Deep eutectic solvent-based adhesive tape extraction combined with enzyme inhibition assay for the determination and distinction of dithiocarbamate pesticides in food samples.

A simple, green extraction method of dithiocarbamate (DTC) pesticides in food samples was developed using adhesive tapes and a green deep eutectic solvent (DES). A rapid and convenient determination and distinction method of DTC pesticides was established using tyrosinase inhibition assay. First, DTC pesticides were extracted by pasting and peeling off the adhesive tape, then eluted by the DES synthesized from xylitol and ethylene glycol. Second, determination of DTC pesticides was conducted by inhibiting the activity of tyrosinase which can catalyze the oxidation of catechol. Less colored products were generated in the reaction system (tyrosinase, catechol, and 4-aminoantipyrine), leading to weak absorbance. In addition, different DTC pesticides (ziram, propineb, zineb, mancozeb, thiram, metiram, and ferbam) were successfully distinguished by sensor arrays (tyrosinase, phenolic compounds, and 4-aminoantipyrine) through principal component analysis. The limit of detection was found to be 0.2 µg kg-1, and the limit of quantification was 0.6 µg kg-1. The recoveries ranging from 89.4% to 103.8% were obtained in vegetable, fruit, and cereal, with a relative standard deviation of less than 4.2%. The method is simple, rapid, and convenient and shows good application prospects in the determination of pesticides in a variety of food samples.

Rapid detection of ziram residues in apple and pear fruits by SERS based on octanethiol functionalized bimetallic core-shell nanoparticles.

Existing approaches for the screening of unsafe materials in food matrices are time-consuming, tiresome and destructive in nature. Therefore, in the current study, a surface-enhanced Raman spectroscopy (SERS) method based on octanethiol-functionalized core-shell nanoparticles (Oct/Au@AgNPs) was established for rapid detection of ziram in apple and pear fruits. The morphology of substrate was evaluated using high-resolution TEM images and superimposed HAADF-STEM-EDS elemental mapping images, which confirmed that Au@AgNPs having gold (Au) core size of 28 nm in diameter and silver (Ag) shell of 5.5 nm in thickness were successfully grafted with octanethiol. The SERS method with the sensitive nanoparticles could detect ziram of up to 0.015 and 0.016 ppm in apple and pear with high coefficients of determination (R2) of 0.9987 and 0.9993, respectively. Furthermore, satisfactory recoveries (80-106%) were also accomplished for the fungicide in real samples. This work demonstrated that the functionalized silver-coated gold nanoparticles were easy to prepare and could be used as sensitive SERS platforms for monitoring of other agrochemicals in foods.

Carbon dots with red emission for bioimaging of fungal cells and detecting Hg2+ and ziram in aqueous solution.

It is of importance for bioimaging of fungal cells using biocompatible and low toxic carbon dots (CDs) as labels in plant protection field because a clearer understanding on the infection mechanism of fungi on plant can be achieved. Meanwhile, long wavelength, especially, red/near-infrared (NIR) emissive CDs are more biocompatible than short wavelength emissive ones. In this work, CDs with red emission were synthesized by solvothermal pyrolysis of citric acid, acrylamide dissolved in formamide. Fungal cells stained by the CDs with red emission were brightly illuminated when imaged on a fluorescent microscope with excitation by a green laser pulse, suggesting the CDs are of an excellent label for bioimaging of fungal cell in red color region. Moreover, the CDs show a selective response to Hg2+ in the NaAc-HAc buffer solution, while ziram can form a more stable complex with Hg2+, leading to a recovery of the quenched fluorescence of the CDs. Therefore, methods for the detections of Hg2+ and ziram based on the "off-on" fluorescence of the CDs were established with limits of detection as low as 0.19 µM and 0.55 µg/mL.

A combination of dispersive liquid-liquid microextraction and surface plasmon resonance sensing of gold nanoparticles for the determination of ziram pesticide.

We have developed a reliable, fast, and highly sensitive analytical method utilizing dispersive liquid-liquid microextraction and gold nanoparticles probes for ziram (zinc bis(dimethyldithiocarbamate)) determination. The method is based on the in situ formation of gold nanoparticles in carbon tetrachloride as an organic phase. It was found that the trace levels of ziram influenced the formation of gold nanoparticles, leading to absorbance change of a sedimented phase. The results of the colorimetric ziram determination were in the concentration range of 0.12-2.52 ng/mL with a limit of detection of 0.06 ng/mL. The formation of the stable and dispersed gold nanoparticles in the organic phase provides a good precision for dispersive liquid-liquid microextraction method, resulting in the relative standard deviation of 3.8 and 1.2% for 0.56 and 1.58 ng/mL of ziram, respectively. This method has been successfully used for the ziram determination in samples of well and river water, soil, potato, carrot, wheat, and paddy soil.

Preparation and characterization of magnetic carboxylated nanodiamonds for vortex-assisted magnetic solid-phase extraction of ziram in food and water samples.

A simple and rapid vortex-assisted magnetic solid phase extraction (VA-MSPE) method for the separation and preconcentration of ziram (zinc dimethyldithiocarbamate), subsequent detection of the zinc in complex structure of ziram by flame atomic absorption spectrometry (AAS) has been developed. The ziram content was calculated by using stoichiometric relationship between the zinc and ziram. Magnetic carboxylated nanodiamonds (MCNDs) as solid-phase extraction adsorbent was prepared and characterized by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) spectrometry and scanning electron microscopy (SEM). These magnetic carboxylated nanodiamonds carrying the ziram could be easily separated from the aqueous solution by applying an external magnetic field; no filtration or centrifugation was necessary. Some important factors influencing the extraction efficiency of ziram such as pH of sample solution, amount of adsorbent, type and volume of eluent, extraction and desorption time and sample volume were studied and optimized. The total extraction and detection time was lower than 10min The preconcentration factor (PF), the precision (RSD, n=7), the limit of detection (LOD) and limit of quantification (LOQ) were 160, 7.0%, 5.3µgL(-1) and 17.5µgL(-1), respectively. The interference of various ions has been examined and the method has been applied for the determination of ziram in various waters, foodstuffs samples and synthetic mixtures.

Selective determination of thiram residues in fruit and vegetables by hydrophilic interaction LC-MS.

Thiram belongs to the most important class of dithiocarbamate (DTC) fungicides including dimethyldithiocarbamates (DMDs), ethylenebis(dithiocarbamtes) (EBDs) and propylenebis(dithiocarbamates) (PBDs). During the surface extraction of fruit and vegetables for the LC-MS determination of residues of DMDs, EBDs and PBDs, thiram is reduced by the penicillamine buffer to the DMD anion, thus resulting in false-positive findings of DMD fungicides like ziram. Therefore, an alkaline sulfite buffer was applied for surface extraction, quantitatively transforming thiram into the DMD anion and a stable DMD-sulfite adduct that was used as a selective marker for thiram. Separation was performed isocratically on a ZIC-pHILIC column with acetonitrile-10 mM ammonium hydroxide solution (85/15). Mass selective detection was carried out on a single-quadrupole mass spectrometer coupled to an electrospray ionisation interface operating in negative mode. Using d12-thiram as the internal standard, recoveries of 80-108% were obtained from apples, tomatoes, grapes and sweet peppers, spiked in the range of 0.02-1 mg kg(-1). Limits of detection and quantification were 0.6 and 2 µg kg(-1), respectively.

Gold nanoparticle-based optical microfluidic sensors for analysis of environmental pollutants.

Conventional methods of environmental analysis can be significantly improved by the development of portable microscale technologies for direct in-field sensing at remote locations. This report demonstrates the vast potential of gold nanoparticle-based microfluidic sensors for the rapid, in-field, detection of two important classes of environmental contaminants - heavy metals and pesticides. Using gold nanoparticle-based microfluidic sensors linked to a simple digital camera as the detector, detection limits as low as 0.6 µg L(-1) and 16 µg L(-1) could be obtained for the heavy metal mercury and the dithiocarbamate pesticide ziram, respectively. These results demonstrate that the attractive optical properties of gold nanoparticle probes combine synergistically with the inherent qualities of microfluidic platforms to offer simple, portable and sensitive sensors for environmental contaminants.

Flow injection-photoinduced-chemiluminescence determination of ziram and zineb.

A simple, sensitive and rapid method for the determination of the pesticides ziram and zineb was described. This new method was based on the coupling of FIA methodology and direct chemiluminescent detection; this approach had not been used up to now with these pesticides. The additional use of an 'on line' photochemical reaction, which was performed by using a photoreactor consisting of a long piece of PTFE helically coiled around a 15W low-pressure lamp, increased by a factor >20 the chemiluminometric response of the pesticides. An additional 3-fold improvement in the analytical signal was also achieved by using quinine as sensitizer. The obtained throughputs were very high (121 and 101 h(-1) for ziram and zineb, respectively); this feature together with its low limit of detection (1 ng mL(-1)) makes this method particularly well suited to routine analyses of environmental samples. On the other hand, its applicability to two members of the dithiocarbamate family of pesticides, makes it promising for the determination of the rest of the members of this family. The method was demonstrated by application to spiked water samples from different origins (ground, river and irrigation).

Preparation of a highly sensitive enzyme electrode using gold nanoparticles for measurement of pesticides at the ppt level.

A highly sensitive enzyme electrode was prepared based on gold nanoparticles for measurement of pesticides. Gold nanoparticles of 25-30 nm were synthesized on a glassy carbon electrode by double-pulse technique while the coverage was controlled by applied potential and time. The gold nanoparticles were modified to form a self-assembled monolayer, followed by covalent binding of tyrosinase. The TYR-AuNP-GC electrode was compared with bare GC, AuNP-GC, and modified AuNP-GC and TYR-Au (plate type) electrodes in terms of cyclic voltammetry. The voltammograms well represent the sensitivity of enzymatic oxidation of catechol, substrates for the enzyme activity. The prepared electrode integrated into a continuous flow system and was tested to detect pesticides, such as 2,4-D, atrazine, and ziram. Under the optimized conditions of the flow system, the electrode performed reasonably according to the inhibition mechanism in the concentration range of 0.001-0.5 ng mL(-1). The enhanced performance was attributed to the favored microenvironment for the enzyme activity provided by SAM on gold nanoparticles.

Determination of dithiocarbamate fungicide residues by liquid chromatography/mass spectrometry and stable isotope dilution assay.

A rapid and very sensitive high-performance liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) method for the simultaneous determination of dithiocarbamate (DTC) fungicide residues in fruits and vegetables was developed. The surface extraction of samples used an alkaline buffer consisting of sodium hydrogen carbonate and DL-penicillamine. The three DTC subclasses, i.e. dimethyldithiocarbamates (DMDs), ethylenebis(dithiocarbamates) (EBDs), and propylenebis(dithiocarbamates) (PBDs), were separated on a Sequant ZIC-pHILIC column using an acetonitrile/10 mM ammonia gradient. Because of the instability of DTC residues extracted from plant samples, a stable isotope dilution assay was applied. For each DTC subclass, the limits of detection and quantification were approximately 0.03 mg kg(-1) and 0.05 mg kg(-1), respectively. Recoveries from grapes, cucumbers, tomatoes, and rucola, spiked in the range of 0.01-0.9 mg kg(-1), averaged between 90 and 100%.

Column preconcentration and spectrophotometric determination of ziram and zineb in commercial samples and foodstuffs using (1,2'-pyridylazo)-2-naphthol (PAN)-naphthalene as adsorbate.

A procedure has been developed for the determination of zinc(II) bis(dimethyldithiocarbamate) (ziram) and zinc(II) ethylenebis(dithiocarbamate) (zineb) after preconcentration on a column using naphthalene-(1,2'-pyridylazo)-2-naphthol (PAN) as adsorbent. Ziram and zineb are quantitatively retained on the column in the pH range of 9.0-12.5 and at a flow rate of 1-2 mL/min. The solid mass consisting of the Zn-PAN complex along with naphthalene is dissolved from the column with 5 mL of dimethylformamide (DMF). Absorbance of the complex was measured at 550 nm; Beer's law is obeyed over the concentration ranges of 2.0-22.0 microg of ziram and 5.0-19.8 microg of zineb in 10 mL of the final DMF solution. Ten replicate determinations on a sample solution containing 20 microg of ziram and 18 microg of zineb gave a mean absorbance of 0.33 with relative standard deviations of 0.80 and 0.70%, respectively. The interference of various ions has been studied. The method has been employed for the determination of ziram and zineb in commercial samples and in various foodstuffs, and the results were compared with the earlier reported methods.

Microwave-assisted extraction (MAE)-acid hydrolysis of dithiocarbamates for trace analysis in tobacco and peaches.

A simple and rapid method is presented for the analysis of residues of ethylenebis(dithiocarbamate) (maneb, zineb, and mancozeb) and N,N-dimethyldithiocarbamate (thiram and ziram) fungicides in dry tobacco leaves and peaches. Residues are extracted and hydrolyzed to CS(2) in a single step by use of microwave energy in a closed-vessel system while the evolved CS(2) trapped in a layer of iso-octane overlaying the reaction mixture is taken for gas chromatographic-flame photometric analysis. This combined extraction-hydrolysis step is carried out in 10 and 15 min for sets of 12 samples of tobacco and peach matrices, respectively. Total sample preparation time for GC analysis is 40 min. The limits of detection (LOD) are 0.005 mg/kg for thiram and ziram on peaches and 0.1 mg/kg for maneb, zineb, and mancozeb on tobacco. The respective LOD and limit of quantification (LOQ) levels in CS(2) equivalents are 0.003 and 0.006 mg/kg on peaches and 0.04 and 0.2 mg/kg on tobacco, respectively. Recoveries in the 0.01-60 mg/kg fortification range are 80-100% with respective relative standard deviations <20%. The method was used for the analysis of >3000 commercial tobacco samples including also different marketed cigarette brands.

Spectrophotometric determination of ziram in a commercial sample and wheat by extraction of its copper dimethyldithiocarbamate complex into molten naphthalene.

A method was developed for the determination of zinc(II) dimethyldithiocarbamate by converting it into the copper(II) dithiocarbamate complex, which is then extracted into molten naphthalene. The absorbance is measured at 430 nm versus a reagent blank. Beer's law is obeyed for concentrations of 0.63 x 10(-3) to 17.2 x 10(-3) g/L in the final solution. The method is sensitive and was applied to the determination of ziram in a commercial sample and in wheat grain.

Flow injection-FTIR determination of dithiocarbamate pesticides.

A flow injection Fourier transform infrared spectrometric procedure has been developed for the determination the dithiocarbamate pesticides Ziram and Thiram in solid samples. All the operations involved, such as extraction, filtration and measurement, were integrated in the experimental set-up in order to avoid excessive manipulation of samples and standards. Ultrasonic assisted and mechanical extraction were evaluated for the solubilization of the analytes and, additionally, the effect of carrier flow rate, sample loop volume and the ratio between sample mass and volume of solvent employed were studied. Quantitative extractions with chloroform were obtained for both Ziram and Thiram, after 5 and 2 min, respectively, of mechanical shaking of sample slurries. Absorbance measurement, in the wavenumber range of 1600-1460 cm-1 for Ziram and 1400-1315 cm-1 for Thiram, was carried out, and the area values of the peaks obtained, as a function of time, were interpolated in external calibration lines prepared from standard solutions of Ziram and Thiram in chloroform. Analyses of commercial formulations and spiked soil samples incubated two weeks were in a good agreement with values found by other methodologies. Absolute detection limits of 400 micrograms for Ziram and 785 micrograms for Thiram and variation coefficients of 6.4% and 2.5% were obtained by use of the aforementioned methodology.

Simple and sensitive spectrophotometric determination of ziram, zineb and ferbam in commercial samples and foodstuffs using phenylfluorone.

A procedure has been developed for the determination of ziram, zineb and ferbam dithiocarbamate pesticides by converting ziram and zineb into a zinc-phenylfluorone complex and ferbam into an iron phenylfluorone complex, which are then dissolved in water in the presence of cetylpyridinium bromide and pyridine as a surfactant. The method is sensitive, highly selective and can be used for the determination of ziram, zineb and ferbam in commercial samples and in foodstuffs.

Identification of causative chemicals of allergic contact dermatitis using a combination of patch testing in patients and chemical analysis. Application to cases from industrial rubber products.

3 cases of allergic contact dermatitis from industrial rubber products were investigated using a combination of patch testing in patients and chemical analysis of causative rubber products by gas chromatography (GC), GC-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC). Our studies revealed N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), a typical rubber allergen, as a causative chemical in a case from a brand of heavy-duty rubber gloves and a case from a black rubber ring for car manufacture, and zinc ethylphenyldithiocarbamate (ZEPC), a dithiocarbamate (DTC)-type accelerator, as a causative chemical in a case from a brand of rubber work gloves: both IPPD and ZEPC, which showed positive patch test reactions, were confirmed in the extracts of the causative rubber products by GC, GC-MS and/or HPLC.