[Determination of dazomet and its metabolite methyl isothiocyanate residues in plant-derived foods by gas chromatography-triple quadrupole mass spectrometry].

Dazomet is a kind of crystal solid that is stable at room temperature and acts as a fumigant. It is commonly used to control soil fungi, as an insecticide, and in sterilization and weeding. It can effectively kill root-knot nematodes, soil pests, weeds, and many soil-borne disease-causing organisms, to provide clean and healthy soil. Dazomet slowly decomposes and releases methyl isothiocyanate, methylamine, carbon disulfide, and hydrogen sulfide in acidic soil, and diffuses upward through the spaces in the soil to kill contact organisms. When agricultural crops are planted in soil treated with cotton wool, the residues in the grown crop can cause harm to human body when consumed. To ensure the quality and safety of food crops, it is important to develop a detection method for dazomet and its metabolites in plant-derived foods. Hence, in this study, a rapid and simultaneous determination method was developed for dazomet and its metabolite methyl isothiocyanate residues in plant-derived foods by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The sample pretreatment and chromatographic conditions were optimized in the experiment. Subsequently, dazomet and its metabolite methyl isothiocyanate residues in vegetables, fruits, grains, nuts, tea, and spices were extracted with ethyl acetate, and purified using graphitized carbon, a primary-secondary amine, stearyl-bonded silica gel, and anhydrous magnesium sulfate as dispersive solid-phase extraction sorbents. After centrifugation and filtration, the target compounds were analyzed in the multiple reaction monitoring (MRM) mode by GC-MS/MS, and quantified by matrix matching external standard method. The matrix effects of the samples were also evaluated. The matrix effect was found to be in the range of 2.5% to 13.6% for methyl isothiocyanate in 16 matrices. As this matrix effect was weak, there was no need for compensatory measures. In contrast, the matrix effect of dazomet in 16 matrices was in the range of 240.3% to 331.2%. This matrix effect was strong and required compensation. Finally, a matrix matching calibration method was used to compensate the matrix effects. The relative matrix effects of other tested substrates were analyzed using lettuce as the representative substrate; it was found that all showed weak matrix effects. Therefore, the use of lettuce as a representative matrix to prepare a matrix standard curve can effectively correct the matrix effects of dazomet and methyl isothiocyanate in other substrates. Under the optimal conditions, the calibration curves were linear in the range of 0.005-1 mg/L with correlation coefficients higher than 0.99. Recovery tests were conducted by adding mixed standards to blank samples at four levels. The recoveries were in the range of 74.2%-117.2% with relative standard deviations (RSDs, n=6) of 2.8%-9.0%. The limits of quantification (LOQs) of dazomet and methyl isothiocyanate were 0.01 mg/kg. The accuracy and precision of this method met the requirements of pesticide residue determination. The established method was used to detect dazomet and its metabolite methyl isothiocyanate residues in six samples of Chinese cabbage, Chinese chives, cowpea, lettuce, eggplant, ginger, celery, potato, orange, kiwifruit, tomato, chili, rice, tea, almond, and Cuminum cyminum L. in the laboratory, and nothing was detected. The method is simple, rapid, and sensitive; overcomes the shortcomings of existing methods that require two pretreatment steps and two sets of equipment; and meets the requirements for the detection of dazomet and its metabolite methyl isothiocyanate residues in plant-derived foods.

Colorimetric determination of xanthine in urine based on peroxidase-like activity of WO3 nanosheets.

Two-dimensional WO3 nanosheets were prepared by ultrasonic exfoliation of bulk WO3·2H2O in water and characterized by transmission electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman, dynamic light scattering. The nanosheets were discovered to possess the peroxidase-like catalytic activity, which can catalyze the oxidation of 3, 3', 5, 5'-tetramethylbenzidine by H2O2. The catalytic mechanism was also investigated by the scavenger experiments. Taking advantage of the peroxidase-like activity of WO3 nanosheets, a facile colorimetric method for xanthine was developed by combining the oxidation reaction of xanthine catalyzed by xanthine oxidase. The linear range for xanthine was ranged from 25 to 200 µmol L-1. The limit of detection for xanthine was 1.24 µmol L-1. The colorimetric method was applied to determine xanthine in urine samples.

Boron- and Phenyl-Doped Graphitic Carbon Nitride (g-C3N4) Nanosheets for Colorimetric Detection of Hydrogen Peroxide in Soaked Foods.

Boron- and phenyl-doped graphitic carbon nitride nanosheets (BPCN NSs) were prepared by thermal polymerization of cyanamide with 3-aminobenzeneboronic acid followed by ultrasonic exfoliation. BPCN NSs exhibited enhanced peroxidase-like activity and catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) and o-phenylenediamine by H2O2. A simple sensitive colorimetric senor was developed for H2O2 by utilizing TMB as the substrate and BPCN NSs as enzyme mimetic. The linear relations between the absorbance and H2O2 concentration over the range from 0 to 280 µmol L-1 and from 280 to 1000 µmol L-1 were obtained with the limit of detection of 1.0 µmol L-1 according to the 3σ rule. The colorimetric sensor was applied for the detection of H2O2 residue in simulated soaked foods with satisfied results. Finally, the portable test kits for H2O2 were prepared and applied for the semi-quantitative assay of H2O2 residues in soaked chicken feet.

Colorimetric assay of copper ions based on the inhibition of peroxidase-like activity of MoS2 nanosheets.

The peroxidase-like catalytic activity of MoS2 nanomaterials has been utilized for colorimetric bioassays and medical diagnostics. However, the application of peroxidase-like catalytic activity of MoS2 nanomaterials in environmental analysis was seldom explored. Herein, copper ions were found to inhibit the peroxidase-like catalytic activity of MoS2 nanosheets, which can catalyze the oxidation of 3, 3', 5, 5'-tetramethylbenzidine by H2O2 to produce a colorimetric product. Based on this finding, a simple sensitive colorimetric method for the detection of copper ions was developed. In the presence of copper ions, the absorbance and color of the solution decreased with the increasing concentration of copper ions. The color of the solution can be used to semi-quantitative on-site assay of copper ions by naked eyes. A linear relationship between the absorbance and the concentration of copper ions was observed in the range of 0.4-4.0µmolL-1 with a detection limit of 92nmolL-1, which was much lower than the maximum contaminant level of copper in drinking water legislated by the Environmental Protection Agency of USA and the World Health Organization. The method was applied to detect copper ions in environmental water samples with satisfactory results.

An ultrasensitive electrochemiluminescent sensor based on a pencil graphite electrode modified with CdS nanorods for detection of chlorogenic acid in honeysuckle.

In this paper, a novel and ultrasensitive electrochemiluminescent sensor employing a solvothermal-synthesized CdS nanorod-modified pencil graphite electrode (CdS/PGE) for the determination of chlorogenic acid (CA) is fabricated. In the first step, the PGE surface is modified using CdS nanorods. In the next step, the developed electrode is used to detect CA using a electrochemiluminescent (ECL) technique, in which potassium persulfate (K2 S2 O8 ) served as a co-reactant. The possible ECL mechanism is investigated, and the influences of pH and cyclic voltammetric scanning rate on the signal response are studied. The ECL intensity decreases quantitatively in relation to the concentration of the target molecule. Under optimized conditions, the linear correlation between the quenched ECL intensity and the logarithm of CA concentration is observed in the range from 2 × 10-9 to 8 × 10-7  mol L-1 with a limit of detection of 1 × 10-9  mol L-1 . This proposed method is applied to the analysis of CA in honeysuckle flower, giving recoveries of 99-107%. The experimental results demonstrate that this ECL sensor shows good stability and reproducibility.

[Study of pH measuring based on i-motif DNA conformation switch and UV-Vis absorption spectroscopy of gold nanoparticles].

A fast, sensitive, colorimetric method for the detection of pH based on the differentiate effect of gold nanoparticles to the configuration of DNA was developed in this study. The UV-Vis absorption spectroscopy of the i-motif DNA-Au NPs system has been investigated, and the effect of the concentration of salt and i-motif DNA, reaction time and DNA sequence on the pH response of the system have been also optimized. Under the optimum conditions, the UV-Vis absorption spectroscopy of the Au NPs is changed regularly with pH in the range of 5.3 - 7.0, the absorbance at 520 nm is increased gradually while at 700 nm decreased. Correspondingly, the color of the Au NPs is varied from violet to red. The pH sensor is no need to modification, low cost, fast and can be carried out by naked eyes. It is promising to use in monitoring some life process which associated with pH variation.

Sensitive turn-on fluorescent detection of melamine based on fluorescence resonance energy transfer.

We here report a novel fluorescent method for the detection of melamine based on the high fluorescence quenching ability of gold nanoparticles. The fluorescence was significantly quenched via fluorescence resonance energy transfer when fluorescein molecules were attached to the surface of gold nanoparticles by electrostatic interaction. Upon addition of melamine, the fluorescence was enhanced due to the competitive adsorption of gold nanoparticles between melamine and fluorescein. Under the optimum conditions, the fluorescence enhancement efficiency [(I-I(0))/I(0)] showed a linear relationship with the concentration of melamine in the range of 1.0 × 10(-7) mol L(-1)~4.0 × 10(-6) mol L(-1), and the detection limit was calculated to be 1.0 × 10(-9) mol L(-1). The proposed method showed several advantages such as high sensitivity, short analysis time, low cost and ease of operation.

Visual detection of melamine in milk products by label-free gold nanoparticles.

A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2ppm, respectively, within 30min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15ppm of melamine in liquid milk and 2.5ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products.