Bifenthrin Residues in Table Grapevine: Method Optimization, Dissipation and Removal of Residues in Grapes and Grape Leaves.

The QuEChERS method was adjusted to determine bifenthrin residues in grapes and grape leaves. Extraction and cleanup procedures were optimized to decrease co-extracted materials and enhance the detection of bifenthrin. The method was validated per the European Union (EU) Guidelines criteria. Accuracy ranged from 98.8% to 93.5% for grapes and grape leaves, respectively. Precision values were 5.5 and 6.4 (RSDr) and 7.4 and 6.7 (RSDR) for grapes and grape leaves, respectively. LOQs (the lowest spiking level) were 2 and 20 µg/kg for grapes and grape leaves, respectively. Linearity as determination coefficient (R2) values were 0.9997 and 0.9964 for grapes and grape leaves, respectively, in a matrix over 1-100 µg/L range of analyte concentration. This was very close to the value in the pure solvent (0.9999), showing the efficiency of the cleanup in removing the co-extracted and co-injected materials; the matrix effect was close to zero in both sample matrices. Dissipation of bifenthrin was studied in a supervised trial conducted in a grapevine field during the summer of 2023 at the recommended dose and double the dose. Dissipation factor k values were 0.1549 and 0.1672 (recommended dose) and 0.235 and 0.208 (double dose) for grapes and grape leaves, respectively. Pre-harvest interval (PHI) was calculated for the Maximum Residue Limit (MRL) values of the EU database. Residues of bifenthrin were removed effectively from grapes using simple washing with tap water in a laboratory study. Residues reached the MRL level of 0.3 mg/kg in both washing treatments, running or soaking in tap water treatments for 5 min. Removal from leaves did not decrease residue levels to the MRL in grape leaves.

Development of Green and Facile Sample Preparation Method for Determination of Seven Neonicotinoids in Fresh Vegetables, and Dissipation and Risk Assessment of Imidacloprid and Dinotefuran.

A facile procedure for extracting and determining seven neonicotinoids was developed. Water was the only extraction solvent without phase separation and cleanup steps. The method was validated according to European Union standards, and the values obtained were compared with the criteria. The accuracy values were between 99.8% (thiamethoxam) and 106.8% (clothianidin) at the spiking levels of 0.01, 0.1, and 1 mg/kg in the tested matrices. The precision as pooled RSD values was ≤6.1% (intra-day) and ≤6.9% (inter-day). The limit of quantification was set and tested at 0.01 mg/kg. The matrix effect was evaluated, and all matrices had a suppressive effect. The matrix of the cucumber was the most effective, with -20.9% for dinotefuran and an average of -9.8% for all compounds, while the tomato matrix had the slightest effect. Real marketed samples were analyzed using the developed and QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methods; the results were not significantly different. A supervised field trial was conducted in the open field to study the dissipation patterns of imidacloprid and dinotefuran in tomatoes. The dissipation of both compounds followed first-order kinetics. The half-life (T½) values were 3.4 and 2.5 days, with dissipation rates k of 0.2013 and 0.2781 days, respectively. Following the EU-MRL database, the calculated pre-harvest interval (PHI) values were 7 and 14 days for imidacloprid and dinotefuran, respectively, and 3 days for both compounds following Codex Alimentarius regulations. The risk of imidacloprid and dinotefuran residues was estimated from chronic and acute perspectives. The risk factors of dinotefuran were lower than those of imidacloprid. Nonetheless, the highest expected residues of both compounds were below the tolerance limits.

Total synthesis of cis-reticulatacin-10-ones A and B: absolute stereochemical assignment.

cis-Reticulatacin-10-ones A and B were synthesised as a predefined mixture of diastereoisomers (dr ∼ 1 : 9) in nine steps from the acid chloride 8, and without the use of hydroxyl protecting groups. Comparison of the chiral HPLC chromatogram of the synthetic sample with that of the natural product isolated from the roots of the tropical fruit tree Annona muricata L. showed the natural product to be a mixture of A and B diastereoisomers (dr ∼ 1 : 1).

Total synthesis and stereochemical assignment of cis-uvariamicin I and cis-reticulatacin.

Diastereoisomeric mixtures of cis-uvariamicin I (15R,16R,19S,20S,36S and 15S,16S,19R,20R,36S) and cis-reticulatacin (17R,18R,21S,22S,36S and 17S,18S,21R,22R,36S) were synthesized to determine the stereochemistry of the natural products isolated from Annona muricata. It was not possible to resolve a mixture of the four synthetic isomers using chiral HPLC, but the mixed isomers could be distinguished using chiral HPLC EIMS with extracted fragment ion analysis. Comparison of synthetic standards with the natural isolate revealed that cis-uvariamicin I and cis-reticulatacin are present in nature as mixtures of threo-cis-threo diastereoisomers. It is suggested that the nomenclature for the natural products is amended as follows: (15R,16R,19S,20S,36S)-cis-uvariamicin I (cis-uvariamicin IA); (15S,16S,19R,20R,36S)-cis-uvariamicin I (cis-uvariamicin IB); (17R,18R,21S,22S,36S)-cis-reticulatacin (cis-reticulatacin A); (17S,18S,21R,22R,36S)-cis-reticulatacin (cis-reticulatacin B).

Microwave-assisted synthesis and antimicrobial activities of flavonoid derivatives.

Eleven flavonoid derivatives were synthesised using a modified Baker-Venkataraman rearrangement, and subsequent microwave-assisted closure of the heterocyclic ring. All of the synthetic compounds displayed antifungal activity against Aspergillus niger and Fusarium oxysporium, and two of the synthetic flavonoid analogues exhibited significant activity against methicillin-resistant Staphylococcus aureus.

Effects of biochar amendment on sorption, dissipation, and uptake of fenamiphos and cadusafos nematicides in sandy soil.

BACKGROUND: The application of biochar to soil is supposed to alter its adsorption/desorption potential toward pesticides, thereby affecting their bioavailability and efficacy. This is particularly relevant in the case of nematicides because these pesticides are directly applied to soil. RESULTS: Biochar was produced from date palm (PB) and eucalyptus (EB) waste at 450 °C and added at a rate of 1% to a sandy soil. The half-life (t½ ) of fenamiphos was increased from 2.7 to 18.3 and 18.6 days in PB- and EB-amended soils, respectively. By contrast, the half-life of cadusafos was unaffected. Freundlich Kf values increased from 1.22 and 0.39 (µg1-Nf g-1 mLNf ) to 4.49 and 6.84 in 1% PB-amended soil, and to 3.49 and 4.62 in 1% EB-amended soil for cadusafos and fenamiphos, respectively. Plant uptake of both nematicides in tomato seedlings was reduced by approximately 97% (cadusafos) and 85% (fenamiphos). Although nematicide efficacy against Meloidogyne incognita was not altered at the recommended dosage, it was negatively affected at a half-dose rate. Under these conditions, it decreased from 43.1% in unamended sandy soil to only 18.3% in 1% PB-amended soil. CONCLUSIONS: Biochar addition increased the sorption capacity of soil. This resulted in a decrease of nematicide bioavailability, together with a reduction of both the dissipation rate and uptake by tomato plants. © 2018 Society of Chemical Industry.

Method validation and dissipation dynamics of chlorfenapyr in squash and okra.

QuEChERS method combined with GC-IT-MS was developed and validated for the determination of chlorfenapyr residues in squash and okra matrices. Method accuracy, repeatability, linearity and specificity were investigated. Matrix effect was discussed. Determination coefficients (R(2)) were 0.9992 and 0.9987 in both matrices. LODs were 2.4 and 2.2µg/kg, while LOQs were 8.2 and 7.3µg/kg. Method accuracy ranged from 92.76% to 106.49%. Method precision RSDs were ⩽12.59%. A field trial to assess chlorfenapyr dissipation behavior was carried out. The developed method was employed in analyzing field samples. Dissipation behavior followed first order kinetics in both crops. Half-life values (t1/2) ranged from 0.2 to 6.58days with determination coefficient (R(2)) ranged from 0.78 to 0.96. The developed method was utilized for surveying chlorfenapyr residues in squash and okra samples collected from the market. Monitoring results are discussed.