Formic acid: A neurologically active, hydrolyzed metabolite of insecticidal formate esters

Formate esters have potential uses as insecticides in both grain fumigation and public health pest management. This research investigated the hydrolytic metabolism and neurological effects of formate ester compounds. Studies were conducted using Drosophila and houseflies as models for other dipteran pests of medical importance. Results indicated significant formic acid liberation from a broad range of formate esters, both in vivo and in vitro. Based on these initial observations, we subsequently investigated neurological effects of formic acid on the larval housefly nervous system. We found that formic acid caused significant neuroexcitation at concentrations lower than previously shown for inhibition of insect cytochrome c oxidase; however, this conclusion does not preclude that mitochondrial effects may also be occurring in non-nervous tissues. Finally, we investigated formate ester hydrolysis by A- and B-type esterases commonly considered in pesticide detoxification research; however, no significant interactions could be identified, suggesting that as yet unidentified carboxylesterases play roles in formate ester hydrolysis. These findings provide information on formate ester metabolism and modes of action, as well as rationale for further studies on formate ester neurotoxicology and mechanisms of selective toxicity.     

Characterization of the mechanism of action of the fungicide fenpicoxamid and its metabolite UK‐2A

BACKGROUND

Fenpicoxamid is a new fungicide for control of Zymoseptoria tritici, and is a derivative of the natural product UK‐2A. Its mode of action and target site interactions have been investigated.

RESULTS

UK‐2A strongly inhibited cytochrome c reductase, whereas fenpicoxamid was much less active, consistent with UK‐2A being the fungicidally active species generated from fenpicoxamid by metabolism. Both compounds caused rapid loss of mitochondrial membrane potential in Z. tritici spores. In Saccharomyces cerevisiae, amino acid substitutions N31K, G37C and L198F at the Qi quinone binding site of cytochrome b reduced sensitivity to fenpicoxamid, UK‐2A and antimycin A. Activity of fenpicoxamid was not reduced by the G143A exchange responsible for strobilurin resistance. A docking pose for UK‐2A at the Qi site overlaid that of antimycin A. Activity towards Botrytis cinerea was potentiated by salicylhydroxamic acid, showing an ability of alternative respiration to mitigate activity. Fungitoxicity assays against Z. tritici field isolates showed no cross‐resistance to strobilurin, azole or benzimidazole fungicides.

CONCLUSION

Fenpicoxamid is a Qi inhibitor fungicide that provides a new mode of action for Z. tritici control. Mutational and modeling studies suggest that the active species UK‐2A binds at the Qi site in a similar, but not identical, fashion to antimycin A. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Characterisation of QoI‐resistant field isolates of Botrytis cinerea from citrus and strawberry

BACKGROUND: In 2004, field isolates of Botrytis cinerea Pers. ex Fr., resistant to strobilurin fungicides (QoIs), were first found in commercial citrus orchards in Wakayama Prefecture, Japan. Subsequently, QoI‐resistant isolates of this fungus were also detected in plastic strawberry greenhouses in Saga, Ibaraki and Chiba prefectures, Japan. Biological and molecular characterisation of resistant isolates was conducted in this study. RESULTS: QoI‐resistant isolates of B. cinerea grew well on PDA plates containing kresoxim‐methyl or azoxystrobin at 1 mg L^?1, supplemented with 1 mM of n‐propyl gallate, an inhibitor of alternative oxidase, whereas the growth of sensitive isolates was strongly suppressed. Results from this in vitro test were in good agreement with those of fungus inoculation tests in vivo. In resistant isolates, the mutation at amino acid position 143 of the cytochrome b gene, known to be the cause of high QoI resistance in various fungal pathogens, was found, but only occasionally. The heteroplasmy of cytochrome b gene was confirmed, and the wild‐type sequence often present in the majority of resistant isolates, indicating that the proportion of mutated cytochrome b gene was very low. CONCLUSION: The conventional RFLP and sequence analyses of PCR‐amplified cytochrome b gene are insufficient for molecular identification of QoI resistance in B. cinerea. Copyright © 2009 Society of Chemical Industry     

Alternative Respiration: a Biochemical Mechanism of Resistance to Azoxystrobin (ICIA 5504) in Septoria tritici

The mechanism of resistance to ICIA 5504 (azoxystrobin) in a Septoria tritici mutant raised in the laboratory has been investigated. This mutant was approximately 10 times less sensitive than the wild-type strain in in-vitro tests towards spore germination or fungal growth. Glucose oxidation in whole cells was inhibited in the wild type (80% inhibition at 0·1 μg ml^-1), whereas in the resistant mutant, oxygen uptake was stimulated (50% stimulation at 1·0 μg ml^-1). Respiration of the wild-type strain was inhibited by antimycin A and cyanide but not that of the mutant. These results indicate the existence of an efficient alternative respiratory pathway in the mutant, which was inhibited by the addition of 2 mM salicylhydroxamate (SHAM). Using mitochondria, antimycin A and ICIA 5504 did not completely inhibit NADH oxidation in either strain. Addition of SHAM inhibited part of the antimycin- and ICIA 5504-insensitive oxygen uptake only in mutant mitochondria. For complete inhibition of oxygen reduction, SHAM and cyanide need to be present. Thus, three systems of electron transfer from exogenous NADH to oxygen are present in S. tritici mitochondria: the cytochrome pathway which is sensitive to ICIA 5504 and antimycin A inhibition in both strains, the system of NADH-cytochrome c reductase which bypasses the methoxyacrylate inhibition at the cytochrome bc₁ complex, and the alternative oxidase which is inhibited by SHAM, and which is partially functioning only in mitochondria isolated from the ICIA 5504-resistant mutant. When the S. tritici isolates were tested for their in-vivo sensitivity to ICIA 5504 on wheat, the resistant strain was controlled better than the wild type. This indicates that the decreased ATP formation by the alternative pathway of respiration was inadequate for efficient parasitic growth on the host. © 1997 SCI.     

Mode of resistance to respiration inhibitors at the cytochrome bc1 enzyme complex of Mycosphaerella fijiensis field isolates

Field isolates of Mycosphaerella fijiensis, causing black Sigatoka of banana, were characterised for their sensitivity to different inhibitors of the cytochrome bc₁ enzyme complex (Qo respiration inhibitors, strobilurin fungicides), using physiological, biochemical and molecular genetic methods. Strobilurin‐resistant isolates exhibited very high resistance factors both in mycelial growth inhibition and NADH consumption assays. Cross‐resistance was observed among all Qo inhibitors, including trifloxystrobin, azoxystrobin, famoxadone, strobilurin B and myxothiazol. However, the Qi and the cytochrome aa₃ inhibitors, antimycin A and potassium cyanide, respectively, were not cross‐resistant to Qo inhibitors. In sensitive but not in resistant isolates, mixtures of Qo inhibitors and SHAM, an inhibitor of the alternative oxidase (AOX), were more active than the components alone, indicating that the alternative pathway is essential in metabolism, but not causal for resistance. In the cell‐free NADH‐consumption assay, the Qo inhibitors affected the sensitive but not the resistant isolates, suggesting that AOX was not active in sub‐mitochondrial particles. In whole cells, however, the AOX has a basic expression level and is probably not inducible by trifloxystrobin. Sequencing of the cytochrome b gene of sensitive and resistant M fijiensis isolates revealed a difference in the nucleotide sequence leading to a single amino acid change from glycine to alanine at position 143 in the resistant isolate. This change is known to occur also in the naturally tolerant basidiomycete Mycena galopoda. It is suggested that the field isolates of M fijiensis can acquire resistance to Qo inhibitors due to a target site alteration with a single base pair change. Resistant isolates do not seem to contain a mixture of mutated and non‐mutated DNA, indicating a complete selection of resistant mitochondria and a maternally donated mode of resistance. © 2000 Society of Chemical Industry     

Neurological disruption by low-molecular-weight compounds from the heterobicyclic and formate ester classes

This research focused on two classes of synthetic and naturally derived toxins with the specific goal of identifying materials that elicit rapid neurological impacts. The insecticidal chemistries studied here included five heterobicyclic compounds and eight formate esters. We also tested four proven neurologically active materials as positive controls (GABA, indoxacarb, fipronil, and permethrin). Our approach involved the use of suction electrode recordings to measure spontaneous electrical activity from the intact larval housefly (Musca domestica) nervous system, before and after ligand treatments. This approach allowed for the quantification and statistical comparison of neurophysiological effects before and after treatment. Our results confirm that all heterobicyclics and several formate esters are neurologically active at the concentrations tested. Of these active compounds, menthofuran (a heterobicyclic) and butyl formate (a formate ester) were the most active. These results corroborate previous results of neurological mutant bioassays suggesting neurological activity by some materials at sodium and chloride channels. These overall findings, which verify neurological modes of action for a subset of low-molecular-weight toxins: (i) reveal key active chemistries, (ii) will enable the future testing of more refined experimental hypotheses, and (iii) will facilitate the design and testing of other novel insecticidal materials.     

Interaction of benzimidazole-N-sulfonamides with the cytochrome b/c1 complex of Pythium aphanidermatum

Experiments with intact cells and submitochondrial fractions of Pythium aphanidermatum (Edson) Fitz. indicated an interference of benzimidazole-N-sulfonamides with the NADH- or succinate-driven electron transport system between cytochromes b and c. Comparison with Ustilago maydis (DC) Corda and Botrytis cinerea Pers. ex Fr. revealed that this effect is Oomycetes specific. The molecular interaction between benzimidazole-N-sulfonamides and the mitochondrial cytochrome b/c₁ complex from P. aphanidermatum has been investigated. Binding assays with [¹⁴C]52232 RP (dimefluazole) indicated a time- and dose-dependent labelling of two proteins. The molecular mass of one labelled protein and the competition of the binding with antimycin A suggest that benzimidazole-N-sulfonamides interact with the Q₁-centre of cytochrome b. Furthermore, experiments with doubly labelled [³H][¹⁴C]CGA 323103 revealed a possible irreversible inactivation of the b/c₁ complex leading to covalent linkage of the dimethylsulfonamoyl moiety to the target site.     

Involvement of cytochrome P‐450 enzyme activity in the selectivity and safening action of pyrazosulfuron‐ethyl

To investigate the selectivity and safening action of the sulfonylurea herbicide pyrazosulfuron‐ethyl (PSE), pyrazosulfuron‐ethyl O‐demethylase (PSEOD) activity involving oxidative metabolism by cytochrome P‐450 was studied in rice (Oryza sativa L cv Nipponbare) and Cyperus serotinus Rottb. Cytochrome P‐450‐dependent activity was demonstrated by the use of the inducers 1,8‐naphthalic anhydride and ethanol, the herbicides PSE, bensulfuron‐methyl, dimepiperate and dymron, or the inhibitor piperonyl butoxide (PBO). Growth inhibition in C serotinus seedlings was more severe than that in rice seedlings. O‐Dealkylation activities of PSE were induced differently in rice and in C serotinus, with distinctly higher activity in rice seedlings. The induced PSEOD activities were slightly inhibited by PBO in rice seedlings, whereas they were strongly inhibited in C serotinus seedlings. Dimepiperate and dymron were effective safeners of rice against PSE treatment. Treatments with herbicide alone resulted in less induction of PSEOD activity compared with combined treatments of the herbicide and safener. PSEOD activity in rice seedlings induced with herbicide alone was strongly inhibited by PBO, whereas it was weakly inhibited in rice seedlings induced with combinations of PSE and two safeners. These results suggest that O‐demethylation by cytochrome P‐450 enzymes may be involved in the metabolism of PSE and may contribute to its selectivity and safening action. Furthermore, these results suggest the existence of a multiple form of cytochrome P‐450 in plants. © 2001 Society of Chemical Industry     

Synthesis and fungitoxic activity of 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles and their complexes

Cyclization of 3‐aryl‐1‐(2‐hydroxyphenyl)prop‐2‐en‐1‐ones with hydrazine hydrate in refluxing formic acid afforded the title ligands, 5‐aryl‐1‐formyl‐4,5‐dihydro‐3‐(2‐hydroxyphenyl)‐1H‐pyrazoles (HL¹–HL⁴, Ar = Ph, 4‐CH₃O‐C₆H₄‐, 2‐furyl, 2‐thienyl). Reaction of HL¹–HL⁴ with the divalent metal ions, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺, afforded novel complexes of the type [ML₂] (M = metal ion; L = deprotonated ligand) which were characterized by elemental analyses, molecular weight determinations, molar conductances, magnetic moments and electronic and infrared spectral data. The ligands behaved as tridentate, coordinating through the phenolic oxygen after deprotonation, N‐2 of the pyrazole ring and oxygen of the 1‐formyl group. The ligands and their complexes were evaluated for growth‐inhibiting activity against four phytopathogenic fungi. Macrophomina phaseoli was generally most sensitive followed by Alternaria alternata and Colletotrichum falcatum while Fusarium oxysporum was least sensitive to the tested compounds. The ligand HL¹ and its complexes showed the best activity against the fungi tested. © 2000 Society of Chemical Industry     

Inhibitory effect of bionic fungicide 2‐allylphenol on Botrytis cinerea (Pers. ex Fr.) in vitro

BACKGROUND: 2‐Allylphenol is a registered fungicide in China to control fungal diseases on tomato, strawberry and apple. It is synthetic and structurally resembles the active ingredient ginkgol isolated from Ginkgo biloba L. bark. 2‐Allylphenol has been used in China for 10 years. However, its biochemical mode of action remains unclear. An in vitro study was conducted on the biochemical mechanism of 2‐allyphenol inhibiting Botrytis cinerea (Pers. ex Fr.). RESULTS: The inhibition was approximately 3 times stronger when the fungus was grown on non‐fermentable source, glycerol, than that on a fermentable carbon source, glucose. Inhibition of B. cinerea and Magnaporthe oryzae (Hebert) Barr mycelial growth was markedly potentiated in the presence of salicylhydroxamic acid (SHAM), an inhibitor of mitochondrial alternative oxidase. Furthermore, at 3 h after treatment with 2‐allylphenol, oxygen consumption had recovered, but respiration was resistant to potassium cyanide and sensitive to SHAM, indicating that 2‐allylphenol had the ability to induce cyanide‐resistant respiration. The mycelium inhibited in the presence of 2‐allylphenol grew vigorously after being transferred to a fungicide‐free medium, indicating that 2‐allylphenol is a fungistatic compound. Adenine nucleotide assay showed that 2‐allylphenol depleted ATP content and decreased the energy charge values, which confirmed that 2‐allylphenol is involved in the impairment of the ATP energy generation system. CONCLUSION: These results suggested that 2‐allylphenol induces cyanide‐resistant respiration and causes ATP decrease, and inhibits respiration by an unidentified mechanism. Copyright © 2009 Society of Chemical Industry     

Mutations in the mitochondrial cytochrome b of Tetranychus urticae Koch (Acari: Tetranychidae) confer cross‐resistance between bifenazate and acequinocyl

BACKGROUND: Resistance of Tetranychus urticae Koch to bifenazate was recently linked with mutations in the mitochondrial cytochrome b Q_o pocket, suggesting that bifenazate acts as a Q_o inhibitor (Q_oI). Since these mutations might cause cross‐resistance to the known acaricidal Q_oI acequinocyl and fluacrypyrim, resistance levels and inheritance patterns were investigated in several bifenazate‐susceptible and bifenazate‐resistant strains with different mutations in the cd1 and ef helices aligning the Q_o pocket. RESULTS: Cross‐resistance to acequinocyl in two bifenazate‐resistant strains was shown to be maternally inherited and caused by the combination of two specific mutations in the cytochrome b Q_o pocket. Although most investigated strains were resistant to fluacrypyrim, resistance was not inherited maternally, but as a monogenic autosomal highly dominant trait. As a consequence, there was no correlation between cytochrome b genotype and fluacrypyrim resistance. CONCLUSIONS: Although there is no absolute cross‐resistance between bifenazate, acequinocyl and fluacrypyrim, some bifenazate resistance mutations confer cross‐resistance to acequinocyl. In the light of resistance development and management, high prudence is called for when alternating bifenazate and acequinocyl in the same crop. Maternally inherited cross‐resistance between bifenazate and acequinocyl reinforces the likelihood of bifenazate acting as a mitochondrial complex III inhibitor at the Q_o site. Copyright © 2009 Society of Chemical Industry     

Structure—activity relationships in pyrethroid esters derived from substituted 2-phenoxy-3-methylbutanoic acids

Non-cyclopropane pyrethroid esters of different substituted 2-phenoxy-3-methylbutanoic acids have been synthesised using the three alcohols—3-phenoxybenzyl alcohol, α-cyano-3-phenoxybenzyl alcohol and 3, 4-methylene-dioxybenzyl alcohol. Among the 35 esters synthesised and tested against Culex quinquefasciatus Say, the Bancroftian filariasis vector, for both larvicidal and adulticidal activities, α-cyano-3-phenoxybenzyl 2-(4-fluorophenoxy)-3-methylbu-tanoate, with an LC₅₀ value of 2.5 × 10^?3 mg litre^?1 for larvicidal activity, and α-cyano-3-phenoxybenzyl-2-(4-chlorophenoxy)-3-methylbutanoate, with an LD₅₀ value of 30 times; 10^?4 ug insect^?1 for adulticidal activity, were found to be as effective as fenvalerate, a well-known non-cyclopropane pyrethroid ester. Structure-activity studies showed that the insecticidal activity is dependent on the nature and position of the substituent in the phenyl ring of the acid moiety and also on the type of alcohol moiety.     

Efficacy of vaporised ethyl formate/carbon dioxide formulation against stored‐grain insects: effect of fumigant concentration,exposure time and two grain temperatures

BACKGROUND: The ethyl formate/carbon dioxide (CO₂) formulation Vapormate? is a rapid‐acting fumigant being developed for the control of stored‐grain insects. The effects have been investigated of concentration, exposure times of 1, 3, 24 and 72 h and two grain temperatures, 15 and 25 °C, on its efficacy against mixed‐stage cultures of Sitophilus oryzae (L.) Tribolium castaneum (Herbst) and strongly phosphine‐resistant Rhyzopertha dominica (F.) strain QRD569. RESULTS: High mortalities (≥92%) of mixed‐stage cultures of all three species were obtained when grain was fumigated with the formulation (193 g m^?3 ethyl formate) for 1 h. Complete control of R. dominica QRD569 and T. castaneum was achieved with 63 and 76 g m^?3 ethyl formate respectively, with exposure for 24 h, whereas mean mortality of S. oryzae was 86% under the same conditions. Mortalities of S. oryzae juvenile stages were significantly lower than adults under the conditions tested, which was due to pronounced tolerance of mid‐stage pupae to the fumigant. Reducing grain temperature from 25 to 15 °C had no effect on insect mortality. CONCLUSION: Ethyl formate/CO₂ formulation is highly effective against stored‐grain insects over a range of concentrations and exposure times. Efficacious fumigations were conducted in as little as 1 h, and a strongly phosphine‐resistant R. dominica strain was readily controlled with the fumigant. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd     

Effects of camptothecin and hydroxycamptothecin on insect cell lines Sf21 and IOZCAS-Spex-II

BACKGROUND: In recent years, concerns over the potential impact of synthetic pesticides on the environment have made the discovery and development of environmentally friendly pesticides a more pressing issue. Camptothecin (CPT) and its derivatives have attracted much attention owing to their unique mechanisms of action against insects. In this paper, two insect cell lines, Sf21 and IOZCAS‐Spex‐II, were used to conduct a preliminary investigation of the potential of CPT and hydroxycamptothecin (HCPT) as inducers of apoptosis in insect cell lines, and to illustrate the mechanism of action of CPT on insects at the cellular level. RESULTS: The results showed that both CPT and HCPT demonstrate potent cytotoxic effects to the tested insect cell lines in a time‐ and dose‐dependent manner. The DNA fragmentation, activation of caspases and cytochrome c release were observed in both IOZCAS‐Spex‐II and Sf21 treated with CPT and HCPT. There is no significant difference in cytotoxicity and caspase‐3 activation (P < 0.05, except when treated for 2 h) between CPT and HCPT, although the caspase‐3 activation was slightly stronger when treated with HCPT in both Sf21 and IOZCAS‐Spex‐II. CONCLUSION: The results confirm the existence of the mitochondrial‐dependent pathway of apoptosis induced by CPT and HCPT in Sf21 and IOZCAS‐Spex‐II cell lines. Further investigations are required to reveal the mitochondrial mechanisms and regulation of caspase activation during apoptosis. These studies will provide basic knowledge needed to understand the mechanisms of action of CPT and to develop CPT and its derivatives as insecticides. Copyright © 2011 Society of Chemical Industry     

The metabolism of fenvalerate in plants: The conjugation of the acid moiety

The metabolism of the pyrethroid insecticide fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate] ( I ), and of its most insecticidal (αS,2S) isomer ( II ), has been examined in cabbage plants grown and treated under laboratory conditions with [¹⁴C]chlorophenyl- and [ring-¹⁴C]benzyllabelled preparations of the two compounds. Both insecticides disappeared from the treated leaves with similar half-lives of approximately 12–14 days; they underwent ester cleavage to a significant extent, together with some hydroxylation at the 2- or 4-position of the phenoxy ring, and hydrolysis of the nitrile group to amide and carboxyl groups. Most of the carboxylic acids and phenols thus produced occurred as glycoside conjugates. In separate experiments, the uptake and metabolism of 2-(4-chlorophenyl)-3-methylbutyric acid ( X ), the acidic half of the molecule, were examined in the laboratory, using abscised leaves of kidney bean, cabbage, cotton, cucumber and tomato plants. The acid X was found to be readily converted, mainly into glucose and 6-O-malonylglucose esters in kidney bean, cabbage and cucumber plants, into glucosylxylose, sophorose and gentiobiose esters in cotton, and into two types of triglucose esters with differing isomerism in tomato. One of the acetyl derivatives of the trisaccharide conjugates was identical with the synthetic deca-acetyl derivative of the [1 → 6]-triglucose ester.     

A new aqueous suspension concentrate formulation of cis‐permethrin and its insecticidal activity

Isomers of pyrethroids usually have different insecticidal activities. Permethrin, a non‐cyano pyrethroid, is not an exception and cis‐permethrin is much more active than the trans‐isomer against Triatoma infestans, vector of Chagas' Disease in Argentina. The large‐scale separation of cis‐ and trans‐permethrin was performed by successive recrystallizations from ethanol‐water mixtures. An aqueous suspension concentrate (flowable) formulation of pure crystalline cis‐permethrin was prepared and assayed for its insecticidal activity on wood and ceramic surfaces against nymph V of T infestans. This formulation was at least three times more effective than deltamethrin, with LC₅₀ values on ceramic of 0.11 µg cm⁻² and 0.33 µg cm⁻² respectively. On wood surfaces, the LC₅₀ value was 0.57 µg cm⁻² compared with 3.20 µg cm⁻² for deltamethrin. Against other insect species such as Periplaneta americana, Aedes aegypti and Culex quinquefasciatus, the suspension concentrate formulation of cis‐permethrin was, however, less effective than similar formulations of deltamethrin or β‐cypermethrin. © 2000 Society of Chemical Industry     

Contact and fumigant activities of constituents of Foeniculum vulgare fruit against three coleopteran stored‐product insects

The insecticidal activities of materials derived from the fruit of fennel, Foeniculum vulgare, against adults of Sitophilus oryzae, Callosobruchus chinensis and Lasioderma serricorne were examined using direct contact application and fumigation methods. The biologically active constituents of the Foeniculum fruits were characterized as the phenylpropenes (E)‐anethole and estragole, and the monoterpene (+)‐fenchone, by spectroscopic analysis. Responses varied with insect species, compound, dose and exposure time. In a filter paper diffusion test, estragole at 0.168 mg cm^?2 caused 91% mortality to S oryzae adults within 1 day after treatment (DAT), whereas (+)‐fenchone and (E)‐anethole gave over 90% mortality at 2 and 4 DAT, respectively. Against C chinensis adults, all test compounds revealed potent insecticidal activities at 0.021 mg cm^?2 at 2 DAT. Against L serricorne adults at 0.105 mg cm^?2, (E)‐anethole gave 100% mortality at 1 DAT, whereas 90 and 60% mortality at 4 DAT was achieved with estragole and (+)‐fenchone, respectively. In a fumigation test, the test compounds were much more effective against adults of S oryzae, C chinensis and L serricorne in closed cups than in open ones, indicating that the insecticidal activity of test compounds was largely attributable to fumigant action. As naturally occurring insect‐control agents, the F vulgare fruit‐derived materials described could be useful for managing field populations of S oryzae, C chinensis and L serricorne. © 2001 Society of Chemical Industry     

Cross‐resistance and possible mechanisms of chlorpyrifos resistance in Laodelphax striatellus (Fallén)

BACKGROUND: Laodelphax striatellus (Fallén) is a major pest of cultivated rice and is commonly controlled in China with the organophosphate insecticides. To develop a better resistance management strategy, a chlorpyrifos‐resistant strain of L. striatellus was selected in the laboratory, and its cross‐resistance to other insecticides and possible mechanisms of the chlorpyrifos resistance were investigated. RESULTS: After 25 generations of selection with chlorpyrifos, the selected strain of L. striatellus developed 188‐fold resistance to chlorpyrifos in comparison with the susceptible strain, and showed 14‐ and 1.6‐fold cross‐resistance to dichlorvos and thiamethoxam respectively. There was no apparent cross‐resistance to abamectin. Chlorpyrifos was synergised by the inhibitor triphenyl phosphate; the carboxylesterase synergistic ratio was 3.8 for the selected strain, but only 0.92 for the susceptible strain. The carboxylesterase activity of the selected strain was approximately 4 times that of the susceptible strain, whereas there was no significant change in the activities of alkaline phosphatase, acid phosphatase, glutathione S‐transferase and cytochrome P450 monooxygenase between the strains. The Michaelis constant of acetylcholinesterase, maximum velocity of acetylcholinesterase and median inhibitory concentration of chlorpyrifos‐oxon on acetylcholinesterase were 1.7, 2.5 and 5 times higher respectively in the selected strain. CONCLUSION: The high cross‐resistance to the organophosphate dichlorvos in the chlorpyrifos‐resistant strain suggests that other non‐organophosphate insecticides would be necessary to counter resistance, should it arise in the field. Enhanced activities of carboxylesterase and the acetylcholinesterase insensitivity appear to be important mechanisms for chlorpyrifos resistance in L. striatellus. Copyright © 2010 Society of Chemical Industry     

Cross‐resistance,inheritance and biochemical mechanisms of imidacloprid resistance in B‐biotype Bemisia tabaci

BACKGROUND: The B‐type Bemisia tabaci (Gennadius) has become established in many regions in China, and neonicotinoids are extensively used to control this pest. Imidacloprid resistance in a laboratory‐selected strain of B‐type B. tabaci was characterised in order to provide the basis for recommending resistance management tactics. RESULTS: The NJ‐Imi strain of B‐type B. tabaci was selected from the NJ strain with imidacloprid for 30 generations. The NJ‐Imi strain exhibited 490‐fold resistance to imidacloprid, high levels of cross‐resistance to three other neonicotinoids, low levels of cross‐resistance to monosultap, cartap and spinosad, but no cross‐resistance to abamectin and cypermethrin. Imidacloprid resistance in the NJ‐Imi strain was autosomal and semi‐dominant. It is shown that enhanced detoxification mediated by cytochrome‐P450‐dependent monooxygenases contributes to imidacloprid resistance to some extent in the NJ‐Imi strain. Results from synergist bioassays and cross‐resistance patterns indicated that target‐site insensitivity may be involved in imidacloprid resistance in the NJ‐Imi strain of B. tabaci. CONCLUSION: Although oxidative detoxification mediated by P450 monooxygenases is involved in imidacloprid resistance in the NJ‐Imi strain of B‐type B. tabaci, target‐site modification as an additional resistance mechanism cannot be ruled out. Considering the high risk of cross‐resistance, neonicotinoids should be regarded as a single group when implementing an insecticide rotation scheme in B. tabaci control. Copyright © 2009 Society of Chemical Industry     

Synthesis and insecticidal activity of new pyrethroids

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D ‐mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)‐3‐formyl‐2,2‐dimethylcyclopropane‐1‐carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D ‐mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)‐3‐[(Z)‐2‐(4‐chlorophenyl)vinyl]‐2,2‐dimethylcyclopropane‐1‐carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana. Copyright © 2009 Society of Chemical Industry