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1.
Four synergists are used to evaluate the relative contribution of esterases and oxidases in the metabolism of four pyrethroids, the (+)-trans- and (+)-cis-isomers of resmethrin and tetramethrin, by five insect species and by mice. Three of these compounds are known pyrethroid synergists, S,S,S-tributyl phosphorotrithioate acting as an esterase inhibitor and piperonyl butoxide and O-(2-methylpropyl) O-(2-propynyl) phenylphosphonate acting as oxidase inhibitors. The fourth synergist, 1-naphthyl N-propylcarbamate, is an esterase inhibitor selected by screening 65 candidate esterase and oxidase inhibitors for maximal potency in synergizing the toxicity of trans-resmethrin to milkweed bugs. Naphthyl propylcarbamate synergizes the toxicity of trans-resmethrin and -tetramethrin to milkweed bugs, cockroaches, houseflies, cabbage loopers, and mealworms but not to mice. The persistence of trans-resmethrin in milkweed bugs treated by injection is increased by the esterase inhibitors while that of cis-resmethrin is increased by the oxidase inhibitors. The optimal synergist varies with the species and the pyrethoid, being related to both the nature of the pyrethroid alcohol moiety and the trans- or cis-configuration of the acid moiety. This probably results from species variations in the relative significance of esterases and oxidases in pyrethroid detoxification.  相似文献   

2.
An esterase or esterases in acetone powder preparations of mouse liver microsomes hydrolyze the cyclopropanecarboxylate ester linkage of pyrethroid insecticide chemicals derived from primary alcohols. The rate of cleavage of (+)-trans-chrysanthemates with various alcohol moieties decreases in the following order: 5-propargyl-2-furylmethyl; 5-benzyl-3-furylmethyl (bioresmethrin); 3-phenoxybenzyl; tetrahydrophthalimidomethyl esters. The hydrolysis rate of benzylfurylmethyl esters with various acid moieties decreases in the order: (+)- or (?)-trans-chrysanthemate; (+)-trans-ethanochrysanthemate; tetramethylcyclopropanecarboxylate; (+)- or (?)-cis-chrysanthemate or (+)-cis-ethanochrysanthemate. The trans-isomers of chrysanthemates and ethanochrysanthemates are hydrolyzed from 2.6- to more than 50-fold more rapidly than the corresponding cis-isomers. This enzyme system does not hydrolyze secondary alcohol esters, i.e., allethronyl (+)-trans- and (+)-cis-chrysanthemates.On intraperitoneal administration to mice, the (+)-trans-chrysanthemate and -ethanochrysanthemate of benzylfurylmethanol are of very low toxicity relative to the corresponding (+)-cis-isomers and the tetramethylcyclopropanecarboxylate. S,S,S-tributyl phosphorotrithioate (DEF) pretreatment increases the toxicity of these five compounds by 2.6- to more than 188-fold, with the exception of bioresmethrin whose toxicity is not altered. When the toxicity is increased, it is probably the result of esterase inhibition since DEF strongly inhibits the esterase activity of fresh liver microsomes while the mixed-function oxidase system remains active. The oxidase system metabolizes the chrysanthemates more rapidly than the ethanochrysanthemates of benzylfuryl-methanol. Depending upon the pyrethroid involved, the esterase or the mixed-function oxidase system, or both may be responsible for limiting the toxicity of these pyrethroids to mice.  相似文献   

3.
Forty-two insect metabolites of [1RS,trans]-and [1RS,cis]-permethrin are tentatively identified in studies with Periplaneta americana adults, Musca domestica adults, and Trichoplusia ni larvae involving administration of 14C preparations labeled in either the alcohol or acid moieties. The less-insecticidal trans isomer is generally metabolized more rapidly than the more-insecticidal cis isomer, particularly in cabbage looper larvae, and metabolites retaining the ester linkage appear in larger amount with cis-permethrin. Although the dichlorovinyl group effectively blocks oxidation in the acid side chain, the permethrin isomers are metabolized by hydrolysis and hydroxylation at the geminal-dimethyl group (either trans- or cis-methyl substituent) and the phenoxybenzyl group (predominantly at the 4′-position in all species but also at the 6-position in house flies). The alcoholic and phenolic metabolites are excreted as glucosides, and the carboxylic acids are excreted as glucosides and amino conjugates (glycine, glutamic acid, glutamine, and serine) with considerable species variation in the preferred conjugating moiety.  相似文献   

4.
Metabolism in mice of the separated cis- and trans-isomers of the pyrethroid insecticide cypermethrin (NRDC 149), (RS)-α-cyano-3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, was investigated in each case with preparations that were 14C-labelled in the benzyl and cyclopropyl moieties. Radioactivity from the trans-isomer was mainly excreted in the urine and that from the cis-isomer in the faeces. Elimination of both isomers was rapid except for a small portion (approximately 2%) of the cis-isomer which was released from the fat with a half-life of approximately 13 days. Metabolism of cypermethrin occurred mainly by ester cleavage and elimination of the cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl- cyclopropanecarboxylic acid moieties as glucuronide conjugates. The α-cyano-3-phenoxybenzyl alcohol released by ester cleavage was mainly converted to 3-phenoxy-benzoic acid which was partly eliminated unchanged, partly conjugated with aminoacids (mainly taurine) and glucuronic acid, and partly oxidised to 3-(4-hydroxyphenoxy) benzoic acid which was excreted as the sulphate conjugate. Metabolites retaining the ester linkage were formed by hydroxylation at various sites in the molecule with more hydroxylation of the cis- than of the trans-isomer occurring.  相似文献   

5.
The toxicity of a number of topically applied pyrethroids has been tested against adult male desert locusts, Schistocerca gregaria: the most potent proved to be 5-benzyl-3-furylmethyl (+)-trans-chrysanthemate (bioresmethrin) with a weighted mean LD50 of 4.0 μg/g. The remaining compounds may be ranked in order of toxicity as follows: 5-benzyl-3-furylmethyl (±)-cis-trans-chrysanthemate (resmethrin) > 4-allyl-2,6-dimethyl-benzyl(+)-trans-chrysanthemate > 4-allylbenzyl (+)-trans-chrysanthemate > 2,4,6-trimethylbenzyl (+)-cis-trans-chrysanthemate > 2,3,4-trimethylbenzyl (+)-cis-trans-chrysanthemate > 2,4-dimethylbenzyl (±)-cis-trans-chrysanthemate; 2-methylbenzyl (±)-cis-trans-chrysanthemate. A small factor of synergism (4.2) was obtained with bioresmethrin following pre-treatment with sesamex, but with resmethrin the synergistic ratio (1.6) was of little practical significance.  相似文献   

6.
Esterases in acetone powder preparations of milkweed bugs, cockroaches, houseflies, cabbage loopers, mealworms, and mouse liver hydrolyze the (+)-trans- and (+)-cis-isomers of resmethrin and tetramethrin but they do not hydrolyze S-bioallethrin. Homogenate fractions are less suitable than acetone powders for assaying the insect esterases due to interfering reactions or inhibitors. The milkweed bug, looper and mouse liver esterases cleave the trans-isomers more rapidly than the cis-isomers of resmethrin and tetramethrin but this isomer specificity is less prominent or not present with the other esterase sources. Pyrethroid-hydrolyzing esterases are much less active in insect than in mouse liver preparations. 1-Naphthyl N-propylcabamate is a more potent inhibitor than S,S,S-tributyl phosphorotrithioate for the insect esterases whereas the latter compound is more effective in inhibiting the mouse esterases. Both of these chemicals are noncompetitive inhibitors in each case suggesting that they carbamoylate and phosphorylate the detoxifying enzymes. Esterase inhibitors acting in the nmolar range may be useful synergists in species where pyrethroid detoxification by esterases limits the insecticidal action.  相似文献   

7.
Studies on the metabolism rates of 44 pyrethroids and 24 model compounds in mouse liver microsomal systems serve to divide the substrates into three groups based on their ease of hydrolysis and oxidation. Primary alcohol esters of trans-substituted cyclopropanecarboxylic acids are most rapidly metabolized with hydrolysis generally serving as the major component of the total metabolism rate. Although hydrolyzed slowly or not at detectable rates, the primary alcohol cis-substituted cyclopropanecarboxylates, tetramethylcyclopropanecarboxylates, and p-chlorophenyl-α-isopropylacetates are rapidly oxidized. The highly insecticidal α-cyano-3-phenoxybenzyl esters are least susceptible to metabolic attack due to both reduced esterase rates attributable to α substitution in the alcohol moiety and reduced oxidase rates for which no adequate explanation is currently available. Other structural modifications in the acid and alcohol moieties are less important in determining the metabolism rates. The substrate specificities of the microsomal esterases and oxidases are compared with in vivo pyrethroid structure-biodegradability relationships.  相似文献   

8.
The cis and trans isomers of the synthetic pyrethroid resmethrin, labelled with radiocarbon in either the alcohol or acid moiety, were individually administered orally to White Leghorn laying hens at a dosage of 10 mg kg?1. With each isomer and label position, greater than 90% of the radiocarbon was eliminated in the excreta within 24 h after the treatment. Radiocarbon residues in the egg white and yolk fractions were low, with peak levels observed 1 and 4-5 days after treatment in white and yolk, respectively. In birds sacrificed 12 h after treatment, radiocarbon residues in tissues were low; the highest levels were found in the liver and kidney.  相似文献   

9.
Permethrin was metabolised by attack at the ester bond, in vivo by adult cockroaches, Periplaneta americana and in vitro by esterase preparations. Metabolites retaining the ester linkage could not be detected. In all cases, the (1RS)-trans-isomer (transpermethrin) was more labile than the (1RS)-cis-isomer. Cypermethrin was metabolised at one-fifth the rate for permethrin. In-vitro and in-vivo studies with synergists indicated that cleavage of the ester bond in permethrin can be both oxidative for the (1RS)-cis-isomer and hydrolytic for the (1RS)-trans-isomer. The penetration of permethrin through the cuticle of the cockroach was significantly greater than that of cypermethrin. The penetration and metabolism of permethrin and cypermethrin in sixth-instar larvae of susceptible and resistant strains of the Egyptian cotton-leafworm, Spodoptera littoralis, were studied as possible factors in resistance. No significant differences were found. It is suggested that the major resistance factor to permethrin in S. littoralis is probably non-metabolic.  相似文献   

10.
Pyrethrins and the pyrethroids, bioallethrin ((+) trans-chrysanthemic acid ester of (±) allethrolone), resmethrin* (5-benzyl-3-furylmethyl (±)-cis,trans-chrysanthemate) and bioresmethrin? (5-benzyl-3-furylmethyl (+)-trans-chrysanthemate) were compared for insecticidal activity against free-flying Aedes aegypti L. in a Peet-Grady chamber using kerosene solutions and an aerosol particle size. The relative potency for kill of female mosquitoes was 1; 2.3; 6.8; 8.0 respectively. In further experiments, resmethrin and bioresmethrin were compared as aerosol formulations in a Comet 4C aircraft using caged and fed female A. aegypti. Both compounds at 0.1% (by wt.) in pressure packs and 35 g of formulation per 100 m3 provided 99% kill. It is suggested that pressure packs containing 0.5% (by wt.) of either compound should be adequate for disinsection of passenger aircraft. However, bioresmethrin would appear to be the compound of choice in view of its greater biological efficiency under laboratory conditions, and consequent probable greater margin of kill in practice.  相似文献   

11.
Esters of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid with appropriate alcohols are more active insecticides than the corresponding 3-isobutenyl compounds (chrysanthemates). (±)-Cis and (±)-trans forms of the dichloro acid are obtained by fractional crystallisation of the mixed acids or by hydrolysis of the ethyl esters separated by fractional distillation. The (±)-cis and (±)-trans acids are resolved into their (+)- and (-)-forms with α-methyl-benzylamine and threo-l-p-nitrophenyl-2-N,N-dimethyiamino-propane-1,3-diol respectively. As for the corresponding chrysanthemates, the (+)-cis and (+)-trans acids give esters more active as insecticides than their enantiomers.  相似文献   

12.
Adult Rana pipiens pipiens (Shreber) are highly sensitive to insecticidal α-cyano-3-phenoxybenzyl esters administered subcutaneously, i.e., LD50 0.13–0.35 mg/kg for deltamethrin and the most potent isomer of each of cis-cypermethrin, fenpropathrin, and fenvalerate and 0.65 mg/kg for (1R,αS)-trans-cypermethrin. Pyrethroids lacking the α-cyano substituent [pyrethrins, S-bioallethrin, kadethrin, and the Cis- and trans-isomers of (1R)-tetramethrin, (1RS)-resmethrin, (1R)-phenothrin, and (1R)-permethrin] vary greatly in their toxicity (LD50 0.14 to > 60 mg/kg) and the trans isomers are much less toxic than the corresponding cis isomers. The trans/cis specificity is due in large part to relative detoxification rates based on synergism studies with the resmethrin and permèthrin isomers and liver pyrethroid esterase assays with the permethrin and cypermethrin isomers. Poisoning by the noncyano compounds involves hyperactivity and tremors whereas by the cyanophenoxybenzyl esters involves tonic seizures and choreoathetosis, i.e., types I and II syndromes, respectively. Picrotoxinin, t-butylbicyclophosphate, and five other small cage compounds give a third type of syndrome with clonic seizures. Diazepam and its 2′-fluoro-4-methyl-4,5-dihydro analog (RO 5-3636) are more effective than 23 other compounds tested in protecting against deltamethrin toxicity. Diazepam is most effective in alleviating the Type II syndrome, intermediate with the type I syndrome, and is not active with picrotoxinin.  相似文献   

13.
Sugar beet, wheat, lettuce and cotton were grown in soil treated with [14C]permethrin, the crops being sown at intervals of 30, 60 and 120 days after treatment of the soil. The uptake of radioactive residues into these crops was measured. Low radioactive residues (up to 0.86 μg g?1) were detected in the mature plants sown 30 days after soil treatment, and this uptake declined significantly as the interval between soil treatment and sowing increased. Metabolites derived from the acid moiety of the permethrin molecule were shown to constitute the greater part of the residue transferring from the soil to the crops. (1RS)-cis- and (1RS)-trans-3-(2,2-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylic acid and 3-(2,2-dichlorovinyl)-1-methylcyclopropane-1,2-dicarboxylic acid were identified as the major acidic metabolites. The latter compound is a metabolite of permethrin which has not previously been identified in soil or plants.  相似文献   

14.
(Z)-cis- and (Z)-trans-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclo-propanecarboxylic acids react with bromine under radical conditions predominantly to open the cyclopropane ring; the stereochemistry and reactions of the dibromides thus formed are described.  相似文献   

15.
Various isomeric mixtures of pyrethroids were examined in topical application tests against houseflies, Musca domestica. On the basis of the activities of the separate isomers of 5-benzyl-3-furylmethyl (±)-cis,trans-chrysanthemate, it was shown that when combined in pairs to give the (±)-trans or (±)-cis or (+)-cis,trans mixtures the observed mortalities did not differ from those expected by simple additive action calculated by the harmonic mean. In contrast the (±)-cis,trans mixture showed considerable antagonism with a mortality only 60% of that expected. Similar evaluations using the separate and combined isomers of bioallethrin [(R,S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (allethronyl) ( + )-trans-[(1R,3R)-chrysanthemate] and the corresponding (+)-cis-(1R,3S)-chrysanthemate indicate antagonism calculated to be correlated with the content of the (R)-isomer of the alcoholic moiety. Hence the activity of the most active isomer of the “allethrin” series, (S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl ( + )-trans-(1R,3R)-chrysanthemate, (S)-bioallethrin, is not fully realised unless it is present in pure form and a substantial part of the value of bioresmethrin (5-benzyl-3-furylmethyl ( + )-trans-chrysanthemate] as a killing agent is lost when the racemic form is used. In racemic mixtures there is mutual antagonism between pairs of isomers so that considerable masking of activity occurs.  相似文献   

16.
The activity of the (+)-trans-chrysanthemic acid ester of (±)-allethrolone (Bio-allethrin) is shown to be superior to that of the (±)-cis, trans-isomers (allethrin), against houseflies, two species of grain beetle and larvae of the yellow fever mosquito. The efficiency of the (+)-trans-isomer compares favourably with that of pyrethrins when each is used alone or with piperonyl butoxide.  相似文献   

17.
1-(4′-Ethylphenoxy)-3,7-dimethyl-6,7-epoxy-trans-2-octene (the ethyl-epoxide), a potent insect morphogenetic agent, is converted to 6,7-diol and other derivatives in living cockroaches and mealworms. Enzyme preparations of these organisms, and of houseflies and several other insect species, also carry out these hydration and/or oxidation reactions. In addition, housefly microsomes epoxidize the ethyl-epoxide to a diepoxide. The diepoxide and diol are then converted by microsomes to at least six cyclic diols, probably via an epoxy-diol intermediate, the major ones being the cis- and trans-tetrahydrofurandiol derivatives. The metabolites formed by these reactions have little or no morphogenetic activity in Tenebrio assays. Attempts to find potent inhibitors for housefly epoxide hydratases were unsuccessful. The corresponding ethylphenyl geranyl ether is epoxidized by housefly microsomes, forming the more morphogenetically active ethyl-epoxide, but the major reaction is oxidation on the geranyl moiety to an unidentified olefinic carboxylic acid. The chemical modifications needed for improved stability and morphogenetic activity in this juvenoid series depend on the insect species and strain and the relative activities of their enzymes involved in various inactivation pathways.  相似文献   

18.
Separate esterase activities of rat and mouse liver microsomes hydrolyzing malathion, trans-permethrin, and cis-permethrin were differentiated on the basis of their sensitivities to inhibition by paraoxon and α-naphthyl N-propylcarbamate (NPC). In rat liver microsomes, the malathionhydrolyzing activity was more sensitive to both inhibitors and showed a different time course of NPC inhibition than the activities hydrolyzing the permethrin isomers. Paraoxon completely inhibited trans-permethrin hydrolysis, but only partially inhibited that of cis-permethrin. The paraoxonsensitive trans- and cis-permethrin-hydrolyzing activities were not differentially inhibited, but separate inhibition curves were obtained for the inhibition of trans- and cis-permethrin hydrolysis by NPC. The mouse liver esterase activity hydrolyzing trans-permethrin showed a similar paraoxon sensitivity to that of rat liver, but that the paraoxon-sensitive portion of the cis-permethrinhydrolyzing activity was 5.5-fold less sensitive to paraoxon than the corresponding rat liver activity and was clearly differentiated from the mouse liver trans-permethrin-hydrolyzing activity. The mouse liver malathion-hydrolyzing activity was 100-fold less sensitive to paraoxon and 14-fold less sensitive to NPC than the corresponding rat liver activity. Rat and mouse liver esterase activities hydrolyzed trans- and cis-permethrin at similar rates under standard assay conditions, but mouse liver esterases were 10-fold less active in hydrolyzing malathion. The higher specific activity of rat liver malathion-hydrolyzing esterases resulted from the greater apparent affinity and maximum velocity for malathion hydrolysis. These results demonstrate that the hydrolysis of malathion, trans-permethrin, and cis-permethrin by rat and mouse liver microsomal preparations involves several esterases with differing substrate specificities and inhibitor sensitivities.  相似文献   

19.
A pyrethrins-resistant strain of houseflies, 213ab, previously selected with a 1:10 (by wt.) mixture of natural pyrethrins and piperonyl butoxide, was further selected either with natural pyrethrins alone (strain NPR) or with resmethrin (strain 104). After 50 generations the two populations differed in their resistance to the natural and synthetic esters. Both were resistant to all pyrethroids. Part of strain NPR was immune and very much more resistant than strain 104 to the natural pyrethrins and allethrin, but it was only 2–3 times more resistant than strain 104 against the new synthetic esters resmethrin (5-benzyl-3-furylmethyl (±)-cis-trans-chrysanthemate), bio-resmethrin (5-benzyl-3-furylmethyl (+)-trans-chrysanthemate), pyresmethrin (5-benzyl-3-furylmethyl pyrethrate) and 5B2Me3FC (5-benzyl-2-methyl-3-furylmethyl (±)-cis-trans-chrysanthemate). Pretreatment of both strains with sesamex diminished but did not eliminate resistance. Synergism was greater in strain NPR, especially with natural pyrethrins and allethrin. Both strains had great resistance to DDT indicating that resistance to DDT and pyrethroids is linked. Differences in resistance to different compounds suggest that at least three factors can confer resistance, one of which, pen, delays penetration and two others involve detoxication, one py a on the acid side of the ester linkage and the other, py b, on the alcohol side. Natural pyrethrins and resmethrin select for different groupings of these factors. Treatment with resmethrin does not select for py b presumably because this mechanism cannot attack the resmethrin molecule. Similarly when piperonyl butoxide is added to the natural pyrethrins py b is inhibited and so removed from selection pressure. Under these conditions, the strain produced contains the same factors as one selected by resmethrin and so shows the same small resistance to natural pyrethrins alone.  相似文献   

20.
Abstract

The toxicity of a number of topically applied pyrethroids has been tested in the laboratory against three species of locusts and parathion-resistant and susceptible strains of the Egyptian cotton leafworm. Bioresmethrin, resmethrin and 5-benzyl-3-furylmethyl (+)-cis-chrysanthemate (NRDC 119) proved to be extremely active against one or more of these pests and there were small but noteworthy improvements with the synergists sesamex and TBTP. The field potential of the pyrethroids is discussed against the background of environmental problems associated with some of the insecticides in current use.  相似文献   

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