Highly-selective complex matrices removal via a modified QuEChERS for determination of triazine herbicide residues and risk assessment in bivalves.

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERs) method for determining triazine herbicide residues in bivalves (Mussels, Scallops, Cockles) was developed. The use of molecularly imprinted polymers (MIPs) as a selective purification material during dispersive-solid phase extraction (d-SPE) increased the removal rate of pigments interference. With 4% acidic acetonitrile as the organic modifier, the modified QuEChERs method achieved good extraction rate of herbicide residues. The satisfactory recoveries (80%-118%) and RSDs (1.0%-11.6%) of herbicide residues were obtained at three spiked levels. The limits of quantification of herbicide residues ranged from 0.10 µg/kg to 1.59 µg/kg. Further, the herbicide residues in bivalves collected in the eastern coasts of China was analyzed. The developed QuEChERs procedure coupled with GC-MS/MS was successfully applied to the herbicide residues detection in bivalves, and due to the extensive use of herbicides and the large consumption of bivalves in globally, the ongoing risk evaluation is needed.

A low-cost and high-efficiency carbazole-based porous organic polymer as a novel sorbent for solid-phase extraction of triazine herbicides in vegetables.

In this study, a porous organic polymer (denoted as Car-DMB) was fabricated by a simple one-step crosslinking polymerization of carbazole and p-dimethoxybenzene for the first time. Then the Car-DMB was served as adsorbent of solid phase extraction to enrich triazine herbicides from white gourd, tomato and soybean milk samples prior to their determination by high performance liquid chromatography. Under the optimal conditions, the response linearity was in the range of 0.3-100.0 ng g-1 for white gourds and tomato samples, and 0.5-100.0 ng mL-1 for soybean milk, with the coefficient of determination higher than 0.996. The detection limits were 0.1-0.2 ng g-1 for white gourd and tomato samples, and 0.15-0.3 ng mL-1 for soybean milk. The adsorption mechanism of the Car-DMB for the triazines was attributed to the strong H-bonding and weak π-π interactions. The efficient extraction for several other compounds demonstrated that Car-DMB holds great potential for diverse analysis applications.

Comparative assessment of metribuzin sorption efficiency of biochar, hydrochar and vermicompost.

In this study, we used two biochars (BC) produced from grapevine pruning residues (BCgv) and red spruce wood (BCrs), two hydrochars (HC) from urban pruning residues (HCup) and the organic fraction of municipal solid wastes (HCuw), and two vermicomposts (VC) obtained vermicomposting digestates from buffalo manure (VCbm) and mixed feedstock (VCmf). Adsorption kinetics and isotherms of metribuzin onto these materials were performed. Sorption kinetics followed preferentially a pseudo-second-order model, thus indicating the occurrence of chemical interactions between the sorbate and the adsorbents. Adsorption constants were calculated using the Freundlich and Langmuir models. Metribuzin sorption data on BCgv and both HC fitted preferentially the Freundlich equation, whereas on the other materials data fitted both isotherms well (r > 0.95). Metribuzin sorption capacity of the materials followed the trend BC > HC > VC. Sorption constants of metribuzin normalised per organic carbon content (KOC) on BCgv, BCrs, HCup, HCuw, VCbm and VCmf were 561, 383, 251, 214, 102 and 84 L kg-1, respectively. A significant positive correlation (P = 0.016) was calculated between distribution coefficients (Kd) of all materials and the corresponding organic carbon contents, thus indicating a prominent role of the organic fraction of these materials in the adsorption of metribuzin.

Assessment of column selection systems using Partial Least Squares.

Column selection systems based on calculation of a scalar measure based on Euclidean distance between chromatographic columns, suffer from the same issue. For diverse values of their parameters, identical or near-identical values can be calculated. Proper use of chemometric methods can not only provide a remedy, but also reveal underlying correlation between them. In this work, parameters of a well-established column selection system (CSS) developed at Katholieke Universiteit Leuven (KUL CSS) have been directly correlated to parameters of selectivity (retention time, resolution, and peak/valley ratio) toward pharmaceuticals, by employing Partial Least Squares (PLS). Two case studies were evaluated, separation of alfuzosin, lamotrigine, and their impurities, respectively. Within them, comprehensive correlation structure was revealed, which was thoroughly interpreted, confirming a causal relationship between KUL parameters and parameters of column performance. Furthermore, it was shown that the developed methodology can be applied to any distance-based column selection system.

Rapid detection of economic adulterants in fresh milk by liquid chromatography-tandem mass spectrometry.

A method to aid in the detection of the economically driven adulteration of fresh milk with a range of small, nitrogen containing compounds, including melamine, ammeline, ammelide, cyanuric acid, allantoin, thiourea, urea, biuret, triuret, semicarbazide, aminotriazine, 3- and 4-aminotriazole, cyanamide, dicyandiamide, guanidine, choline, hydroxyproline, nitrate, and a range of amino acids, has been developed. (15)N2-Urea is used as an internal standard. The adulteration of milk with exogenous urea has previously been difficult to detect because of the variation in the naturally occurring levels of urea in milk. However, by monitoring the contaminants biuret and triuret, which comprise up to 1% of synthetic urea, the adulteration of milk with urea-based fertilizer can be detected. We estimate that to be economically viable, adulteration of the order of 90-4000ppm of the above adulterants would need to be added to fresh milk. For most of the compounds, an arbitrary detection threshold of 2ppm is therefore more than sufficient. For biuret, a lower detection threshold, better than 0.5ppm, is desirable and the sensitivity for biuret and triuret can be improved by the post-column addition of lithium to create lithium adducts under electrospray ionisation. Sample handling involves a two-step solvent precipitation method that is deployed in a 96-well plate format, and the hydrophilic interaction liquid chromatography uses a rapid gradient (1.2min). Three separate injections, to detect the positively charged compounds, the negatively charged compounds and amino acids and finally the lithium adducts, are used. This rapid and qualitative survey method may be deployed as a second tier screening method to quickly reduce sample numbers indicated as irregular by an FTIR based screening system, and to direct analysis to appropriate quantification methods.

A validated LC method for determination of 2,3-dichlorobenzoic acid and its associated regio isomers.

A simple, selective and sensitive gradient reversed-phase liquid chromatography method has been developed for the separation and determination of 2,3-dichlorobenzoic acid, which is an intermediate of the lamotrizine drug substance, and its regio isomers. The separation was achieved on a reversed-phase United States Pharmacopeia L1 (C-18) column using 0.01 M ammonium acetate buffer at pH 2.5 and methanol (50:50 v/v) mixture as mobile phase A and a methanol and water mixture (80:20 v/v) as mobile phase B in a gradient elution at flow rate 1.2 mL/min with ultraviolet detection at 210 nm. The method is found to be selective, precise, linear, accurate and robust. It was used for quality assurance and monitoring the synthetic reactions involved in the process development of lamotrizine. The method is found to be simple, rapid, specific and reliable for the determination of unreacted levels of raw materials and isomers in reaction mixtures and finished product lamotrizine. The method was fully validated as per International Conference of Harmonization guidelines and results from validation confirm that the method is highly suitable for its intended purpose.

Determination of triazine herbicides in environmental samples by dispersive liquid-liquid microextraction coupled with high performance liquid chromatography.

A simple, rapid, efficient, and environmentally friendly method for the determination of five triazine herbicides in water and soil samples was developed by using dispersive liquid-liquid microextraction (DLLME), coupled with high performance liquid chromatography-diode array detection (HPLC-DAD). The water samples were directly used for DLLME extraction. For soil samples, the target analytes were first extracted by water-methanol (99:1, v/v). In the DLLME extraction method, chloroform was used as an extraction solvent, and acetonitrile as a dispersive solvent. Under the optimum conditions, the enrichment factors of DLLME were in the range between 183-221. The linearity of the method was obtained in the range of 0.5-200 ng/mL for the water sample analysis, and 1-200 ng/g for the soil samples, respectively. The correlation coefficients ranged from 0.9968 to 0.9999. The limits of detection were 0.05-0.1 ng/mL for the water samples, and 0.1-0.2 ng/g for the soil samples. The proposed method has been successfully applied to the analysis of target triazine herbicides (simazin, atrazine, prometon, ametryn, and prometryn) in water and soil samples with satisfactory results.

A simple and fast method for chlorsulfuron and metsulfuron methyl determination in water samples using multiwalled carbon nanotubes (MWCNTs) and capillary electrophoresis.

A new method to determine metsulfuron methyl (MSM) and chlorsulfuron (CS) in different water samples was developed. It consists in a solid phase extraction (SPE) procedure using multiwalled carbon nanotubes (MWCNTs) as sorbent material in combination with capillary zone electrophoretic determination. To carry out the pre-concentration step, a simple flow injection system was developed and optimized. Thus, 250 µL of aqueous solution containing methanol 50% (v/v) and acetonitrile 2% (v/v) as eluent, 10 mL of sample and a flow rate of 1.15 mL min(-1) were selected. The CE variables also were optimized. A rapid determination and good resolution of two herbicides were obtained within 9 min using a simple electrophoretic buffer (50 mmol L(-1) sodium tetraborate with 3% of methanol, pH=9.0). Under the optimum conditions, the calibration curves were linear between 0.5 and 6 µg L(-1) for MSM and CS with R(2)=0.995 and 0.997, respectively. The repeatability of the proposed method, expressed as relative standard deviation (RSD), varied between 4.1% and 5.4% (n=10) and the detection limits for MSM and CS were 0.40 and 0.36 µg L(-1), respectively. Good results were achieved when the proposed method was applied to spiked real water samples. The recoveries percentages of the two analytes were over the range 86-108%.

An attractive agro-industrial by-product in environmental cleanup: dye biosorption potential of untreated olive pomace.

This research deals with the evaluation of highly available and cost effective waste biomass of olive pomace for the removal of reactive textile dye, RR198 from aqueous medium and a real effluent. The experiments were conducted to assess the effects of process variables such as initial pH, biosorbent dosage, contact time, temperature and ionic strength. The results showed that the highest dye biosorption capacity was found at pH 2 and the needed time to reach the biosorption equilibrium was 40 min with a biosorbent concentration of 3.0 g L(-1). The sorption kinetics of dye was best described by the pseudo-second-order kinetic model. The equilibrium biosorption data were analyzed by Langmuir, Freundlich and Dubinin-Radushkevich isotherm models and the results from the isotherm studies showed that the RR198 biosorption process occurred on a homogenous surface of the biosorbent. The waste biomass of olive oil industry displayed biosorption capacities ranging from 6.05 x 10(-5) to 1.08 x 10(-4)mol g(-1) at different temperatures. The negative values of Delta G degrees and the positive value of Delta H degrees suggest that the biosorption process for RR198 was spontaneous and endothermic. Dye-biosorbent interactions were examined by FTIR and SEM analysis. Finally, high biosorption yield of olive waste for the removal of RR198 dye from real wastewater makes it possible that the olive pomace could be applied widely in wastewater treatment as biosorbent taking into account that no pretreatment on the solid residue is carried out.

Fluorophor-linked immunosorbent assay: a time- and cost-saving method for the characterization of antibody fragments using a fusion protein of a single-chain antibody fragment and enhanced green fluorescent protein.

A novel assay, referred to as fluorophor-linked immunosorbent assay (FLISA), for the characterization of single-chain antibody fragments (scFvs) is described. The principle of the method is the fusion of an scFv to enhanced green fluorescent protein (EGFP). The scFv domain, which binds to the immobilized hapten, can be detected by measuring the fluorescence of the EGFP domain. The time-consuming binding of secondary antibodies and enzyme reaction, necessary for enzyme-linked immunosorbent assays (ELISAs) are not required. Consequently, the assay time of 1.5 h needed to complete the FLISA is much shorter than that of comparable ELISAs, which require about 5 h. This renders the FLISA suitable for applications where a short assay time is essential, such as screening of mutant libraries of scFvs in directed evolution experiments or monitoring of the amount of functionally expressed recombinant protein during production processes. In contrast to a comparable ELISA, the FLISA showed no saturation when determining the relative amount of functional scFv. The amount of the soluble fraction of cell extracts from Escherichia coli expressing the fusion protein and the normalized fluorescence signal showed a linear correlation with R(2)>0.99. The usefulness of a competitive FLISA for the detection of analytes is shown exemplarily by the detection of s-triazines with the s-triazine-specific scFv K411B.