Research Progress on Benzimidazole Fungicides: A Review.

Benzimidazole fungicides are a class of highly effective, low-toxicity, systemic broad-spectrum fungicides developed in the 1960s and 1970s, based on the fungicidal activity of the benzimidazole ring structure. They exhibit biological activities including anticancer, antibacterial, and antiparasitic effects. Due to their particularly outstanding antibacterial properties, they are widely used in agriculture to prevent and control various plant diseases caused by fungi. The main products of benzimidazole fungicides include benomyl, carbendazim, thiabendazole, albendazole, thiophanate, thiophanate-methyl, fuberidazole, methyl (1-{[(5-cyanopentyl)amino]carbonyl}-1H-benzimidazol-2-yl) carbamate, and carbendazim salicylate. This article mainly reviews the physicochemical properties, toxicological properties, disease control efficacy, and pesticide residue and detection technologies of the aforementioned nine benzimidazole fungicides and their main metabolite (2-aminobenzimidazole). On this basis, a brief outlook on the future research directions of benzimidazole fungicides is presented.

Four Propiconazole Stereoisomers: Stereoselective Bioactivity, Separation via Liquid Chromatography-Tandem Mass Spectrometry, and Dissipation in Banana Leaves.

In this study, we evaluated the stereoselective bioactivity of four propiconazole stereoisomers against the causal agents of the banana leaf spot disease (Curvularia lunata and Colletotrichum musae). We also evaluated the stereoselective degradation of the stereoisomers in banana leaves under field test conditions. The Superchiral S-OX column successfully separated the four propiconazole stereoisomers. X-ray single-crystal diffraction confirmed that the absolute configuration of the cis-stereoisomer-(+)-A of propiconazole was (2R,4S)-propiconazole and that of the cis-stereoisomer-(-)-A of propiconazole was (2S,4R)-propiconazole. In vitro antibacterial results revealed that (2R,4S)-(+)-propiconazole had the highest activity against the two target plant fungi. In this study, a new and efficient high-performance liquid chromatography tandem mass spectrometry method was developed for the determination of the four stereoisomeric residues of propiconazole in banana leaves. The mean recoveries of the method for the stereoisomers were 76.3-103% with relative standard deviations of 1.25-11.4%. The four propiconazole stereoisomers had a detection limit of 0.002-0.006 mg/kg and a limit of quantification of 0.02-0.03 mg/kg in banana leaves. Propiconazole-(-)-B and propiconazole-(-)-A degraded slightly faster than their corresponding enantiomers propiconazole-(+)-B and propiconazole-(+)-A in banana leaves collected from three typical banana production areas.

Dissipation Dynamics, Terminal Residues and Dietary Risk Assessment of Two Isomers of Dimethacarb in Rice by HPLC-MS/MS.

Dimethacarb is a carbamate insecticide developed in China that contains 3,5-dimethylphenyl methylcarbamate (XMC) and 3,4-dimethylphenyl methylcarbamate (MPMC) isomers. Dimethacarb has been registered for use in rice in China, but no residue or degradation of dimethacarb in rice has been reported and the maximum residue limits (MRLs) for rice have not been established. A versatile high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed with modified QuEChERS sample preparation to determine two isomers of dimethacarb in rice. The average recovery of XMC and MPMC in brown rice, rice husk, and rice straw ranged from 71.69 to 100.60%, with spike levels of 0.01 to 1 mg/kg and relative standard deviations (RSDs) of 0.21 to 8.41%. Field experiments showed that the half-lives of XMC and MPMC in rice straw were 4.08 to 4.23 days and 3.48 to 3.69 days, respectively. Final residues of XMC and MPMC in rice husk after 21 days of spraying at six sites ranged from 0.23-2.65 mg/kg and 0.06-1.10 mg/kg, and <0.01-0.16 mg/kg and <0.01-0.04 mg/kg in brown rice. The ratio of XMC to MPMC content in the rice husk differed from the original 50% dimethacarb EC, indicating the difference in the degradation rate of XMC and MPMC. The estimated risk quotient (RQ) for both XMC and MPMC was less than 30%. These data for residues from six representative locations could provide a reference for establishing the MRL of dimethacarb in rice.

Enantioselective Analysis and Degradation Studies of Four Stereoisomers of Difenoconazole in Citrus by Chiral Liquid Chromatography-Tandem Mass Spectrometry.

Four difenoconazole stereoisomers were well separated on a Superchiral S-OX column. The absolute configurations of the four stereoisomers of difenoconazole eluted in an orderly fashion with the chiral column were confirmed as (2S,4S), (2S,4R), (2R,4R), and (2R,4S)-difenoconazole, respectively, by single-crystal X-ray diffraction. For the first time, a simple and efficient trace detection method for the determination of residues of the four stereoisomers of difenoconazole in a plant sample by HPLC-MS/MS was developed. The mean recoveries were 78.23-104.38% with RSDs of 0.33-9.95%. The limits of detection for the four difenoconazole enantiomers were 0.0002-0.0004 mg/kg, and the limits of quantitation were 0.0044-0.011 mg/kg in citrus leaves and whole fruits. There was no obvious enantioselectivity upon degradation of the four stereoisomers in citrus leaves and whole fruits in Hunan and Guizhou. In Guangzhou, the rate of degradation of (2R,4R)-difenoconazole was the slowest among the four stereoisomers of difenoconazole.

Bagging and non-bagging treatment on the dissipation and residue of four mixed application pesticides on banana fruit.

BACKGROUND: Bananas are vulnerable to disease and insect pests after producing fruit. In order to increase the yield and produce high-quality fruit, the insecticides and fungicides are mixed and applied 2-3 times on banana, then the fruit is bagged. Buprofezin, imidacloprid, difenoconazole, and pyraclostrobin are widely used on banana. However, there is a lack of research on the effect of fruit bagging on pesticide dissipation and residues on bananas. RESULTS: A versatile liquid chromatography-tandem mass spectrometry method with modified QuEChERS sample preparation has been developed for the determination of buprofezin, imidacloprid, difenoconazole, and pyraclostrobin in bananas. The recovery of four pesticides was satisfactory (74.96-98.63%) with reasonable relative standard deviation (≤ 8.78%). In Hainan and Guangzhou, the half-lives of the four pesticides were 4.68-13.9 and 5.63-20.4 days in non-bagged and bagged bananas, respectively. The significance analysis of the half-lives in the two sites showed that the dissipation rates of the three pesticides (imidacloprid, difenoconazole, pyraclostrobin) on whole bananas were significantly decreased by the effect of bagging (P < 0.05). However, there was no significant difference in the degradation of half-life of buprofezin under bagging and without bagging (P > 0.05). CONCLUSION: The high vapor pressure and the non-systemic property cause buprofezin to evaporate and dissipate the fastest among the four studied pesticides. The ultimate residues of four pesticides in bananas are lower than the maximum residue limits in China after three times of mixed applications under bagging or non-bagging. The results provide scientific data for evaluating the safety of four pesticides in banana bagging. © 2020 Society of Chemical Industry.