Soil dissipation and biological activity of metolachlor and S-metolachlor in five soils

The resolved isomer of metolachlor, S-metolachlor, was registered in 1997. New formulations based primarily on the S-metolachlor isomer are more active on a gram for gram metolachlor basis than formulations based on a racemic mixture of metolachlor containing a 50:50 ratio of the R and S isomers. The labelled use rates of S-metolachlor-based products were reduced by 35% to give equivalent weed control to metolachlor. However, several companies have recently registered new metolachlor formulations with the same recommended use rates for weed control as S-metolachlor. This research was done to compare the soil behaviour and the biological activity of metolachlor and S-metolachlor in different soils under greenhouse and field conditions. Although K(d) ranged from 1.6 to 6.9 across the five soils, there were no differences in the binding of metolachlor and S-metolachlor to soil or in the rate of soil solution dissipation in a given soil. However, both greenhouse and field studies showed that S-metolachlor was 1.4-3-fold more active than metolachlor against Echinochloa crus-galli (L.) Beauv. in five different soils and that S-metolachlor was more active than metolachlor in three Colorado field locations. When the rates of metolachlor and S-metolachlor were adjusted for S isomer concentrations in the formulations, there were no differences between the formulations in field, greenhouse or bioassay studies. Thus herbicidal activity is due to the S isomers, with the R isomers being largely inactive.     

Contribution to the toxic action of S-methyl fenitrothion

The toxicity of the S-methyl isomer of fenitrothion was found to be higher than that of both fenitrothion and technical fenitrothion. Repeated administration of the compound showed a rapid decrease in toxicity with decreasing doses.Excretion of p-nitro-m-cresol into the urine of rats was more rapid and the excreted amounts were larger from a single dose of the isomer than from fenitrothion.Single doses of the isomer increased the pentobarbitone sleeping time in mice at both 24 and 48 hr, but showed no change after 4 days. Administration of the isomer and purified fenitrothion to mice for 1 week had no effect on the pentobarbitone sleeping time, nor did a single dose of fenitrothion change the effectiveness of pentobarbitone.Dominant lethal tests in rats revealed a possible mutagenic effect from this compound.The anticholinesterase activity of the fenitrothion S-methyl isomer in vitro was found to be two to three times higher than that of fenitrothion.     

Biological Activity of Two Stereoisomers of the N-Thienyl Chloroacetamide Herbicide Dimethenamid

Due to the presence of an asymmetrically substituted C atom, dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide], a recently introduced N-thienyl chloroacetamide herbicide, exists as two stereoisomers (S and R) having differing herbicidal activities as demonstrated with a selection of weeds and Lemna minor. The activity of the two isomers was investigated in greater detail with the green alga Scenedesmus acutus and compared to that of alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide]. As with alachlor, the S isomer (5 μM ) strongly inhibited algal growth and fatty acid desaturation while the R isomer had no effect. In short-term experiments (up to 5·5 h), the S isomer and alachlor (100 μM ) inhibited [¹⁴C]acetate uptake and its incorporation into fatty acids in the same manner, while the R isomer did not. Incorporation of [¹⁴C]acetate into a non-lipid fraction of the algae was strongly inhibited by alachlor and the S isomer (100 μM ) and only slightly by the R isomer. A 50% inhibition of incorporation of [¹⁴C]oleic acid into the same non-lipid fraction was attained with less than 10^-7 M of the S isomer while 10^-5 M of the R form of dimethenamid achieved only a 40% inhibition. The same stereospecificity of the compound on growth, fatty acid desaturation, acetate uptake and oleic acid incorporation provides strong evidence that dimethenamid may act upon a primary, specific target in lipid metabolism. Furthermore, the comparable biological activities of dimethenamid and alachlor indicate that this target is common to both N-phenyl and N-thienyl chloroacetamide herbicides. © 1997 SCI.     

Toxicokinetics of dicamba (3,6-dichloro-2-methoxy-benzoic acid) and its 3,5-dichloro isomer following intravenous administration to rats

The distribution and elimination of dicamba (3,6-dichloro-2-methoxy benzoic acid) and another isomer present in dicamba formulation (3,5-dichloro-2-methoxy benzoic acid) were studied in rats following single intravenous injections. Concentrations of dicamba and the isomer were measured at various times in whole blood by EC-GLC after extraction and derivatization with diazomethane. The isomer had different toxicokinetic parameters compared to dicamba. The elimination of dicamba from the blood was rapid with a biological half-life of 0.64 hr (following 100 mg/kg iv dose) while the elimination of the isomer from the blood was much slower with a biological half-life of 16.5 hr (following 20 mg/kg iv dose). However, upon combined dosing of the two compounds the elimination rate constant of dicamba significantly decreased. The isomer had a greater degree of binding to blood serum proteins than dicamba.     

Indol-3-ylacetic acid- and calmodulin-regulated Ca2+-ATPase: A target for the phytotoxic action of hexachlorocyclohexane

In rice seedlings, the organochlorine insecticide hexachlorocyclohexane (HCH) and its four major isomers—α,β, γ, and δ—have been shown to elicit their phytotoxic action by interacting with indol-3-ylacetic acid (IAA)-regulated growth and Ca²⁺-ATPase activity. When rice seedlings were grown in the presence of 0.34 mM HCH, seedling vigour was reduced to 33% of the control. A similar effect was observed when seedlings were grown in the presence of the γ and δ isomers, but not with the α and δ isomers of HCH. This reduced vigour could be restored by treating the seedlings with 100 nM IAA, suggesting that HCH and its isomers (γ and δ) limit either IAA synthesis or action or both. In a microsomal fraction from rice seedlings grown in the presence of either HCH or its isomers, the calmodulin-regulated Ca²⁺-ATPase activity was inhibited as follows: technical HCH = 46%, α isomer = 80%, β isomer = 72%, γ isomer = 65% and δ isomer = 62% of the control value, respectively. TLC analysis suggested that the various isomers of HCH are metabolised by the plant, except for the δ isotner, which accumulated. This isomer, along with the degraded products of other isomers, may be responsible for the phytotoxic action of HCH.     

Residues of tetrachlorvinphos and its breakdown products on treated crops. I.—Method development

Procedures are described for the analysis of crops for residues of tetrachlorvinphos (Gardona, trans-isomer of dimethyl 1-(2′,4′,5′-trichlorophenyl)-2-chloroyinyl phosphate) insecticide together with methods for the analysis for residues of its isomer and its conjugated and non-conjugated breakdown products. Suitable procedures for the extraction are described together with procedures for the cleanup of the extracts by partition or column chromatography and final analysis down to 0·01 ppm or less by gas-liquid chromatography with electron capture detection.     

New 2-phenyl-4,5,6,7-tetrahydro-2H-indazole derivatives as paddy field herbicides

A series of 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives containing various substituted isoxazolinylmethoxy groups at the 5-position of the benzene ring were synthesized and their herbicidal activities assessed under greenhouse and flooded paddy conditions. Among them, compounds having a phenyl or cyano substituent at the 3-position of the 5-methyl-isoxazolin-5-yl structure demonstrated good rice selectivity and potent herbicidal activity against annual weeds at 16-63 g AI ha(-1) under greenhouse conditions. Field trials indicated that these two compounds controlled a wide range of annual weeds rapidly with a good tolerance on transplanted rice seedlings by pre-emergence application. They showed a low mammalian and environmental toxicity in various toxicological tests.     

Pharmacokinetics of dicamba isomers applied dermally to rats

The pharmacokinetic profile of the herbicide dicamba (3,6-dichloro-2-methoxybenzoic acid) and its isomer (3,5-dichloro-2-methoxybenzoic acid) present in dicamba formulation was examined in rats given single dermal applications of 100 mg/kg of dicamba, 20 mg/kg of the isomer, or their combination at those rates. The concentration of the isomer in blood increased up to 9 hr following application and then declined slowly. The rate of clearance of dicamba from the blood greatly exceeded that of the isomer and was apparently of first order for both. The rate constants for first-order elimination (k_e) were 1.7 and 0.19 hr⁻¹ for dicamba and the isomer, respectively. The rates of absorption of the two chemicals through the skin as determined by urinary excretion was 0.0029 hr⁻¹ for dicamba and 0.0012 hr⁻¹ for the isomer. Urinary excretion of the original dose was 16.5% for dicamba and 7.5% for the isomer. Following the combined application, the kinetics of uptake and clearance was similar to that determined for each chemical administered alone.     

Photochemical isomerization of fluazifop-butyl

Fluazifop-butyl, butyl (RS)-2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]propionate, as a thin film on glass, was photo-rearranged by ultraviolet irradiation at 254 nm to the isomer, butyl (RS)-2-[4-hydroxy-3-(5-trifluoromethyl-2-pyridyl)phenoxy]propionate. The reaction followed first-order kinetics. A mechanism that accounts for the formation of this product is proposed.     

烟草甲性信息素及其异构体的简易合成法

从2,4-二甲基戊二酸出发,经酯化、还原、格氏反应、选择性保护分子中的一个羟基后,再经氧化及脱保护反应,以61%的总收率合成了烟草甲性信息素及其异构体——4,6-二甲基-7-羟基-3-壬酮(7);7经脱水环化反应,得到另一种烟草甲性信息素及其异构体——2,6-二乙基-3,5-二甲基-3,4-二氢呋喃(8)。各产物结构均经核磁共振氢谱、碳谱及质谱分析确证。     

Pyrethroid-hydrolyzing esterases in southern armyworm larvae: Tissue distribution,kinetic properties,and selective inhibition

Esterase activity hydrolyzing both [1RS,trans]- and [1RS,cis]-permethrin was detected in crude homogenates of the following southern armyworm (Spodoptera eridania Cramer) larval tissues: cuticle, gut, fat body, head capsule, Malpighian tubules, and silk gland. Neither substrate was detectably hydrolyzed by hemolymph. The highest esterase activities per insect equivalent of tissue were found in cuticle, gut, and fat body for the trans isomer and in cuticle and gut for the cis isomer. Each preparation hydrolyzed the trans isomer more rapidly, but the degree of specificity varied greatly between tissues. Differences in apparent K_m and V_max values between the three most active tissues were threefold or less for trans isomer hydrolysis, but differences between tissues of up to 100-fold were found for K_m and V_max values for cis isomer hydrolysis. Hydrolysis of the trans isomer in cuticle, gut, and fat body homogenates was only partially inhibited by α-naphthyl N-propylcarbamate (NPC). Concentrations of NPC giving maximal inhibition of trans isomer hydrolysis had little effect on the hydrolysis of the cis isomer. These results demonstrate that pyrethroid-hydrolyzing activity is broadly distributed in insect tissues and results from the combined activity of several esterases with different properties. It is likely that the trans and cis isomers of permethrin are hydrolyzed by separate enzymes in this insect.     

Residues of tetrachlorvinphos and its breakdown products on treated crops. III.—Residues on a range of field crops

A wide range of crops including top fruit, cereals, brassicas, root vegetables and cotton from field trials in several countries in 1965, 1966, 1967 and 1968 have been analysed for residues of tetrachlorvinphos (Gardona, trans-homer of dimethyl 1-(2′,4′,5′-trichlorophenyl)-2-chlorovinyl phosphate) foliar insecticide, its isomer and its potential breakdown products. The residues under field conditions were mainly of tetrachlorvinphos, its isomer and 1-(2′,4′,5′-trichlorophenyl)ethan-1-ol in free and sugar-conjugated forms. Tetrachlorvinphos was not unduly persistent on the crops and its initial half-life varied from 2 days on cabbage, to 7 days on potato foliage and to 12 days on pears (after the last of five applications). From one week after the final application onwards the highest residues of tetrachlorvinphos observed were on olives (1 ppm after 18 days after a single application of 0·1 % active material), maize leaf (2·8 ppm at 9·5 weeks after the last of two applications at 3 kg/ha), and cabbage (1·9 ppm at 12 days after the last of three applications at 0·5 kg/ha). The maximum residues of the alcohol in the free form were 3·2 ppm on maize leaf at 8 weeks from the second application at 1·5 kg/ha and in the conjugated form were 1·0 ppm on cauliflowers at 6 days after the last of four applications at 0·5 kg/ha.     

Stability and Biological Activity of Cyfluthrin Isomers

A GC-MS method capable of completely separating the four pairs of diastereoisomers of cyfluthrin is presented and the method used to show that isomerisation of the cyfluthrin enantiomers occurs in methanol. This methanol-induced isomerisation could also be demonstrated by bioassays using water fleas. The biological activities of the various cyfluthrin isomers contained in the commercial products cyfluthrin and beta-cyfluthrin were assayed using several strains of lepidopteran larvae including Plutella xylostella, Heliothis virescens and Spodoptera frugiperda. With the susceptible strains, the efficiencies of the isomers mixtures of cyfluthrin and beta-cyfluthrin were shown to obey the rules of additivity. However, in tests with a resistant strain of P. xylostella originating from Thailand, the ‘inactive’ isomer III acted synergistically with the active isomer IV. Resistance factors in strains of H. virescens and P. xylostella were found to be higher with cis than with trans isomers. This probably contributes to the superior action of cyfluthrin and beta-cyfluthrin against various pests of agricultural importance since the commercial products contain a high content of trans isomers (‘high trans pyrethroids’).     

Defense enzymes induced in cucumber roots by treatment with plant growth-promoting rhizobacteria (PGPR) and Pythium aphanidermatum

Root and crown rot of cucumber caused by Pythium aphanidermatum can be suppressed by various rhizobacteria or PGPR (plant growth-promoting rhizobacteria). When cucumber roots were treated with Pseudomonas corrugata 13 or Pseudomonas aureofaciens 63–28, phenylalanine ammonia-lyase (PAL) activity was stimulated in root tissues in 2 days and this activated accumulation lasted for 16 days after bacterization. Peroxidase (PO) and polyphenol oxidase (PPO) activities were increased in roots 2–5 days after bacterization with P. corrugata strain 13. After bacterized cucumber roots were challenged with P. aphanidermatum, the enzyme activities of PAL, PO and PPO increased as the disease developed on the roots. These accumulations peaked 4–6 days after pathogen inoculation. A split root system demonstrated that the three enzymes could be systemically induced by the Pseudomonas strains 63–28 and 13, as well as P. aphanidermatum. Furthermore, isoperoxidase native PAGE (polyacrylamide gel electrophoresis) analysis indicated that the peroxidase isomer forms in cucumber roots induced by rhizobacteria were different from that in roots infected with P. aphanidermatum. These results suggest that the plant defense enzymes could be stimulated in cucumber roots which have been colonized by non-pathogenic rhizobacteria or in a compatible interaction between cucumber and P. aphanidermatum. The mechanisms of PO activation by the rhizobacteria may be different from those of pathogen infection.     

Study of UV-shielding properties of novel porous hollow silica nanoparticle carriers for avermectin

The shielding protection given by self-prepared porous hollow silica nanoparticles (PHSN) to pesticides from degradation by UV light was investigated using avermectin as a model pesticide. It was demonstrated that PHSN carriers with a shell thickness of approximately 15 nm and a pore diameter of 4-5 nm have an encapsulation capacity of 625 g kg(-1) for avermectin using a supercritical fluid loading method. PHSN carriers exhibited remarkable UV-shielding properties for avermectin. This was affected by the intensity of UV light, the pH and the temperature of the release medium. Rises in UV intensity, pH and/or temperature reduced the UV protection of PHSN for avermectin. In addition, avermectin loaded into the inner core of the PHSN carriers was released slowly into the release medium for about 30 days following a typical sustained-release pattern. It thus appears that PHSN carriers have a promising future in applications requiring sustained pesticide release.     

Molluscicidal and antifungal activity of Erigeron speciosus steam distillate

The steam-distilled fraction of the aerial parts of Erigeron speciosus (Lindl) DC was tested for activity against strawberry plant pathogenic fungi Botrytis cinerea Pers ex Fr, Colletotrichum acutatum Simmonds, C fragariae Brooks, C gloeosporioides (Penz) Penz & Sacc, and the intermediate host snail Planobdella trivolvis that harbors the trematode, Bolbophorus confusus, that infests and causes severe infections in pond-raised catfish in the Mississippi Delta region of the USA. Bioautography on silica TLC plates demonstrated antifungal activity in the steam distillate. Preliminary bioassays of the steam distillate indicated the presence of phytochemicals toxic to P trivolvis. The bioactive compounds methyl 2Z, 8Z-deca-2,8-diene-4,6-diynoate and its 2E, 8E isomer were isolated by bioassay-guided fractionation and chromatographic techniques and identified by 1H NMR spectroscopy.     

Determination of residues of endosulfan and endosulfan sulfate on eggplant,mustard and chickpea

Extractable residues of endosulfan stereoisomers and its toxic metabolite, endosulfan sulfate, on a vegetable, an oilseed and a pulse crop were determined by gas-liquid chromatography. The study revealed that the alpha isomer degraded faster than the beta isomer. Beta-endosulfan accumulated during the first three days following the treatment. Endosulfan sulfate residues appeared a few days after application and decreased with time. The total endosulfan residues in the seeds from treated mustard ranged from 0.08 to 0.12 mg kg^?1 and were at or below the limit of determination (0.02 mg kg^?1) in chickpea seeds following harvest.     

Delayed toxicity after intravenous administration of bioresmethrin to rats

Capillary gas-liquid chromatographic analysis of seven commercial samples of bioresmethrin [5-benzyl-3-furylmethyl (1R)-trans-chrysanthemate] demonstrated that each contained toxicologically significant amounts (1-5%) of the (1R)-cis-isomer (cismethrin) as an impurity. Intravenous injection of the labelled compounds to rats indicated that the concentrated solutions of these compounds may precipitate in the blood and subsequently become trapped in the lung. Slow release of the toxic isomer impurity probably accounts for the delay in appearance of symptoms after intravenous administration of impure bioresmethrin. Similarly, higher doses of cismethrin can be tolerated when concentrated solutions are administered intravenously.     

Synthesis and insecticidal and acaricidal activity of new N-(α-substituted phenoxybenzyl)-4-pyrimidinamines

A new class of insecticides and acaricides containing N-(α-substituted phenoxybenzyl)-4-pyrimidinamines as core structure were synthesized and their insecticidal and acaricidal potencies assessed. Among these, both the N-(3 or 4-phenoxybenzyl)-4-pyrimidinamine showed remarkable activity against diamondback moth, Plutella xylostella L., brown rice planthopper, Nilaparvata lugens (Stal) and two-spotted spider mite, Tetranychus urticae Koch. The potency of the new pyrimidinamines was particularly increased when a methyl, ethyl, iso-propyl, or cyclopropyl group was introduced at the α-position of benzyl moiety and it was evident that a single (+) optical isomer is more active than its antipode. Structure-activity relationships are discussed.     

Opportunities for chiral agrochemicals

Chiral compounds account for 25% of all agrochemical compounds used commercially and for 26% of the total value of the world agrochemical market. However, those sold in single isomer form contribute only 7% to the market value despite many potential advantages in terms of regulatory, intellectual property and marketing benefits. Limited access to chiral raw materials and economic synthesis routes are key reasons why single isomers are less common than they might be. The development of more chiral routes will encourage the development of single isomer compounds to capitalise on their advantages.