Adsorption of Lead Ion Using Polymer-Modified Wheat Straw Carboxymethylcellulose

The wheat straw carboxymethylcellulose (WSC), a typical natural polymer, was modified by functional poly(acrylic acid) (PAA) with in situ polymerization, which afforded natural and synthetic polymer composite (WSC/PAA). The polymer (WSC/PAA) was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis techniques. WSC/PAA was used as polymer adsorbent for removing Pb(II) ions in wastewater. The removal rate of 99.8% was obtained when the experimental conditions were chosen as follows: initial Pb(II) ion concentration; 600 mg/L, WSC/PAA concentration; 0.1 g/100 mL, pH; 5.0, contact time; 60 minutes at 20°C. Adsorption dynamics were consistent with pseudo-second-order kinetic model and the isotherm model can meet the Langmuir isotherm.     

Determination of Procymidone, Pentachloroaniline and Methyl-pentachloro-phenylsulfide Residues in Wine by MSPD-GC-ECD

A rapid method based on matrix solid-phase dispersion (MSPD) was developed for the determination of procymidone, pentachloroaniline and methyl-pentachloro-phenylsulfide in wine. After the optimisation of different parameters such as the type of adsorbent, the extraction solvent, and the extraction assistance by sonication. The analysis of samples was accomplished using gas chromatography with electron-capture detector (GC-ECD). Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. The recovery of the method was in the range 82.4–93.7% and a good linear relationship (R ² ≥ 0.9992) with relative standard deviations lower than 8%. The limits of detection (LOD) ranged from 0.1 to 0.4 μg L^?1. The proposed method was applied to the analysis of these compounds in commercial wine samples.     

Analysis of triallate residue and degradation rate in wheat and soil by liquid chromatography coupled to tandem mass spectroscopy detection with multi-walled carbon nanotubes

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method for the analysis of triallate residue in wheat and soil was developed and validated. Multi-walled carbon nanotubes were used as clean-up sorbent. The residual levels and dissipation rates of triallate in wheat and soil were determined by liquid chromatography–tandem mass spectrometry. The limit of quantification was established as 0.01, 0.02 and 0.05 mg kg^?1 for soil, wheat and wheat plant samples, respectively. The average recoveries of triallate ranged from 77% to 108% at fortified levels of 0.01–0.5 mg kg^?1 with relative standard deviations of 3.0–8.4% (n = 5). From residue trials at three geographical experimental plots in China, the results showed that the half-lives of triallate in soils were 1.13–1.63 days. For trials applied according to the label recommendation, the final residues of triallate in wheat at harvest time were all below 0.05 mg kg^?1 (the maximum residue levels of China, Japan, Korea and the US).     

An Improved UPLC Method for Rapid Analysis of Levofloxacin in Human Plasma

A rapid, specific, and sensitive ultra-performance liquid chromatographic method for analysis of levofloxacin in human plasma has been developed and validated. Plasma samples were spiked with the internal standard (enoxacin) and extracted with 10:1 (v/v) ethyl acetate–isopropanol. UPLC was performed on a 100 × 2.1 mm i.d., 1.7 µm particle, C₁₈ column with 88:12 (v/v) 0.4% triethylamine buffer (pH 3)–acetonitrile as mobile phase, pumped isocratically at a pressure of 11,000 psi (758 bar) and a flow-rate of 0.3 mL min^?1. Ultraviolet detection was performed at 300 nm. The retention times of levofloxacin and enoxacin were 3.4 and 2.8 min, respectively, and the run-time was 5 min. Calibration showed that response was a linear function of concentration over the range 0.05–10 µg mL^?1 (r ² ≥ 0.99) and the method was validated over this range for both precision and accuracy. The relative standard deviation was <15% for both intra-day and inter-day assay (n = 5). Levofloxacin and enoxacin were stable in plasma; there was no evidence of degradation during three freeze–thaw cycles, post-preparative stability at 20 °C was ≥24 h, short-term stability at room temperature was ≥6 h, and long-term stability at ?70 °C was ≥30 days. The method was successfully used in a study of the bioequivalence of two levofloxacin tablet formulations in healthy volunteers.     

Multivariate optimisation of a rapid and simple automated method for bismuth determination in well water samples exploiting long path length spectrophotometry

An automated spectrophotometric system is proposed for the determination of bismuth in well water samples, using multi-syringe flow injection analysis (MSFIA) and exploiting a liquid waveguide capillary cell (LWCC). This method is based on the colorimetric reaction of bismuth and methylthymol blue (MTB) in the presence of polyvinylpyrrolidone (PVP) in acid medium (0.1 mol L^?1 HNO₃). The Bi(III)–MTB complex was measured at 600 nm. The method was optimised by multivariate techniques. Some figures of merit of the proposed system are worth being highlighted, such as its wide linear working range (between 4.9 and 600 μg L^?1), its low detection limit (1.5 μg L^?1 of bismuth) and its high intra-day precision and inter-day precision (0.7% (n = 12) and 1.4% (n = 5), respectively, both expressed as RSD). Moreover, a high injection frequency of 30 h^?1 is achieved, as the proposed analyser is a powerful tool for fast Bi(III) determination. The method developed was successfully validated by analysing reference samples (pharmaceutical samples) by comparing the results with those obtained by ICP-OES and it was satisfactorily applied to well water samples. Besides, the present system is miniaturised allowing in situ measurements in control processes and field analysis.     

Prediction of Rheological and Chemical Properties of Different Starches Used in the Paper Industry by Near Infrared Spectroscopy (NIRS)

Starch is one of the most abundant biopolymers, consisting of the polysaccharides amylose and amylopectin and other minor but characteristic constituents depending on the origin. Potatoes, maize, wheat, rice and tapioca are the sources of commercial interest with a large variety of applications both in food and non food areas. The measurements of over hundred starch samples were accomplished over a range of 4000–10000 cm⁻¹ in diffuse reflectance and transmission mode. Quantitative prediction models, based on a partial least squares (PLS) algorithm for the determination of fat content, the main fatty acids, water content, tendency to retrogradation and viscosity were developed. All models are characterized by high correlation coefficients (R² > 0,98). Principal components analysis (PCA) was applied successfully to distinguish starches regarding their source, provenience and their degree of modification. Both quantitative and qualitative models are cross validated.     

Assay of actinides in human urine by rapid method

A method using DGA resin (N,N,N′,N′-tetra-n-octyldiglycolamide on an inert support) was developed for the rapid analysis of actinides in urine samples. Samples acidified with HCl to 4 M were loaded directly (without digestion) onto a DGA column. Actinides were stripped simultaneously, α-sources were prepared by co-precipitation with NdF₃. Americium, plutonium and uranium were separated with acceptable high recoveries (40–80%). The americium, plutonium and uranium content of 100–200 ml urine samples was determined within 24 h with detection limits as low as 0.01 Bq l^?1. Based on model experiments using ¹⁴C-spiked urea, it was proven that high urea content can affect americium separation deleteriously due to irreversible fixing of americium on DGA resin.     

Compositional analysis of Miscanthus giganteus by near infrared spectroscopy

Fourier transform near infrared spectroscopy was applied to ball-milled and dried whole plant Miscanthus × giganteus samples in combination with partial least square regression analysis for prediction of main constituents of the biomass. The developed models with 172 calibration samples had an R² in the range of 0.96–0.99. For the first time, the acetyl content was modeled for Miscanthus. An independent calibration set of 58 samples revealed a low root mean square error of prediction of 0.414 % for extractives, 0.485 % for glucan, 0.249 % for xylan, 0.061 % for arabinan, 0.050 % for acetyl, 0.198 % for Klason lignin, 0.226 % for total ash and 0.133 % for ash after extraction, an indication of a high level of accuracy. The results showed major improvement over previously reported models, which was attributed to the smaller particle size used. The models are a valuable tool for the fast monitoring of the composition of M. × giganteus in e.g. plant breeding studies.     

Complexation of Eu3+ with cone conformers of three substituted calix[4]arenes in nitrobenzene saturated with water

From extraction experiments and $ \gamma Accurate knowledge of the trace elemental concentrations in wheat and its products is of great importance from a nutritional point of view. In this study, six wheat samples were prepared from the agriculture research center of Arak named Sardari, Amir, MV-17, Batava, Karaj-2 and Alvand; they were analyzed by neutron activation method (NAA). In this method, Isfahan miniature reactor as a neutron source and relative NAA method has been used as the analysis type. In this design in order to record gamma spectrum the MCA system and high purity germanium detector were used. Finally, the concentration of the trace elements such as Br, K and Na value was determined for the Sardari, Amir, Alvand, MV-17, Batava, Karaj-2 wheat samples. The average concentration of trace elements in all wheat samples in the studied area are 2.41(0.8597?6.1175) mg kg^?1 for Br, 13.42(8.7063?24.696) mg kg^?1 for Na and 463.30(434.22?505.45) mg kg^?1 for K, respectively. These were compared with other reports results. This study has been conducted as the first time for this region.     

Tandem dispersive liquid–liquid microextraction coupled with micro-sampling flame atomic absorption spectrometry for rapid determination of lead(II) and cadmium(II) ions in environmental water samples

ABSTRACT

Tandem dispersive liquid liquid microextraction coupled with micro - sampling flame atomic absorption spectrometry for rapid determination of lead2 and cadmium2 ions in environmental water samples. A simple method termed as tandem dispersive liquid–liquid microextraction coupled with micro-sampling flame atomic absorption spectrometry is used for determination of the lead(II) and cadmium(II) ions in different environmental water samples. According to the proposed method, the target analytes are extracted from an aqueous sample solution (10 mL) into a micro-volume of an organic solvent, and then they are selectively back-extracted into an aqueous acceptor solution (150 μL) to increase the compatibility of the extractant phase with a final analyser system and provide a suitable enrichment factor. The developed method is very fast, implemented in just about 7 min, and provides a high sample clean-up. The factors influencing the extraction efficiency including the type and volume of the organic solvent, pH and volume of the acceptor solution, and number of extractions are thoroughly examined and optimised. Under the optimal experimental conditions, the developed method provides a good linearity (in the range of 0.4–300 ng mL^?1 (R² ≥ 0.994)), and low limits of detection (in the range of 0.07–0.31 ng mL^?1). Finally, the method is successfully applied for the direct determination of the understudied analytes in the river, dam, and well water samples.     

Determination of melatonin in bakery products using liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS)

Melatonin (N-acetyl-5-methoxytryptamine), the hormonal product of the pineal gland, has recently been reported as a multifaceted free radical scavenger and antioxidant. Melatonin production declines progressively with age. Therefore, supplemental administration or increased intake of melatonin from dietary sources may be beneficial in delaying age-related degenerative conditions. This study aimed to determine melatonin in commonly eaten bakery products based on wheat, rye or spelt flour formulations, which represented the most popular types of bread and roll in Europe. Melatonin was extracted from freeze-dried bread samples with methanol and its content was determined by micro-HPLC system coupled to triple quadrupole mass spectrometry (LC–MS/MS) of target analysis. Melatonin was identified in all types of bread and rolls, however, its content varied significantly, ranging from 0.26 ng/g to 3.21 ng/g of dry matter (DM). The best source of melatonin was mixed wheat-rye bread (average 3.02 ng/g DM) followed by rye bread (average 2.50 ng/g DM), whereas spelt bread, wheat and graham rolls were poor sources (below 0.54 ng/g DM). These findings may help consumers to select bread with high melatonin content. This study showed that micro-HPLC system coupled to triple quadrupole mass spectrometry can be successfully applied for the determination of melatonin in bakery products. Because of the relevance of melatonin as bioactive molecule with implications for food, nutritional sciences and human health, it was of interest to explore its levels in commonly daily taken bakery products.     

On-line Micro Solid-Phase Extraction of Clodinafop Propargyl from Water,Soil and Wheat Samples Using Electrospun Polyamide Nanofibers

An on-line extraction/determination set up was designed for micro solid-phase extraction of clodinafop propargyl from water, soil and wheat samples using electrospun polyamide nanofiber mats. The prepared mats were packed in a stainless steel tube which conveniently acted as a high-performance liquid chromatography injection loop. Influential parameters affecting the extraction efficiency were optimized using a distilled water sample fortified with 25 μg L^?1 of clodinafop propargyl. An enrichment factor of 440 was achieved for clodinafop propargyl indicating the ability of the whole procedure. Under the optimum conditions, the linearity for the analyte was in the range of 6–700 μg L^?1, while a limit of detection and limit of quantification of 2 and 6 μg L^?1 were achieved, respectively. The intra-day and inter-day RSD% at the concentration level of 25 μg L^?1 were 4.6 and 9.3 %, respectively. To investigate the matrix effect, the developed method was applied to the analysis of real water samples including paddy and river waters as well as the wheat and soil samples. The relative recovery percentages for the spiked samples were in the range of 63–95 %.     

Determination of europium(III) in environmental samples using a flow injection analysis system with on-line preconcentration and spectrophotometric detection

A simple and accurate flow injection analysis system coupled with spectrophotometric detector was developed for preconcentration and determination of europium(III) in aqueous samples. The developed flow system includes a europium preconcentration step in a column packed with Amberlite XAD-4 resin impregnated with nalidixic acid at pH 7.0. The europium complex was desorbed from the resin by 0.1 mol L^?1 HCl and mixed with arsenazo-III solution (0.05 % solution in 0.1 mol L^?1 HCl) and taken to the flow through cell of spectrophotometer where its absorbance was measured at 661 nm. The optimum preconcentration system, chemical and FIA variables were investigated. The preconcentration factors obtained were 115 and 500, detection limits of 0.43 and 0.1 μg L^?1, sample throughputs of 40 and 10 were obtained for preconcentration time of 60 and 300 s respectively. The proposed system showed good precision and accuracy with relative standard deviation of 1.5 %. The method has been applied to the determination of europium(III) in real water samples and certified reference material IAEA-SL-1 (Lake sediment).     

Simultaneous Determination of Sildenafil,Tadalafil, and Vardenafil in Pharmaceutical Preparations by High-Temperature Gas Chromatography/Mass Spectrometry

Sildenafil (SD), tadalafil (TD), and vardenafil (VD) are drugs used to treat erectile dysfunction (ED). Pharmaceutical counterfeiting-related SD, TD, and VD compounds are becoming a critical problem due to their harmful side-effects. Especially, SD and TD are two major counterfeit ED drugs in South Korea. In this study, a new high-temperature gas chromatography/mass spectrometry (HTGC/MS) method was developed for the rapid determination of SD, TD, and VD in pharmaceutical preparations. A HT GC column was introduced for the rapid analysis of high molecular weight and high boiling point compounds. High-speed centrifugation led to shortened time for results. Calibration curves were linear (R ² ≥ 0.9972) over the concentration ranges of 12.5–100 µg mg⁻¹ for TD and VD, and 25–175 µg mg⁻¹ for SD. The intra- and inter-day precisions were within 7.5 %, while the intra- and inter-day accuracies ranged from –3.0 to 8.0 %. The limits of quantification were 0.7 µg mg⁻¹ (SD and TD) and 0.13 µg mg⁻¹ (VD). The recoveries were in the range of 87.3–102.4 %. The developed method was rapid and accurate both for routine quantitative measurement of SD, TD, and VD in pharmaceutical preparations as well as screening their suspected counterfeit compounds.

     

Development of carbon paste electrode modified with cadmium ion-imprinted polymer for selective voltammetric determination of Cd2+

A simple and fast voltammetric method based on a new electrode composed of carbon paste electrode/bifunctional hybrid ion imprinted polymer (CPE/IIP) was developed for the quantification of Cd²⁺ in water samples. The voltammetric measurements by Differential Pulse Voltammetry were performed by using CPE containing 11.0 mg of IIP under phosphate buffer solution at concentration 0.1 mol L^?1 and pH 6.5. The electrochemical method was carried out by Cd²⁺ preconcentration at ?1.2 V during 210 s, followed by anodic stripping. The performance of IIP towards Cd²⁺ determination was evaluated by comparison to non-imprinted polymer, whose detectability of IIP was much higher (45%). The sensitivity of the sensor was found to be 0.0105 µA/µg L^?1. The limits of detection and limits of quantification were found to be 4.95 μg L^?1 and 16.4 μg L^?1, respectively. The developed method was successfully applied to Cd²⁺ determination in mineral, tap and lake water samples, whose results are in agreement with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) used as reference analytical technique. According to achieved results, the developed method can be used for routine analysis of quality control of water samples from different sources.     

Analysis of Pterins in Urine by HILIC

Pterins are a class of compounds excreted in urine. Levels of the pterins are found to be significantly elevated in a variety of diseases. A new method involving hydrophilic interaction chromatography with fluorescence detection has been developed for analysis of neopterin, biopterin, and isoxanthopterin in urine samples. Separation of these pterins on an aminopropyl hydrophilic interaction column was achieved by isocratic elution. The effects of the organic modifier content, ionic strength, and pH of the mobile phase on the hydrophilic behavior of the pterins were studied and the mechanism of their separation was also investigated. Under the optimum chromatographic conditions the linearity (r ≥ 0.9995) and repeatability (relative standard deviation < 4.0%) of the method are good. Compared with reversed-phase high-performance liquid chromatography, the method is simple and convenient. The method was applied to the analysis of pterins in urine samples with satisfactory results.     

Development and Validation of LC-UV for Simultaneous Estimation of Rosiglitazone and Glimepride in Human Plasma

A simple, sensitive and specific liquid chromatographic method with UV detection (228 nm) was developed for the simultaneous estimation of rosiglitazone and glimepride in human plasma. Rosiglitazone and glimepride were extracted from plasma using liquid–liquid extraction. Separation was achieved with an RP C₁₈ Column using a mixture of phosphate buffer (50 mM) with octane sulfonic acid (10 mM), methanol and acetonitrile as a mobile phase (55:10:35, v/v). pH was adjusted to 7.0. Amlodipine was used as an internal standard (IS). LOD of the method was found to be 20 ng mL^?1 for both drugs. Results were linear over the studied range 40.994–2007.556 ng mL^?1 for rosiglitazone (r ² ≥ 0.99) and 41.066–2094.84 ng mL^?1 for glimepride( r ² ≥ 0.99). The method was found to be simple, selective, precise and reproducible for the estimation of both drugs from spiked human plasma.     

Development and Validation of LC-UV for Simultaneous Estimation of Rosiglitazone and Glimepride in Human Plasma

A simple, sensitive and specific liquid chromatographic method with UV detection (228 nm) was developed for the simultaneous estimation of rosiglitazone and glimepride in human plasma. Rosiglitazone and glimepride were extracted from plasma using liquid–liquid extraction. Separation was achieved with an RP C₁₈ Column using a mixture of phosphate buffer (50 mM) with octane sulfonic acid (10 mM), methanol and acetonitrile as a mobile phase (55:10:35, v/v). pH was adjusted to 7.0. Amlodipine was used as an internal standard (IS). LOD of the method was found to be 20 ng mL⁻¹ for both drugs. Results were linear over the studied range 40.994–2007.556 ng mL⁻¹ for rosiglitazone (r ² ≥ 0.99) and 41.066–2094.84 ng mL⁻¹ for glimepride( r ² ≥ 0.99). The method was found to be simple, selective, precise and reproducible for the estimation of both drugs from spiked human plasma.

     

Rapid Determination of Meropenem in Biological Fluids by LC: Comparison of Various Methods for Sample Preparation and Investigation of Meropenem Stability

A rapid and sensitive LC-UV method was developed and validated for the determination of meropenem, in human plasma and urine. Meropenem retention time was 4.8 min. Method development was based on comparative analysis of different extraction methods published as well as careful study of meropenem stability in biological samples under different conditions. Best results in plasma sample preparation were obtained from protein precipitation with methanol. LOQ was 0.1 µg mL^?1 for plasma and 1 µg mL^?1 for urine samples. Meropenem in plasma has low stability at room temperature (<20% of original content after 12 h), but had acceptable stability when the whole analysis procedure was designed to minimize the exposure of meropenem-containing samples and solutions to temperatures higher than 4 °C. The developed method was applied to a human pharmacokinetic study in patients with acute peritonitis.     

Highly Sensitive Determination of Traces of Co(II) in Pharmaceutical and Urine Samples Using Kinetic–Spectrophotometric Method

Abstract

A high sensitive, accurate and simple kinetic method has been developed for determination of trace of Co(II) ions, based on its strongly catalytic effect in the reaction oxidation of disodium-6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphtalenesulfonic acid (artificial color, Sunset Yellow FCF, E110 in text selected as SY) by hydrogen peroxide in borate buffer at pH of 9.5, by monitoring the rate of disappearance of SY. Reaction rate was monitored spectrophotometrically, at λ_max of the SY at 478.4 nm. The optimum operating conditions regarding reagents concentration and temperature were established. The tangent method was adopted for constructing the calibration curve, which was found to be linear over the concentration range 1.18–17.67 ng ml^?1 and 17.67–58.90 ng ml^?1 of Co(II). The limit of detection (3σ) is 0.15 ng ml^?1, and limit of quantification (10σ) is 0.5 ng ml^?1. The effects of the other ions on the reaction rate were determined for an assessment of the selectivity of the method. The developed kinetic procedure was successfully applied for the determination of Co(II) in pharmaceutical and urine samples. The unique features of this procedure are that the determination can be performed at room temperature, and the analysis time is short. The newly developed method is high sensitive, simple, inexpensive and efficient for use in the analysis of a large number of samples.