsten nachweisbaren Mengen sind 0,01 ppm für Chlorpropham und Propham sowie 0,02 und 0,3 ppm für Propoxur und Terbucarb. Die Eichkurven verlaufen zwischen 0,05 und 7,5, 0,05 und 10, 0,5 und 50 sowie zwischen 1 und 50 ppm für Chlorpropham, Propham, Propoxur bzw. Terbucarb linear. Das Verfahren für Chlorpropham wurde zur Analyse eines festen Handelsproduktes angewendet.

     

Glutathione Amperometric Enzyme Microsensor

Abstract

Glutathione micro-enzyme sensors were developed based on the immobilization of glutathione oxidase at the tip of a 25 μm Pt wire sealed in glass. An inner membrane constructed from cellulose acetate (CA) was deposited onto the tip of the Pt microelectrode prior to enzyme immobilization with glutaraldehyde. The final outer diameter of the microelectrodes is approximately 30 μm. The analytical characteristics of the microelectrodes, including calibration curves, apparent K_M′, pH response curves, stability and selectivity over enzymatic interferences were determined. The response was linear in the concentration range 1.0 × 10^?5 M - 1.9 × 10^?4 M glutathione, reaching 95% steady-state current in 15–20 seconds. The microelectrodes were useful for more than two months.     

Determination of the pesticides monuron,diuron, and fenuron by low temperature phosphorimetry

Summary Simple, direct, and sensitive low temperature phosphorimetric methods for the determination of monuron, diuron, and fenuron in EPA solvent are described. The minimum detectable amounts are 0.2, 0.1, and 0.02 p. p. m. for monuron, diuron, and fenuron respectively. The ranges in linearity of the analytical calibration graphs are 0.2–10, 0.1–7.5, and 0.1–20 p. p. m. for monuron, diuron, and fenuron respectively. The procedure for monuron has been applied to the analysis of a solid commercial formulation.

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Bestimmung der Pestizide Monuron, Diuron und Fenuron durch Messung der Chemilumineszenz bei tiefer Temperatur

Zusammenfassung Die Messung der Chemilumineszenz bei tiefer Temperatur ist ein einfaches, direktes und empfindliches Verfahren zur Bestimmung der Pestizide Monuron, Diuron und Fenuron in EPA-Lösung (DiethyletherIsopentan absol. Alkohol, 522). Die erfaßbaren Mindestmengen sind 0,2, 0,1 bzw. 0,02 ppm. Die Eichkurven sind zwischen 0,2 und 10, 0,1 und 7,5 bzw. zwischen 0,1 und 20 ppm geradlinig. Das Verfahren wurde zur Analyse von Monuron in einem festen Handelsprodukt verwendet.

     

Highly sensitive chemiluminescence flow sensor for ascorbic acid

A highly sensitive chemiluminescence(CL) flow sensor is proposed for the determination of ascorbic acid. The analytical reagents luminol and iron(II) are immobilized on anion-exchange and cation-exchange resins, respectively, and can be eluted by sodium sulphate. The calibration graphs are linear in the range 1 × 10^–9 to 1 × 10^–6 g mL^–1 and the detection limit is 4.0 × 10^–10 g mL^–1. The sensor has been applied successfully to the determination of ascorbic acid in vegetables.     

A novel,rapid and sensitive UPLC–MS/MS method for the determination of macitentan in patients with pulmonary arterial hypertension

Macitentan is an endothelin receptor antagonist commonly used in the treatment of pulmonary arterial hypertension (PAH). A novel, rapid, simple and sensitive UPLC–MS/MS method was developed and validated for pharmacokinetic study and the determination of macitentan in PAH patients. Macitentan and bosentan, which are used as internal standards, were detected using atmospheric pressure chemical ionization in positive ion and multiple reaction monitoring mode by monitoring the mass transitions m/z 589.1 → 203.3 and 552.6 → 311.5, respectively. Chromatographic separation was performed on a reverse‐phase C18 column (5 μm, 4.6 × 150 mm) with an isocratic mobile phase, which consisted of water containing 0.2% acetic acid–acetonitrile (90:10, v/v) at a flow rate of 1 mL/min. Retention times were 1.97 and 1.72 min for macitentan and IS, respectively. The calibration curve with high correlation coefficient (0.9996) was linear in the range 1–500 ng/mL. The lower limit of quantitation and average recovery values were determined as 1 ng/mL and 89.8%, respectively. This method is the first UPLC–MS/MS method developed and validated for the determination of macitentan from human plasma. The developed analytical method was fully validated for linearity, selectivity, specificity, accuracy, precision, sensitivity, stability, matrix effect and recovery according to US Food and Drug Administration guidelines. The developed method was applied successfully for pharmacokinetic study and the determination of macitentan in PAH patients.     

Determination of paeoniflorin,calycosin‐7‐O‐β‐d‐glucoside,ononin, calycosin and formononetin in rat plasma after oral administration of Buyang Huanwu decoction for their pharmacokinetic study by liquid chromatography–mass spectrometry

The purpose of this study was to simultaneously investigate the pharmacokinetics of five bioactive compounds in rat plasma after oral administration of Buyang Huanwu decoction (BYHWD) using high‐performance liquid chromatography coupled with mass spectrometry (HPLC‐MS). The separations were performed on a Thermo Hypersil Gold C₁₈ analytical column (50 × 2.1 mm, 3 µm) with the column temperature kept at 30°C. The quantitative analysis was performed using a quadrupole mass spectrometer detector operated under selected ion monitoring mode. A linear gradient elution of A (0.1% formic acid solution) and B (100% acetonitrile) was used at a flow rate of 0.2 mL/min. The method was validated within the concentration ranges 1.8–450, 6.0–1500, 2.0–500, 1.2–300 and 1.2–150 ng/mL for paeoniflorin, calycosin‐7‐O‐β‐d ‐glucoside, ononin, calycosin and formononetin, respectively. The calibration curves were linear with correlation coefficients > 0.99. The lower limits of quantitations were < 6.0 ng/mL. The method was further applied to assess the pharmacokinetics of the five bioactive constituents of BYHWD in rat plasma. Copyright © 2010 John Wiley & Sons, Ltd.     

Adsorptive stripping voltammetry of bovine serum albumin

The behaviour of bovine serum albumin in cyclic voltammetry and differential-pulse adsorptive stripping voltammetry is described. Under the optimized conditions, with an accumulation potential of +0.15 V (vs. Ag/AgCl) and accumulation times of 50 s or 120 s, linear calibration graphs were obtained for 1.0–4.0×10^?8 M BSA and 0.2–1.5×10^?8 M BSA, respectively.     

Voltammetric Behavior and Determination of Cinnarizine in Pharmaceutical Formulations and Serum

Abstract

The electrochemical reduction of cinnarizine was investigated by cyclic and linear sweep adsorptive voltammetry at glassy carbon electrode in Britton-Robinson buffers over the pH range 2.5–11.5. For analytical purposes, a well-defined adsorption-controlled cathodic peak was obtained at pH 2.5. By cathodic adsorptive linear sweep voltammetry, a linear calibration plot was obtained in the range of 2.0 × 10^?7 to 5.0 × 10^?6 mol L^?1 with detection limit of 9.0 × 10^?9 mol L^?1. The method was successfully applied to the determination of cinnarizine in commercial formulations with mean recovery and relative standard deviation of 100.24% and 1.46, respectively. The proposed method was also applied for drug determination in spiked serum samples by applying the standard addition method with a mean recovery of 97.80% and standard deviation of 3.06.     

Application of a liquid chromatography–tandem mass spectrometry method to the pharmacokinetics,tissue distribution and excretion in the study of anemoside B4, a novel antiviral agent candidate,in rats

A simple, sensitive and reliable LC–MS/MS method was developed and validated for the quantification of anemoside B4, a potential antiviral constituent isolated from Pulsatilla chinensis in rat plasma, tissue, bile, urine and feces. All biological samples were prepared by protein precipitation method, and ginsenoside‐Rg1 was chosen as the internal standard (IS). The analyte and IS were separated using a C₁₈ column (2.1 × 50 mm, 1.8 μm) and a mobile phase consisting of 0.1% formic acid in water (v /v) and acetonitrile running at a flow rate of 0.2 mL/min for 5 min. The multiple reaction monitoring transitions were monitored at m /z 1219.5–749.5 for anemoside B4 and 845.4–637.4 for ginsenoside‐Rg1 in electrospray ionization negative mode. The calibration curve was linear in the range of 10–2000 ng/mL for all biological matrices with a lower limit of quantification of 10 ng/mL. The validated method was successfully applied to a pharmacokinetics, tissue distribution and excretion study. These preclinical data will be beneficial for further development of anemoside B4 in future studies.     

Determination of copper,nickel, manganese and cadmium ions in aqueous samples by flame atomic absorption spectrometry after simultaneous coprecipitation with Co(OH)2

A separation-preconcentration procedure was developed for the determination of trace amounts of copper, nickel, manganese and cadmium ions in water samples by flame atomic absorption spectrometry after coprecipitation by Co(OH)₂ as a carrier without a chelating agent. The influence of the various analytical parameters such as pH, amount of carrier reagent, standing time, centrifugation rate and time, sample volume and matrix effects on the recovery of the analyte ions was studied. Under the specified experimental conditions the calibration curves for Ni(II) and Cu(II) were linear from 0.5 to 200 ng mL^?1 and for Mn(II) and Cd(II) from 0.5 to 250 and 0.3 to 80 ng mL^?1, respectively. The relative standard deviations for seven replicate determinations of a mixture of 40.0 ng mL^?1 of Cu(II), Ni(II), Mn(II) and 20 ng mL^?1 of Cd(II) in the original solution were 1.9%, 1.7%, 1.8% and 2.1%, respectively. The detection limits based on 3S_b/m for Cu(II), Ni(II), Mn(II) and Cd(II) in the original solution were 0.2, 0.2, 0.3 and 0.07 ng mL^?1, respectively. The limits of quantification based on 10S_b/m for Cu(II), Ni(II), Mn(II) and Cd(II) in the original solution were 6.7, 6.7, 10.0 and 2.3 ng mL^?1, respectively. The proposed method has been applied to the determination of trace amounts of the analyte ions in two certified reference materials (the National Institute for Environment Studies (NIES) No. 1 Pepperbush and NIES No. 7 Tea Leaves) and water samples and satisfactory results were obtained.     

Resolution of Ternary and Quaternary Mixtures of Drugs in Pharmaceutical Preparations by Use of Spectrophotometric Data in Conjunction with PLS-1 and PLS-2 Data Processing Methods

Abstract

Two variants of partial least-squares methodology (PLS-1 and PLS-2) have been used for the analysis of ternary and quaternary mixtures of acetaminophen-acetylsalicylic acid-codeine and caffeine, respectively. This methodology permits the simultaneous quantification of the aforementioned drugs even with closely overlapping spectral bands without any separation step. The concentration ranges are 4.0–12.0, 0.2–1.0 and 4.0–12.0 μg·ml^?1 for acetaminophen-acetylsalicylic acid-codeine and 10.0–20.0, 6.0–16.0, 1.0–5.0 and 0.2–1.0 μg·ml^?1 for acetaminophen-acetylsalicylic acid-caffeine and codeine, respectively. A systematic study of the experimental data by applying an exhaustive statistical analysis to demostrate the validity of the proposed methods is presented. The results of the determination of these drugs in pharmaceutical preparations are also presented. The analytical results were quite good in all cases.     

Simultaneous spectrophotometric determination of La, Ho, Mn 5-Br-PADAP complexes using multivariate calibration with partial least-squares (PLS) data evaluation

A simple and fast analytical pocedure is proposed for the simultaneous spectrophotometric determination of lanthanum, holmium and manganese in synthetic ceramics, (La_(0.8–x) Ho_x Sr_0.2 MnO₃), by using the partial least-squares (PLS) method. As chromogenic agent 5-Br-PADAP [2-(5-bromo-2-pyridylazo)-5-diethylaminophenol] was used, which form colored complexes with the three elements studied. To avoid metal hydrolysis, a mixture ¶of ethanol and Triton X-100 at pH 9.5 was used for all ¶experiments. A set of 17 calibration solutions measured throughout the 400–700 nm wavelength range was used in the calibration step. The concentration range for Mn(II) was 1–12 × 10^–6 mol L^–1, while the range for the rare earth elements La(III) and Ho(III) was 2–8 × 10^–6 mol L^–1. In order to demonstrate the applicability of the proposed method, a set of artificial samples containing the three analytes in variable proportions was prepared and analyzed. The analytical results obtained were quite acceptable with relative errors not greater than 7% in most cases.     

Derivative Spectrophotometric Determination of Copper and Palladium Simultaneously by Using MDTC as a Reagent

Abstract

A selective, sensitive, and economical derivative spectrophotometric method has been developed for the determination of trace amount of Cu(II) and Pd(II) with MDTC as a reagent in the presence of CTAB, a solubilizing agent. The molar absorption coefficient and analytical sensitivities of the 1:2 Cu(MDTC)₂ and Pd(MDTC)₂ complexes are 2.467×10⁴ and 2.989×10⁴ l mol^?1, respectively. The developed derivative procedure, is applied for the rapid and selective simultaneous determination of Cu(II) and Pd(II) in the range of 0.2–15 and 0.1–10 µg/ml, respectively. Complex matrices, including alloys, biological samples, pharmaceutical samples and synthetic mixtures have been successfully analyzed for trace amounts of two metal ions.     

Development of a targeted method for quantification of gypenoside XLIX in rat plasma,using SPE and LC–MS/MS

A sensitive, selective and rapid liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was developed for the quantification of gypenoside XLIX, a naturally occurring gypenoside of Gynostemma pentaphyllum in rat plasma and then validated according to the US Food and Drug Administration's Guidance for Industry: Bioanalytical Method Validation . Plasma samples were prepared by a simple solid‐phase extraction. Separation was performed on a Waters XBridgeTM BEH C₁₈ chromatography column (4.6 × 50 mm, 2.5 μm) using a mobile phase of acetonitrile and water (62.5:37.5, v /v). Gypenoside XLIX and the internal standard gypenoside A were detected in the negative ion mode using selection reaction monitoring of the transitions at m/z 1045.6 → 913.5 and 897.5 → 765.4, respectively. The calibration curve was linear (R ² > 0.990) over a concentration range of 10–7500 ng/mL with the lower quantification limit of 10 ng/mL. Intra‐ and inter‐day precision was within 8.6% and accuracy was ≤10.2%. Stability results proved that gypenoside XLIX and the IS remained stable throughout the analytical procedure. The validated LC–MS/MS method was then applied to analyze the pharmacokinetics of gypenoside XLIX after intravenous administration to rats (1.0, 2.0 and 4.0 mg/kg).     

Poly (Vinyl Chloride) Matrix Membrane Electrodes Responsive to Thiocyanate,Perchlorate and Periodate

Abstract

Three types of PVC matrix membrane ion-selective electrodes (ISEs) are described. These are based on membranes containing nitron thiocyanate with 2-nitro-phenyl phenyl ether, 2-nitrophenyl phenyl ether alone and tetraphenylarsonium thiocyanate with 2-nitrophenyl octyl ether. Each type is conditioned and stored in 0.1M sodium thiocyanate. The first two electrodes have been evaluated for thiocyanate and perchlorate response and the best linear long range (linear range down to 2.5×10^?5M) response was obtained for perchlorate. The third electrode is suitable as a periodate ISE with linear calibration range down to 2×10^?4M. The plasticized (2-nitrophenyl phenyl ether) PVC electrode for thiocyanate and perchlorate had a much longer pH interference free range (1.5–12.5) than either of the other electrodes.     

LC–ESI–MS/MS determination of copanlisib,a novel PI3K inhibitor,in mouse plasma and its application to a pharmacokinetic study in mice

A sensitive, selective and rapid LC–ESI–MS/MS method has been developed and validated for the quantification of copanlisib in mouse plasma using enasidenib as an internal standard (IS) as per regulatory guideline. Copanlisib and the IS were extracted from mouse plasma using ethyl acetate as an extraction solvent and chromatographed using an isocratic mobile phase (0.2% formic acid–acetonitrile; 25:75, v/v) on a HyPURITY C₁₈ column. Copanlisib and the IS eluted at ~0.95 and 2.00 min, respectively. The MS/MS ion transitions monitored were m/z 481.1 → 360.1 and m/z 474.0 → 456.0 for copanlisib and the IS, respectively. The calibration range was 3.59–3588 ng/mL. The intra‐ and inter‐batch accuracy and precision (RE and RSD) across quality controls met the acceptance criteria. Stability studies showed that copanlisib was stable in mouse plasma for one month. This novel method has been applied to a pharmacokinetic study in mice.