A liquid chromatography with tandem mass spectrometry method to simultaneously determinate chlorpyrifos,imidacloprid and imidacloprid metabolites in wheat

A liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously determine chlorpyrifos, imidacloprid, and imidacloprid metabolites in soil, wheat grain, and wheat straw matrices. Satisfactory linearity (R² ≥ 0.9965) of the method was obtained for all analytes. The ranges of limits of detection and limits of quantification for seven analytes in three matrices were 0.17–66.7 and 0.5–200 μg/kg, respectively. Average recoveries were 72.85–81.25% for chlorpyrifos, 78.54–84.70% for imidacloprid, 73.83–81.03% for imidacloprid olefin, 71.47–80.61% for 5‐hydroxy imidacloprid, 71.79–81.32% for imidacloprid urea, 70.42–82.20% for imidacloprid nitroguanidine, and 70.91–82.46% for imidacloprid 6‐chloronicotinic acid in soil, wheat grain, and wheat straw. The intra‐ and interday relative standard deviations were less than 8%. The established method was successfully applied for the residual analysis of chlorpyrifos, imidacloprid, and imidacloprid metabolites in actual soil, wheat grain, and wheat straw samples. The results indicated that the established method could be used to detect trace amounts of chlorpyrifos, imidacloprid, and imidacloprid metabolites in wheat and that the method might be able to provide some data on the detection of these seven compounds in other crops.     

Disposable Screen‐Printed Edge Band Ultramicroelectrodes for Use as Nitric Oxide Gas Sensor in Designing an Easily Applicable Method for Real Sample Analysis of Nitrite with Superior Selectivity and Sensitivity

We report here an easily applicable method for the quantification of nitrite (NO₂^?) in real samples. This approach simplified the two steps of sample preparation and detection into a 2‐in‐1 single step process. Samples were digested in sulfuric acid and the as‐generated nitric oxide (NO) was detected by an electrochemical sensor in the gas phase. It eliminated almost all of the interferents in the solution phase and hence resulted in a highly selective determination of nitrite suitable for food samples with complicated matrix. We successfully demonstrated the determination of nitrite in sausage and vegetables and further validated the results with an AOAC official reference method.     

Hadamard transform CE-UV detection for biological samples

A Hadamard transform-capillary electrophoresis-UV (HT-CE-UV) detection technique is described for the analysis of biological samples. Pseudorandom injections of sample and buffer according to a simplex matrix obtained from the corresponding Hadamard matrix is performed with conventional capillaries. Alternating injections are achieved with a novel capillary "T" connector created by drilling conventional capillary dimensions through a 1-cm diameter polycarbonate disc. This connector design coupled with a switching system allows for rapid, electrokinetic injections of solution into alternating sample and buffer capillary arms for UV detection. The standard mixtures of nitric oxide (NO) metabolites, nitrite and nitrate, dissolved in physiological saline solution are injected into the separation capillary according to an 83-element injection sequence to obtain a signal-to-noise ratio (S/N) enhancement of ca. 4.5 over a single injection. Nitrite, being the less concentrated metabolite in NO detection and thereby more difficult to detect, was calibrated with the HT-CE-UV method and a limit of detection (LOD) of 0.56 microM was obtained. Rat blood plasma was analyzed with this detection system and demonstrated to be comparable with NO metabolite concentrations of previously published results. This HT-CE-UV method is described where a unique reservoir tube design that contains 8-microL standard nitrite sample volumes is placed over the end of the capillary arm to explore low volume limits for biological samples.     

Simultaneous determination of clozapine, clozapine N-oxide, N-desmethylclozapine, risperidone, and 9-hydroxyrisperidone in plasma by high performance liquid chromatography with ultraviolet detection

A simple high performance liquid chromatography techniques with ultraviolet detection (HPLC–UV) method is described for the simultaneous determination of clozapine (CZP), clozapine N-oxide (CNO), N-desmethylclozapine (NCZ), risperidone (RSP) and 9-hydroxyrisperidone (9-OHRSP) in human plasma. After extraction process, the analytes were separated on a C₁₈ column (150 mm×3.9 mm i.d.) by the mobile phase (methanol–water–dimethylamine, 60:40:0.04 (v:v:v)). Relative recoveries of five analytes were quantitative. The precision and accuracy of intra- and interday assays were all below 8.2% for R.S.D. and 5.6% for RE, respectively. Based on 1 ml of plasma, the limits of detection were 2.0 ng/ml for CZP, 0.2 ng/ml for CZP N-oxide, 1.0 ng/ml for NCZ, 1.0 ng/ml for RSP, and 0.5 ng/ml for 9-OHRSP (S/N=3). The calibration curves were linear (r≥0.988). This method was applied to therapeutic drug monitoring of schizophrenia patients receiving CZP or RSP therapy.     

Solubilisation and binding characteristics of a recombinant beta2-adrenergic receptor expressed in the membrane of Escherichia coli for the multianalyte detection of beta-agonists and antagonists residues in food-producing animals

The on-line incorporation of cloud point extraction (CPE) to flow injection analysis (FIA) was previously based on the use of a cotton-packed column to entrap the analyte-containing surfactant aggregates after salt-induced CPE, and then the preconcentrated analyte was eluted into a separate detection cell for subsequent chemiluminescence (CL) detection (via the peroxyoxalate CL reaction). In the work, the on-line CPE/FIA technique was improved by the following: (1) sample preconcentration and CL detection were both carried out directly inside the collection column, thus avoiding the decrease in detection sensitivity due to sample dispersion and dilution, and (2) CL detection was performed through the reaction between nitrite and hydrogen peroxide, which is compatible with aqueous samples and should allow for chemical excitation to occur more efficiently inside the collection column. In addition to more effective sample preconcentration, the CL detection of the entrapped analytes directly inside the collection column, i.e., a unique heterogeneous microenvironment in which analyte-containing surfactant aggregates were embedded within the densely packed filtering material, may also contribute to the overall increase in CL intensity (e.g., a CL enhancement factor of ca. 1000). Under optimum experimental conditions, the calibration curve was found to be linear for the CL detection of bilirubin (5 to 120 μg L⁻¹), the limit of detection (S/N = 3) was 1.8 μg L⁻¹, and the R.S.D. was ca. 2.6% (n = 30) for 20 μg L⁻¹ bilirubin. Good agreements were obtained for the determination of total bilirubin in certified reference human serum samples between the present approach and an established clinical method.     

Simple flow-injection system for the simultaneous determination of nitrite and nitrate in water samples

A novel spectrophotometric reaction system was developed for the determination of nitrite as well as nitrate in water samples, and was applied to a flow-injection analysis (FIA). The spectrophotometric flow-injection system coupled with a copperised cadmium reductor column was proposed. The detection was based on the nitrosation reaction between nitrite ion and phloroglucinol (1,3,5-trihydroxybenzene), a commercially available phenolic compound. Sample injected into a carrier stream was split into two streams at the Y-shaped connector. One of the streams merged directly and reacted with the reagent stream: nitrite ion in the samples was detected. The other stream was passed through the copperised cadmium reductor column, where the reduction of nitrate to nitrite occurred, and the sample zone was then mixed with the reagent stream and passed through the detector: the sum of nitrate and nitrite was detected. The optimised conditions allow a linear calibration range of 0.03–0.30 μg NO₂⁻-N ml⁻¹ and 0.10–1.00 μg NO₃⁻-N ml⁻¹. The detection limits for nitrite and nitrate, defined as three times the standard deviation of measured blanks are 2.9 ng NO₂⁻-N ml⁻¹ and 2.3 ng NO₃⁻-N ml⁻¹, respectively. Up to 20 samples can be analyzed per hour with a relative standard deviation of less than 1.5%. The proposed method could be applied successfully to the simultaneous determination of nitrite and nitrate in water samples.     

Flow analysis-vapor phase generation-Fourier transform infrared (FA-VPG-FTIR) spectrometric determination of nitrite

In this work, the coupling between flow analysis (FA)–vapor phase generation (VPG) and Fourier transform infrared spectrometry (FTIR) has been proposed as a novel and alternative strategy for the determination of nitrite. The analyte was transformed into the gaseous nitric oxide (NO) by on-line reaction with potassium iodide (KI) or ascorbic acid in acidic medium. The gaseous NO generated was transported by means of a N₂ gas carrier stream inside the IR gas cell and the corresponding FTIR spectrum was acquired in a continuous mode. The absorbance at 1876 cm⁻¹, corrected by a baseline established between 1879 and 1872 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. The effect of different spectroscopic and flow analysis experimental parameters, such as nominal resolution, number of scans, reducing agent and its concentration, acidic medium, reagents and sample flow rates, and the carrier gas flow rate on the analytical signal, and then in the figures of merit were initially evaluated by using a standard short path length (10 cm) IR gas cell. The optimization of the system was carried out by the univariate method. The main aims of this study were: (i) to investigate the on-line generation of gaseous nitric oxide in a continuous flow system, and (ii) the use of Fourier transform infrared spectrometry as an alternative and selective detector for the determination of nitrite. The proposed method was initially tested and applied for the determination of nitrite in samples with very high concentration of nitrite, such as frankfurters.     

Synthesis of Ag nanospheres particles in ethylene glycol by electrochemical-assisted polyol process

The synthesis of monodispersed Ag nanosphere particles from silver nitrite in ethylene glycol at room temperature essentially promoted with the use of an electrochemical method was demonstrated. Poly(N-vinylpyrrolidone) (PVP) behaves electrochemically stable and facilitates the formation of well-defined Ag nanospheres of average size in the range of 11 nm. Further characterization by high-resolution transmission electron microscopy (HRTEM) image and nano-beam electron diffraction (NBED) pattern indicate that the growth direction of Ag nanosphere particles is the 1 1 1 direction. The time evolution of absorption spectra by UV–Vis spectroscopy illustrates that silver nanoparticles in the electrolyte increase rapidly upon electrochemical process.     

Determination of telmisartan in human blood plasma: Part I: Immunoassay development

Telmisartan is an angiotensin II receptor antagonist and a known drug against high blood pressure. In this report, the development of a new and rapid analytical technique, an enzyme-linked immunosorbent assay (ELISA) for the determination of telmisartan in human blood plasma is described. The immunoassay is based on a conversion of 4-(N-methylhydrazino)-7-nitro-2,1,3-benzooxadiazole (MNBDH) to 4-(N-methylamino)-7-nitro-2,1,3-benzooxadiazole (MNBDA), which is detected by fluorescence spectroscopy. The limit of detection was 0.1 ng/mL, the limit of quantification was 0.3 ng/mL and the working range extended from 0.3 ng/mL to 300 ng/mL.     

Electrochemical determination of nitrite and nitrate by pneumatoamperometry

Nitrite in aqueous solution is reduced to nitric oxide with hydroquinone in pH 2 phosphate buffer. The nitric oxide is swept with nitrogen to an anodically polarized membrane-covered platinum electrode, where it is oxidized to nitrate. The resulting current is linearly related to nitrite concentration in the original solution from the detection limit of 18 nmol to 5 μmol of nitrite. Nitrate is subsequently determined similarly after reduction to nitric oxide with hydroquinone in 50% sulfuric acid containing ammonium molybdate catalyst. The linear range is from the detection limit of 40 nmol to 10 μmol of nitrate.     

Microbiosensor for acetylcholine and choline based on electropolymerization/sol–gel derived composite membrane

Amperometric enzyme biosensors for the determination of acetylcholine (ACh) and choline (Ch) have been described. For the fabrication of the biosensors, N-acetylaniline (nAN) was first electropolymerized on a Pt electrode surface to be served as a permselective layer to reject interferences. Bovine serum albumin (BSA) and choline oxidase (CHOD) were co-immobilized in a zinc oxide (ZnO) sol–gel membrane on the above modified Pt electrode for a Ch sensor, or CHOD, acetylcholinesterase (AChE) and BSA immobilized together for an ACh/Ch sensor. The poly (N-acetylaniline) (pnAN) film was the first time used for an ACh/Ch sensor and found to have excellent anti-interference ability, and the BSA in the sol–gel can improve the stability and activity of the enzymes. Amperometric detection of ACh and Ch were realized at an applied potential of +0.6 V versus SCE. The resulting sensors were characterized by fast response, expanded linear range and low interference from endogenous electroactive species. Temperature and pH dependence and stability of the sensor were investigated. The optimal ACh/Ch sensor gave a linear response range of 1.0 × 10⁻⁶ to 1.5 × 10⁻³ M to ACh with a detection limit (S/N = 3) of 6.0 × 10⁻⁷ M and a linear response range up to 1.6 × 10⁻³ M to Ch with a detection limit of 5.0 × 10⁻⁷ M. The biosensor demonstrated a 95% response within less than 10 s.     

Analysis of NO and its metabolites by mass spectrometry. Comment on 'Detection of nitric oxide in tissue samples by ESI-MS' by Z. Shen, A. Webster, K. J. Welham, C. E. Dyer, J. Greenman and S. J. Haswell

Recently, Shen et al. (Analyst, 2010, 135, 302) reported on a flow injection analysis (FIA) ESI-MS/MS approach for the determination of the short-lived gaseous nitric oxide (NO) in biological samples. This method is based on the reaction of NO, and presumably of other NO-derived oxides such as N(2)O(3), with the vicinal amino groups of methylpiperazinobenzendiamine to form a benzotriazole derivative. Under MS/MS conditions, the protonated derivative loses molecular nitrogen (N(2)) from the triazole ring and the product ion formed is utilized for quantitative analyses. This seems to be the first ESI-MS/MS method for authentic NO detection and quantification. However, the ESI-MS/MS method reported by Shen et al. deserves some critical discussion.     

Gluten determination by gliadin enzyme-linked immunosorbent assay kit: interlaboratory study

An interlaboratory study with 10 participants was performed to obtain validation and performance data for an enzyme-linked immunosorbent assay (ELISA) kit developed for quantitative gluten determination in foods. The ELISA kit used for this study is based on 2 monoclonal and 1 polyclonal antibody developed by Immunotech, a Beckman Coulter Co. This kit did not show any false positive results or cross-reactivity with oat, rice, maize, and buckwheat. The gliadin standard from the Working Group on Prolamin Analysis and Toxicity was included in the kit as reference material for calibration. All participants obtained a gliadin ELISA kit with Standard Operational Procedure and a form for recording test results. The study included 13 samples labeled as "gluten-free" and 2 samples spiked by wheat flour. Seven samples had gliadin content below the limit of quantitation (LOQ) of the method, and 1 sample exceeded the highest calibration level. Gliadin content in the range from 10 to 157 mg/kg (1st day) and from 11 to 183 mg/kg (2nd day) was found in 7 samples (including 2 spiked samples). Results of these samples were used for further statistical analysis and evaluation. The Cochran, Dixon, and Mandel statistical tests were applied for detection of outliers. The LOQ of the kit was estimated.     

A novel method for the spectrophotometric determination of nitrite in water

A rapid, simple, selective and sensitive method for the spectrophotometric determination of nitrite in water has been developed and optimum reaction conditions along with other analytical parameters have been evaluated. Nitrite reacts with barbituric acid in acidic solution to give the nitroso derivative, violuric acid. At analytical wavelength of 310 nm, Beer's law is obeyed over the concentration range 0.00–3.22 ppm of nitrite. The molar absorptivity is 15330 ± 259.7 (95%) with pooled standard deviation of 355.57 and R.S.D. of 2.32%. As well as the method is sensitive (2.99 × 10⁻³ μg NO₂ cm⁻²) and selective, it tolerates most of the potential interferents. It has been successfully applied to nitrite determination in natural waters by use of a calibration graph with determination limit of 1.66 μg NO₂ in 100 mL working solution corresponding to minimum 9.5 ppb NO₂–N in water samples. Lower concentrations of nitrite (3.0 μg NO₂/L sample) is precisely analyzed by using the method of dilution with sample, with R.S.D. of lower than 0.5%. The results were compared with standard N-(1-naphtyl)ethylenediamine dihydrochloride method and very good agreement between the data was observed. The method can easily be applied in the field.     

Dialysis membrane sampler for on-line flow injection analysis/chemiluminescence-detection of peroxynitrite in biological samples

Peroxynitrite, as a derivative of nitric oxide, is a potent oxidant. It reacts with several biological molecules, makes cellular and tissue damages, and is related with many diseases; therefore, it is of major concern in current medical research works. In this work, a special perm-selective cellulose acetate membrane sampler is used to implement flow injection analysis (FIA)/chemiluminscence (CL)-detection method for the detection of peroxynitrite with Luminol CL-reagent. Optimum detection conditions were established, and the permeability of peroxynitrite through cellulose acetate (CA) membrane, as well as the interference from matrix constituents were studied. The proposed method has the high sensitivity of the CL-detection and the selectivity of perm-selective membrane sampler. The obtained detection limit of 1×10⁻¹¹ M (without dialysis membrane) and 1×10⁻¹⁰ M (with dialysis membrane), makes it possible to monitor the elusive peroxynitrite in biological samples. The mechanism of luminol CL-emission generated during oxidation by peroxynitrite and the kinetics of peroxynitrite decomposition were also studied using FIA/CL-detection set-up.     

Pungency evaluation of onion cultivars from the Venezuelan West-Center region by flow injection analysis-UV-visible spectroscopy pyruvate determination

A flow injection analysis (FIA) method was developed for the determination of pyruvate in onion cultivars (Allium cepa L.) from the West-Center region of Venezuela. The reference Schwimmer and Weston (1961) (J. Agric. Food Chem. 9 (1961) 301) Batch method was modified and adapted to FIA conditions. The formation kinetic of the 2,4-dinitrophenylhydrazine (DNPH)–pyruvate complex was evaluated at room temperature and at 37 °C. It was demonstrated the suitability of the chromopher formation at room temperature. The optimal values for the FIA parameters were: sample injection volume 3 mL, flow rate 6 mL min⁻¹, reactor length 1.5 m, sodium hydroxide concentration 1.0 mol L⁻¹ and hydrochloric acid concentration 0.5 mol L⁻¹. The working calibration range was extended from 80 mg L⁻¹ (Batch method) to 700 mg L⁻¹ with the FIA set up. The sample dilution step is thus avoided, simplifying the whole analysis process. The pungency in representative samples of the cultivars Yellow granex 438, Ultra Hybrid and Red onion “Sangre de Toro” was evaluated by the flow injection analysis (FIA)–pyruvate method and the results were compared to the reference Batch pyruvate method and to the taste panel test. Non-significant differences were found at the 95% of confidence level between the FIA method and the Batch reference method. Correlation coefficient when comparing the FIA results to the taste panel test was r² = 0.8353. Significant differences (P < 0.05) were found in the pungency of the cultivars, the Ultra Hybrid having the highest pungency. The pungency order from minor to major was: Red onion, Texas Grano 438 and Ultra Hybrid.     

Selective and sensitive detection of nitrite based on NO sensing on a polymer-coated rotating disc electrode

A new effective way of nitrite detection in complex samples is presented. It is based on chemical conversion of nitrite to nitric monoxide (NO) in acidic aqueous solution containing hexacyanoferrate(II) as a reductor. NO is then detected on a poly-eugenol coated platinum electrode. When the electrode is rotating and the reduction medium is continuously purged with nitrogen, the addition of a nitrite-containing sample produces narrowed current spikes. The peak current is proportional to nitrite content in the sample over the range of 5.0–100 μM and detection limit is 0.6 μM. The method is simple and highly reproducible. Relative standard deviation of 10 repetitions is less than 4%. Practical utility of the proposed approach is demonstrated by nitrite determination in human saliva.     

Flow Injection Biamperometric Determination of Nitrite and Nitrate

Abstract

A simple and efficient FIA method was used with good results to determine nitrite in residual waters and nitrate in natural waters. Nitrite determination is based on the reaction with iodide occurring in acidic medium and biamperometric detection of the formed iodine at two platinum electrodes polarised at a potential of 100 mV. Nitrate is similarly determined after its previous reduction to nitrite in a cadmium column. The method does not need the solution deaeration. However, the calibration graphs present two regions of linearity owing to the catalytic effect of the dissolved oxygen on the iodide oxidation by nitrite.     

Development of Polarization Fluoroimmunoassay for the Detection of s-Triazine Herbicides

Abstract

A rapid, non-isotopic polarization fluoroimmunoassay (PFIA) for the monitoring of the simazine (striazine herbicide) level in water was developed. Polyclonal antiserum was raised in rabbits by immunization with simazine – Keyhole Limpet Haemocyanin conjugate. Sensitivity of the PFIA with the use of heterologous tracer with the shortest bridge between antigen and fluorescein proved to be the highest. All analytical criteria for PFIA were satisfied. The detection limit of simazine (3 ng/ml in 50 μl of sample) was comparable to that for liquid or gas chromatography method. The detection limit of ELISA using the same antiserum and conjugate derivative of atrazine with horseradish peroxidase was 0.1 ng/mL of simazine. The cross-reactivity for PFIA with widely used s-triazine herbicides: atrazine, propazine, terbuthylazine was 100%, 32% and 20%, respectively. The cross-reactivity for PFIA with some metabolites of s-triazines and other herbicides was negligible.     

Design of a flow injection method for chlorophyll determination in in vitro plants

A flow injection (FIA) method was designed for the determination of chlorophylls a and b in small in vitro Dieffenbachia maculata “Sublime” plants. In the first step, the pigments from spinach leaves were separated, purified by solvent extraction and freeze–dried, to obtain standards for the FIA optimization. The sample extraction procedure was optimized. Four solvents were tested: diethyl ether, methanol, acetone and ethanol. The ethanol 96% was the optimal solvent for FIA purposes. It allows to the efficient extraction of the pigments and water can be used as carrier. The best FIA conditions found for the quasi-simultaneous quantification of chlorophylls a and b were a flow rate of 10.84 mL min⁻¹, a sample injection volume of 1.45 mL and a reactor length of 63 cm. The detection was performed with the automatic wavelength scanning Cintra 10e spectrometer, at 649 and 665 nm. The results obtained by the FIA method were compared to those obtained by the Arnon method. A deviation less than 5% was found between results for both methods. The concentration (mg g⁻¹) of chlorophylls a and b during three periods of the plants (in vitro, acclimatization, and adult) was determined to evaluate the whole in vitro procedure. It was found an increment of both pigment concentrations since the in vitro step till the adult stage, while the chlorophylls a to b ratio decreases. The designed method is suitable especially for the determination of the pigments at low concentrations in small samples with appropriate analytical quality.