Cross-resistance, fitness costs, and biochemical mechanism of laboratory-selected resistance to tenvermectin A in Plutella xylostella.

BACKGROUND: Tenvermectin A is a new avermectin derivative that has good insecticidal and acaricidal effects. In order to study the resistance of Plutella xylostella to tenvermectin A, a sensitive strain (SS) and a laboratory-selected tenvermectin A-resistant strain (RS, 33.57-fold) were used to evaluate cross-resistance and fitness costs as well as to determine the resistance mechanism. RESULTS: There was no cross-resistance with common pesticides except for moderate cross-resistance with cypermethrin (resistance ratio = 10.26-fold) observed in RS. The activities of metabolic enzymes were measured, and the results showed that mixed function oxidase (MFO) and carboxylate esterase (CarE) in RS increased significantly by 2.92- and 2.86-fold, respectively, compared with SS. In addition, there was no obvious difference in glutathione-S-transferase (GST), which indicated that enhanced MFO and CarE activities may be the main mechanisms of detoxification. In the four typical resistance-related genes, expression of GluCl (4.86-fold), ABCC2 (3.85-fold), and CYP6 (2.94-fold) in RS were significantly promoted, but expression of GST was not. The clone and sequence of the PxGluClα subunit displayed six mutations that could lead to changes in the amino acid residues. CONCLUSION: High suitability related to tenvermectin A resistance was observed in RS, and it was found that the developmental stages of RS were significantly shortened and the survival rate of females was reduced. In addition, the mechanism of resistance to tenvermectin A may be regulated by the glutamate-gated chloride channel, ATP-binding cassette transporter, and MFO. In general, the study of resistance and biochemical mechanisms can provide beneficial and rational information for the management of resistance in P. xylostella. © 2021 Society of Chemical Industry.

Controllable Soil Degradation Rate of 5-Substituted Sulfonylurea Herbicides as Novel AHAS Inhibitors.

Chlorsulfuron has been applied in wheat fields as a recognized herbicide worldwide, yet it was officially banned in China since 2014 for its soil persistence problem. On the basis of our previous research that 5-dimethylamino distinctively accelerated degradation rate in soils, a modified amino moiety (Ia-c) and monosubstituted amino group (Id-e) were introduced onto the fifth position of the benzene ring in sulfonylurea structures, as well as heterocyclic amino substituents (If-g) to seek a suitable soil degradation rate during such an in situ crop rotation system. Referring to the biological data and ScAHAS inhibition and ScAHAS docking results, they turned out to be AHAS inhibitors with high potent herbicidal activities. The various influence on soil degradation rate along with crop safety indicated that different substituents on the fifth position have exerted an apparent impact. Their united study of structure-activity-safety-degradation relationship has great potential to provide valuable information for further development of eco-friendly agrochemicals.

Research on the controllable degradation of N-methylamido and dialkylamino substituted at the 5th position of the benzene ring in chlorsulfuron in acidic soil.

Owing to the lengthy residual problems associated with chlorsulfuron, metsulfuron-methyl, and ethametsulfuron, which prevents them from being used in the "annual multi-crop planting system", the application of these sulfonylurea herbicides (SU) has regrettably been terminated in China since 2014. In this field, we were the first to discover that the 5th position of the benzene ring in chlorsulfuron is a key point for influencing its degradation rate and the amino moiety at this position showed faster degradation rates and maintained their original potent bioactivity. In this study, we further elaborated on N-methylamido and dialkylamino substituents at the same position in chlorsulfuron to obtain 18 novel structures as M and N series. Their half-life degradation (DT50) values were faster, to varying degrees, than chlorsulfuron in acidic soil. It was found that most of the titled structures also retained their potent herbicidal activity and the crop safety of the M series towards corn greatly increased. Based on these data, a comprehensive graph describing the structure/degradation relationship was established first. Relating to the new molecules, their herbicidal activity (A), degradation rates (D), and crop safety (S) relationship were correlated and we used this approach to predict and explore the most preferable molecule, which coincided to the corresponding experimental data. The new concept of controllable degradation will provide us with more insight when searching for new ecological bioactive molecules in the future.

Research on Controllable Degradation of Novel Sulfonylurea Herbicides in Acidic and Alkaline Soils.

The degradation issue of sulfonylurea (SU) has become one of the biggest challenges that hamper the development and application of this class of herbicides, especially in the alkaline soils of northern China. On the basis of the previous discovery that some substituents on the fifth position of the benzene ring in Chlorsulfuron could hasten its degradation rate, apparently in acidic soil, this work on Metsulfuron-methyl showed more convincing results. Two novel compounds (I-1 and I-2) were designed and synthesized, and they still retained potent herbicidal activity in tests against both dicotyledons and monocotyledons. The half-lives of degradation (DT50) assay revealed that I-1 showed an accelerated degradation rate in acidic soil (pH 5.59). Moreover, we delighted to find that the degradation rate of I-1 was 9-10-fold faster than that of Metsulfuron-methyl and Chlorsulfuron when in alkaline soil (pH 8.46), which has more practical value. This research suggests that a modified structure that has potent herbicidal activity as well as accelerated degradation rate could be realized and this approach may provide a way to improve the residue problem of SUs in farmlands with alkaline soil.

Design, synthesis and herbicidal activity study of aryl 2,6-disubstituted sulfonylureas as potent acetohydroxyacid synthase inhibitors.

A series of sulfonylurea derivatives containing a 2,6-disubstituted aryl moiety were designed, synthesized and evaluated for their herbicidal activities. Most of these compounds showed excellent inhibitory rates against both monocotyledonous and dicotyledonous weeds, especially 10a, 10h and 10i. They exhibited equivalent or superior herbicidal efficiency than commercial chlorsulfuron at the dosage of 15g/ha and the preliminary SAR was summarized. In order to illuminate the molecular mechanism of several potent compounds, their apparent inhibition constant (Kiapp) of Arabidopsis thaliana acetohydroxyacid synthase (AHAS) were determined and the results confirmed that these compounds were all potent AHAS inhibitors. 10i have a Kiapp of 11.5nM, which is about 4 times as potent as chlorsulfuron (52.4nM).