Optimization and Validation of HS-SPME-GCMS Method for Determination of Multifumigant Residues in Grain, Oilseeds, Nuts, and Dry Fruit

Background: Fumigants are approved in many countries and used to treat food, feed, and seed. The amount of residue that remains in fumigated materials is measured and reported. Objective: The optimization and validation of a high-sensitivity headspace solid-phase microextraction gas chromatograph mass spectrometer (HS-SPME-GCMS) method for determination of eight fumigant residues—phosphine, methyl bromide, cyanogen, sulfuryl fluoride, ethylene oxide, propylene oxide, ethyl bromide and ethyl formate—in a range of food matrices were developed. The food matrices included grain, oilseed, dried fruit, and nut. Methods: The new method was used to determine residue levels from a fumigant complex in food matrices by monitoring the change of the absorption of spiked standards and desorption of fumigant from fumigated samples. Results: Based on the observation, the process of physical sorption and chemisorption was defined. The equilibrium time of the sample analysis was chosen at 5 hours. The LODs of the fumigants were in the range of 0.03 to 1.99 ng/g. Response to a range of diluted authentic standards gave significant linear regressions (r2 > 0.9983), and the RSDs were ≤8.7% at the 3 ng/g level of aged spiking standard, except for sulfuryl fluoride, for which the LOD was 1.99 ng/g and the RSD value was 39.7% (6.64 ng/g). Conclusions: The performance of the HS-SPME-GCMS method was more sensitive than the use of a gas syringe, except for sulfuryl fluoride. Highlights: An innovative multifumigant residue detection method based on HS-SPME sampling technology with gas chromatograph-mass selective detection (GC-MSD) analysis was established, including phosphine, methyl bromide, cyanogen, sulfuryl fluoride, ethylene oxide, propylene oxide, ethyl bromide, and ethyl formate; The first report of a sorption study of the process of physical sorption and chemisorption of residual fumigant in fruit and food matrices by an HS-SPME-GCMS method; Consider the effect of time on fumigant behavior in dried fruit, grain, and nut; The LODs of the fumigants were in the range of 0.03 to 1.99 ng/g.

Optimization and Validation of HS-SPME-GCMS Method for Determination of Multifumigant Residues in Grain, Oilseeds, Nuts, and Dry Fruit

Background: Fumigants are approved in many countries and used to treat food, feed, and seed. The amount of residue that remains in fumigated materials is measured and reported. Objective: The optimization and validation of a high-sensitivity headspace solid-phase microextraction gas chromatograph mass spectrometer (HS-SPME-GCMS) method for determination of eight fumigant residues—phosphine, methyl bromide, cyanogen, sulfuryl fluoride, ethylene oxide, propylene oxide, ethyl bromide and ethyl formate—in a range of food matrices were developed. The food matrices included grain, oilseed, dried fruit, and nut. Methods: The new method was used to determine residue levels from a fumigant complex in food matrices by monitoring the change of the absorption of spiked standards and desorption of fumigant from fumigated samples. Results: Based on the observation, the process of physical sorption and chemisorption was defined. The equilibrium time of the sample analysis was chosen at 5 hours. The LODs of the fumigants were in the range of 0.03 to 1.99 ng/g. Response to a range of diluted authentic standards gave significant linear regressions (r2 > 0.9983), and the RSDs were ≤8.7% at the 3 ng/g level of aged spiking standard, except for sulfuryl fluoride, for which the LOD was 1.99 ng/g and the RSD value was 39.7% (6.64 ng/g). Conclusions: The performance of the HS-SPME-GCMS method was more sensitive than the use of a gas syringe, except for sulfuryl fluoride. Highlights: An innovative multifumigant residue detection method based on HS-SPME sampling technology with gas chromatograph-mass selective detection (GC-MSD) analysis was established, including phosphine, methyl bromide, cyanogen, sulfuryl fluoride, ethylene oxide, propylene oxide, ethyl bromide, and ethyl formate; The first report of a sorption study of the process of physical sorption and chemisorption of residual fumigant in fruit and food matrices by an HS-SPME-GCMS method; Consider the effect of time on fumigant behavior in dried fruit, grain, and nut; The LODs of the fumigants were in the range of 0.03 to 1.99 ng/g.

S-Alkylated 1,2,4-Triazoles Derivatives Synthesis, spectral analysis and cytotoxicity evaluation

This paper presents synthesis, characterization and cytotoxicity assessment of six S-alkylated 1,2,4-triazoles derivatives that were obtained by treatment of some 1,2,4-triazole-3-thiones containing in the molecule phenylsulfonylphenyl and propyl or 4-bromophenylsulfonylphenyl and 4-methoxyphenyl fragments with different alkylation agents (ethyl bromide, ethyl chloroacetate or phenacyl bromide) in basic media. The synthesized compounds were physico-chemically characterized and the IR, 1H-NMR, 13C-NMR spectra were consistent with the assigned structures. The cytotoxicity of S-alkylated derivatives was evaluated on Daphnia magna crustacean.

Synthesis and Spectral Characterization of New S-Alkylated 1,2,4-Triazoles as Potential Biological Agents

In the work we presented the behavior of 5-(4-(4-X-phenylsulfonyl)phenyl)-4-(n-propyl)-2H-1,2,4-triazole-3(4H)-thiones (X= Cl or Br) with some alkylation agents. Thus, new S-alkylated 1,2,4-triazole derivatives were synthesized by reaction of the corresponding 1,2,4-triazole-3-thione derivatives with different �-halogenated compounds (ethyl bromide, ethyl chloroacetate or phenacyl bromide), in basic medium. The structures of synthesized compounds were elucidated by spectral data (1H-NMR, 13C-NMR, mass spectrometry) and elemental analysis.

Electronic spectroscopy of ethyl bromide probed by VUV photoabsorption and quantum chemical calculations

A comprehensive study of the electronic absorption spectra of C2H5Br and C2D5Br using synchrotron radiation photoabsorption spectroscopy and TDDFT calculations.

Dissociative ionization and Coulomb explosion of ethyl bromide under a near-infrared intense femtosecond laser field

The dissociation pathways for H2 and H2+ elimination from the parent ions C2H5Br+ and C2H5Br2+ are theoretically and experimentally demonstrated.