The interactions between piperonyl butoxide and E4, a resistance‐associated esterase from the peach‐potato aphid,Myzus persicae Sulzer (Hemiptera: Aphididae)

BACKGROUND: It has been reported previously that piperonyl butoxide (PBO) can inhibit both P450 and esterase activity. Although the method by which PBO combines with cytochrome P450 has been identified, the way in which it acts as an esterase inhibitor has not been established. This paper characterises the interactions between PBO and the resistance‐associated esterase in Myzus persicae, E4. RESULTS: After incubation with PBO/analogues, hydrolysis of 1‐naphthyl acetate by E4 is increased, but sequestration of azamethiphos is reduced. Rudimentary in silico modelling suggests PBO docks at the lip of the aromatic gorge. CONCLUSIONS: PBO binds with E4 to accelerate small substrates to the active‐site triad, while acting as a blockade to larger, insecticidal molecules. Structure–activity studies with analogues of PBO also reveal the essential chemical moieties present in the molecule. © 2012 Society of Chemical Industry     

增效剂与三种杀虫剂混配对石榴蓟马的毒力测定

为了解增效剂对不同杀虫剂的增效作用和参与石榴蓟马抗药性形成的解毒酶，采用三种杀虫剂与增效剂混配对石榴蓟马（西花蓟马、黄胸蓟马）进行毒力测定。结果表明：增效醚（PBO）对三种杀虫剂（毒死蜱、啶虫脒和吡虫啉）都有显著增效作用，其中毒死蜱 PBO的增效比最强，对黄胸蓟马三龄若虫、成虫的增效比分别为5.188、5.869；对西花蓟马三龄若虫、成虫的增效比分别为4.727、5.152。表明多功能氧化酶（MFO）参与了石榴蓟马体内抗药性的形成。     

噻虫嗪对褐飞虱的毒力及解毒代谢酶活性的影响

【目的】明确噻虫嗪对褐飞虱Nilaparvata lugens的抗药性及解毒代谢酶活性的影响。【方法】采用稻苗浸渍法测定褐飞虱温室种群对吡虫啉、噻虫嗪、噻嗪酮和毒死蜱的抗药性,以及对新型防控药剂氟啶虫胺腈和三氯苯嘧啶的敏感性;研究增效剂胡椒基丁醚(PBO)、马来酸二乙酯(DEM)和磷酸三苯酯(TPP)对噻虫嗪的增效作用;测定了羧酸酯酶、谷胱甘肽S-转移酶和细胞色素P450s酶活性。【结果】褐飞虱种群对噻虫嗪表现出高水平抗性,抗性倍数达到277.92倍,对氟啶虫胺腈和三氟苯嘧啶仍处于敏感水平,对三氟苯嘧啶无交互抗性。PBO对噻虫嗪的增效作用最强,增效倍数为1.99倍。温室抗性种群的细胞色素P450s活性达到4.70×10-3 IU/mg,为室内敏感品系的2.13倍。【结论】细胞色素P450s活性的增强可能是褐飞虱对噻虫嗪产生代谢抗性的主要原因。氟啶虫胺腈和三氟苯嘧啶轮换使用可有效防控褐飞虱。     

Effect of pretreatment with piperonyl butoxide on pyrethroid efficacy against insecticide-resistant Helicoverpa armigera (Lepidoptera: Noctuidae) and Bemisia tabaci (Sternorrhyncha: Aleyrodidae)

Pyrethroid resistance in B-type Bemisia tabaci Gennadius and Australian Helicoverpa armigera Hübner field populations is primarily conferred by esterase isoenzymes which metabolise and sequester pyrethroid insecticides. It has been shown previously that pyrethroid resistance-associated esterases in H. armigera are inhibited by the insecticide synergist piperonyl butoxide (PBO) over a 22-h period. It is demonstrated here that similar inhibition can be obtained against B-type B. tabaci. Small-scale field trials showed excellent levels of pyrethroid control when insects were pretreated with PBO and then dosed with pyrethroid during the time of maximum esterase inhibition. These results demonstrate that PBO can restore pyrethroid efficacy in the field against both B-type B. tabaci and resistant H. armigera.     

Quantitative structure-activity studies of substituted benzyl chrysanthemates: 1. Correlations between symptomatic and neurophysiological activities against American cockroaches

A number of substituted benzyl (1R)-trans-chrysanthemates and related compounds were synthesized. Their symptomatic activities in terms of levels which induce convulsions as well as cause death in American cockroaches were determined by injection with and without application of synergists as inhibitors of metabolism. The neuroexcitatory and neuroblocking activities were also determined in terms of minimum effective concentrations to induce repetitive train of impulses and conduction blockage, respectively, to central nerve cords excised from the cockroaches and immersed in Ringer's solution. Correlations between symptomatic and neurophysiological activities were analyzed quantitatively with the aid of molecular hydrophobicity parameter and regression analysis. Each symptomatic activity from which the effect of metabolism is eliminated was found to be analyzable by means of a linear combination of indices for two types of neurophysiological activity when the transport factor is separated by using the hydrophobicity parameter. A closer correlation was found between neuroblocking activity and the “convulsive” effect than between neuroexcitatory activity and the “convulsive” effect, whereas both neurophysiological effects operate together on the cockroaches resulting in paralysis and death.     

Does synergized pyrethrin applied over wetlands for mosquito control affect Daphnia magna zooplankton or Callibaetis californicus mayflies?

BACKGROUND: Public health agencies may apply aerosolized synergized pyrethrin over wetlands repeatedly to control mosquitoes. This concerns wildlife managers because studies have shown the accumulation of pyrethroids, which are chemically similar to pyrethrin, in sediments in amounts that can be toxic to invertebrates. The authors tested whether repeated applications of synergized pyrethrin over wetlands caused mortality of two aquatic invertebrates: the zooplankton Daphnia magna Straus and a mayfly, Callibaetis californicus Banks. Fifteen wetland mesocosms were either exposed to repeated pyrethrin sprays or were protected by lids. Invertebrates in screened cages were placed in mesocosms before the fifth and eleventh spray, and directly into wetlands before spray 11. Six mesocosms were exposed to spray deposition. Caged adult mosquitoes were used to verify that sprays drifted over mesocosms. Sediments were analyzed for insecticide residues.RESULTS: There were no detectable effects of synergized pyrethrin on 36 h survival of Daphnia or mayflies, but most exposed adult mosquitoes died. Some exposed sediments yielded pyrethrin (< or =34.5 ng g(-1)); most showed piperonyl butoxide (PBO) (< or =14.9 ng g(-1)).CONCLUSIONS: Deposition of aerosolized 25% pyrethrin + 5% PBO may contaminate wetlands, but its application at rates used for mosquito control did not produce detectable effects on indicator species.     

Aldrin epoxidation and dihydroisodrin hydroxylation as probes of in vivo and in vitro oxidative metabolic capability of some caterpillars

Comparative biochemical studies are productive means to study factors that limit both beneficial and harmful effects of chemicals. Reactions such as aldrin epoxidation and dihydroisodrin hydroxylation are valuable assays of oxidative metabolism in scientific studies of chemical biology in insects, subhuman primates and other living things. The tissue distribution of activity in caterpillars may have functional significance. Localization of relatively high concentrations of these cytochrome P450 monooxygenases in gut tissue of lepidoptera may represent an important means to minimize absorption of lipophilic foreign chemicals in food. Some polychlorocycloalkanes permit in vivo and in vitro studies owing to their stability, acceptable toxicity and relatively simple pattern of metabolism. In vivo studies to assess the significance of in vitro findings are feasible with substrates such as aldrin, dihydroisodrin (DHI) and oxidative methylenedioxyphenyl inhibitors such as piperonyl butoxide (PBO) or carbon monoxide. Biphasic dose-dependent decreased and increased DHI-OH formation resulted from PBO pretreatment by gut, fat body, head and Malpighian tubule homogenates of cutworms and gut and fat body (the only tissues tested) of cabbage looper Trichplusia ni (Hübner) and black cutworm Agrotis ipsilon (Hüfnagel). The biphasic in vivo responses of caterpillars to PBO are a reminder of the complexity of biochemical and physiological responses of organisms coexposed to chemicals that are classified, often glibly, as toxic substances and metabolic inhibitors and inducers. Knowledge of dose and time relationships demands very careful evaluation in living things in the environment.     

Laboratory evaluation of natural pyrethrins, pymetrozine and triflumuron as alternatives to controlCeratitis capitata adults

Three insecticides, pyrethrins + piperonil butoxide (PBO), pymetrozine and triflumuron, were tested as potential alternatives for controlling the Mediterranean fruit flyCeratitis capitata (Wiedemann) (Diptera: Tephritidae). The compounds were administered to adult flies in the laboratory by different uptake methods at the recommended rates currently used in fruit crops in Spain. Pyrethrins + PBO (80 + 320 ppm a.i.) exhibited a comparable knock-down effect to malathion (1,500 ppm a.i.) in the laboratory, irrespective of the method of application used. After these results were obtained, the number of concentrations tested was increased to carry out a dose-response analysis. Pymetrozine (300 ppm a.i.) and triflumuron (150 ppm a.i.) did not kill adults at the concentrations tested. However, pymetrozine diminished the fecundity, especially when adults were fed the insecticide; egg hatch was decreased by 59.3% compared with controls. Further experiments showed that increased period of ingestion and higher concentrations had a clear effect in reducing both fecundity and fertility. The possible use of pyrethrins + PBO and pymetrozine to reduce populations ofC. capitata is discussed. http://www.phytoparasitica.org posting July 22, 2006. Corresponding author     

Enhancement of thiazopyr bioefficacy by inhibitors of monooxygenases

The preceding paper described inhibition of thiazopyr metabolism in plant seedlings by inhibitors of cytochrome P450 monooxygenases, and the lack of inhibition by esterase inhibitors. We now describe greenhouse evaluation of the effects of these metabolic inhibitors on the bioefficacy of thiazopyr. Inhibitors of cytochrome P450 monooxygenases, piperonyl butoxide (PBO), 1-aminobenzotriazole (ABT), metyrapone (MET) and tetcyclacis (TET), all enhanced the bioefficacy of thiazopyr against pigweed and other plant species. In contrast, inhibitors of esterases, tributyl phosphate (TBP) and triphenyl phosphate (TPP), produced only slight enhancement of thiazopyr activity. The effect of PBO was dose-dependent and was demonstrated against barnyardgrass, grain sorghum, redroot pigweed, seedling johnsongrass, and giant foxtail. PBO demonstrated no enhancement of thiazopyr activity in velvetleaf, tall morningglory, cotton, or soybeans. Bioefficacy was most enhanced via exposure of seedling shoots to PBO and thiazopyr. The combination of results from the present and the preceding papers suggests that PBO enhances thiazopyr bioefficacy by effectively inhibiting thiazopyr metabolism in plants.