Photolysis of Diniconazole-M under Sunlight

The photodegradation of diniconazole-M [(E)-(R)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-pentene-3-ol] was studied as thin film on glass surface under sunlight. Photoproducts were separated and identified by NMR, IR, UV and mass spectroscopy. They were characterised as the (Z)-isomer of diniconazole-M, a cyclic alcohol and its corresponding ketone and an isoquinoline derivative. © 1997 SCI.     

Inactivation of triforine by u.v. and sunlight on glass and on leaves of bean plants

Triforine is sensitive to u.v. and sunlight. The photochemical inactivation rate was higher in aqueous solution than in the solid state. In aqueous solution 50% of triforine was inactivated after 3 h irradiation with u.v. light and after 30 h exposure to sunlight. Eighty hours were necessary to decompose 25% of triforine in the solid state with sunlight on glass. The half life of triforine residues on the leaves of bean plants was about 60 h when exposed to solar irradiation. The inactivation of triforine by u.v. light and sunlight was accelerated in the presence of the sensitising chemicals riboflavin and xanthene; however, rhodamine B (C.I. 45170) showed only a small photosensitising activity.     

Photolysis of fluotrimazole

The major product identified in the photochemical degradation of fluotrimazole, in aqueous suspension, as a thin film on glass, and sprayed on barley leaves, was 3-(trifluoromethyl)triphenylmethanol. This was also detected after photolysis in methanol, although methyl 3-trifluoromethyltrityl ether was the major product. Moreover, under all these conditions, 3-(trifluoromethyl)triphenylmethane was also present. 3-Trifluoromethylbenzophenone was produced only by irradiation of an aqueous suspension. The photolysis products, in contrast to fluotrimazole, were inactive at 1 mmol against barley powdery mildew (Erysiphe graminis).     

Studies on photodegradation of chlorimuron-ethyl in soil

Photolysis of chlorimuron-ethyl was studied on a soil surface under sunlight and UV light. Eight photoproducts were isolated and characterised by spectroscopic methods. Major photoproducts are formed by cleavage of the sulfonylurea bridge and minor products are formed via dechlorination, hydrolysis and cyclisation. The rates of photodegradation of chlorimuron-ethyl on different soils followed first-order rate kinetics, with half lives of 22·3 h, 9·4 h, 4·9 h (UV) and 20·7 days, 11·1 days and 11·1 days (sunlight) for alluvial, red and laterite soils, respectively. The differences in rates of photodegradation were dependent upon the soil pH. © 1997 SCI     

A monoclonal antibody‐based ELISA for the analysis of the insecticide flucythrinate in environmental and crop samples

A competitive enzyme‐linked immunosorbent assay (ELISA) has been developed for the detection of the insecticide flucythrinate in environmental and food samples. Two types of haptens, the acid moiety that is the hydrolyzed product of flucythrinate, and the carboxylated propyl derivative of the alcohol moiety, were used to prepare monoclonal antibodies (MAbs). Five MAbs, which raised against the former hapten, were reactive with flucythrinate. Among them, MAb F1A27‐4 showed the highest activity toward flucythrinate, and did not cross‐react with other pyrethroids such as cycloprothrin, fenvalerate, fluvalinate, etofenprox and silafluofen. The assay conditions of indirect competitive ELISA with MAb F1A27‐4 were studied to optimize the detection of flucythrinate in environmental and food samples. Incubation at 4 °C in the assay buffer, pH 8, with 300 mM sodium chloride improved the sensitivity. The addition of rabbit serum albumin or rabbit antiserum and the presence of 50 ml litre^?1 of methanol reduced matrix effects of the samples. Under optimized conditions, the ELISA detected flucythrinate spiked in water, soil, and extracts of apple and tea samples down to 10 mg litre^?1, 0.2 mg litre^?1, 0.3 mg litre^?1 and 0.3 mg litre^?1, respectively. The mean recovery and CV ranged from 91% to 120% and from 5% to 12%, respectively. The ELISA results in apple samples correlated well with those from LC–MS analysis (r² = 0.99, n = 12). © 2001 Society of Chemical Industry     

Photolysis and hydrolysis of rimsulfuron

The degradation in the liquid phase of rimsulfuron and its commercial 250 g kg⁻¹ WG formulation (Titus®) was investigated. Photolysis reactions were carried out at 25 °C by a high-pressure mercury arc (Hg-UV) and a solar simulator (Suntest), while the hydrolysis rate was determined by keeping aqueous buffered samples in the dark. The effects of solvent and water pH on reaction kinetics were studied, and the results compared to literature data. Photoreactions of the commercial product in organic solvents were faster than pure rimsulfuron. Under simulated sunlight in water, the half-life for the photolysis reaction ranged from one to nine days at pH 5 and 9, respectively. The hydrolysis rate was as high as the photolysis rate, but decreased on increasing water pH. The main metabolite identified in neutral and alkaline conditions as well as in acetonitrile was N-[(3-ethylsulfonyl)-2-pyridinyl]-4,6-dimethoxy-2-pyridinamine, while N-(4,6-dimethoxy-2-pyrimidinyl)-N-[(3-(ethylsulfonyl)-2-pyridinyl)]urea and minor metabolites prevailed in acidic conditions. © 1999 Society of Chemical Industry     

Photostabilization of bioresmethrin by organic cations on a clay surface

Photostabilization of the pyrethroid insecticide bioresmethrin (BR) was achieved by adsorbing it onto the ciay montmorillonite with a cationic organic chromophore. Experiments in the dark showed that adsorption of BR to the surface of the clay did not inhibit its insecticidal activity. Complexes containing the organic cations methyl green (MG) or naphthylammonium (NA) retained their insecticidal activity against the flour beetle, Tribolium castaneum for 3-5 days in sunlight whereas unprotected BR was inactivated within a few hours. Optimum stabilization was achieved by definite amounts of BR and MG adsorbed, indicating that photostabilization was due to specific intermolecular interactions on the clay surface rather than to a UV-screening effect. The interactions between BR and MG at the clay surface were studied by Fourier transform infra-red spectroscopy.     

Photodecomposition of pendimethalin

The photodecomposition of pendimethalin (N-(l-ethylpropyl)-2,6-dinitro-3,4-xylidine, l) in solution, as a thin film, and on soil surfaces under ultraviolet light and sunlight was investigated. Irradiation of pendimethalin in methanol yielded, in addition to the minor dealkylated product, the major products 2-amino-6-nitro-N-(l-ethylpropyl)-3,4-xylidine and 2-nitroso-6-nitro-3,4-xylidine. Pendimethalin was found to degrade rapidly through reductive cyclisation of a nitro group and an adjacent N-ethylpropyl group to give a cyclised benzimidazole product. The photodecomposition of pendimethalin involves oxidative dealkylation, nitro reduction and cyclisation.     

Pharmacokinetics of pyrethroids in twospotted spider mites

The penetration and degradation of six pyrethroids were examined in the twospotted spider mite, Tetranychus urticae Koch, and the results were related to their toxicity as measured by inhibition of respiration using the Warburg technique and mortality using the slide-dip bioassay. FMC-54800 [1,1′-biphenyl-3ylmethyl cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate] was the most toxic pyrethroid to the mites based on both respiration and mortality studies. It and flucythrinate had the highest pharmacokinetic efficiency as determined by delivery and maintenance of internal levels of parent compounds. Permethrin, fenvalerate, and fluvalinate were intermediate in pharmacokinetic efficiency, whereas cypermethrin was significantly lower. The highest intrinsic activity, as estimated by the percentage inhibition of respiration per microgram of internal parent, was possessed by cypermethrin and FMC-54800. Fenvalerate and fluvalinate had intermediate levels, while permethrin and flucythrinate had significantly lower capacities to inhibit respiration. The combination of relatively high pharmacokinetic efficiency and intrinsic activity of FMC-54800 appeared to be responsible for its high toxicity. In addition to these findings, differences in the kinetics for cis and trans isomers were observed for permethrin but not cypermethrin. This study has yielded evidence that acaricidal activity of pyrethroids can be enhanced by optimizing the structure for increased pharmacokinetic efficiency and increased intrinsic activity.     

不同栽培模式茶园黑刺粉虱发生规律

为明确北方茶园黑刺粉虱发生规律, 2016年—2017年于山东烟台系统研究了日光温室盖保温被?日光温室及露地3种栽培模式茶园黑刺粉虱发生规律?结果表明, 3种栽培模式茶园黑刺粉虱均以若虫在叶片背面越冬, 1年发生4代, 世代重叠严重?日光温室盖保温被栽培模式越冬代成虫羽化较日光温室和露地栽培发生早28 d左右, 日光温室和露地栽培模式下黑刺粉虱发生期差异不显著?3种栽培模式茶园黑刺粉虱成虫全年均有4次发生高峰期, 第1次高峰期日光温室盖保温被栽培模式较日光温室早20 d左右, 日光温室较露地早30 d左右?黑刺粉虱发生量依次为日光温室>露地>日光温室盖保温被, 均于10月上旬陆续以3龄若虫在叶片背面越冬?     

Phototransformation of Triadimefon on Glass and Soil Surfaces

Photodegradation of triadimefon has been studied on glass and soil surfaces. A number of photoproducts have been isolated and characterised by NMR, IR and MS. Photolysis resulted in considerable amounts of 1-(4-chlorophenoxymethyl)-1,2,4-triazole, 1-(4-chlorophenoxy)-2,2-dimethyl-1-(1,2,4-triazol-1-yl)propane, 1-(1,2,4-triazol-1-yl)-3,3-dimethylbutan-2-one and 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-ol. Rates of photodegradation on glass and soil surfaces under UV and sunlight followed first-order kinetics with a significant correlation coefficient. Photodegradation was greater on alluvial soil than on laterite soil.     

Antifeedant activity of solvent extracts of neem seed kernel against Spodoptera litura F. and their persistency against sunlight through encapsulation

Abstract

Different solvent extracts of neem seed kernels were evaluated against Spodoptera litura F. on cauliflower, Brassica oleracea var. botrytis leaves. Based on this evaluation, aqueous extract was dissolved in ethanol, and methanol extract in ethanol, and dissolved parts were designated as fraction I and fraction II, respectively. The extracts having more antifeedant activity were encapsulated to achieve stability against the sunlight. Among the solvent extracts tested at 1.0% concentration, methanol extract provided maximum protection (100%) of the leaves followed by ethanol (98.39%) and aqueous (93.01%) extracts. Fraction I and fraction 11 were equally effective at 0.1 % concentration against S. litura larvae and checked more than 70% of leaf damage. However, such extracts were found to be unstable when exposed to sunlight. The pre‐gelatinized starch‐encapsulated products, viz. ρre‐gel I and pre‐gel II were quite stable and afforded more than 68.0% protection to the cauliflower leaves even after 6 days of exposure to sunlight.     

Photolysis of dimepiperate in aqueous solution

Dimepiperate, S-(1-methyl-1-phenylethyl) piperidine-1-carbothioate ( I ) was degraded in aqueous solution by ultraviolet irradiation into piperidine ( II ), α-methylstyrene ( III ), acetophenone ( IV ), and formaldehyde ( V ). The reaction followed first-order kinetics. In sunlight the reaction occurred only in the presence of a sensitiser and afforded the same four photolytic degradation products. In the absence of oxygen the herbicide was converted much more rapidly, but yielded only ( II ) and ( III ) as products. A mechanism which accounts for the formation of the photoproducts is proposed.     

Light-induced transformations of tribenuron-methyl in aqueous solution

Tribenuron-methyl a sulfonylurea herbicide, readily photodegraded in aqueous solution under sunlight and UV light. The photoproducts identified were N-methyl-4-methoxy-6-methyl-1,3,5-triazine-2-amine, methyl 2-(aminosulfonyl) benzoate, o-benzoic sulfimide, N-(4-methoxy-6-methyl1,3,5-triazin-2-yl)-N-methyl urea and N-(2-carbomethoxyphenyl)-N-(4-methoxy-6-methyl-1,3,5triazin-2-yl)-N′-methyl urea. The rate of photodegradation of tribenuron-methyl in different types of water followed first-order kinetics with significant correlation coefficient, increased with increase in pH and was also dependent upon the dissolved impurities. © 1999 Society of Chemical Industry     

The degradation of (Z)- and (E)-1,3-dichloropropenes and 1,2-dichloropropane in soil

The degradation in soil of the major constituents of a 1,3-dichloropropene-1,2-dich-loropropane nematicide has been studied under laboratory and outdoor conditions. In sealed glass containers, ( Z)- and ( E)-1,3-dichloropene- 2-¹⁴C were converted in soil into the corresponding 3-chloroallyl alcohols and these alcohols were in part strongly bound to the soil. The ( Z)- and ( E)-3-chloroacrylic acids were also found as minor products. More polar products were detected and these released the chloroacrylic acids in 20–30% yield upon hydrolysis. Although the 1,3-dichloropropenes were lost by volatilisation from soil stored in open glass jars outdoors, they also underwent degradation to the same products that were detected in sealed containers. There was evidence of only slight degradation of 1,2-dichloropropane- 2-¹⁴C (4 % or less of the applied radioactivity remained unextracted from a loam soil after 5 months). When soil treated with the 1,2-dichloropropane was stored outdoors in an open glass container, less than 1 % of the original radiolabel remained in the soil after 10 days under these conditions due to volatilisation of the applied material. In a separate experiment potatoes were grown in soil 6 months after treatment with a mixture of both ( Z)- and ( E)-1,3-dichloropropene- 2-¹⁴C and 1,2-dichloropropane- 2-¹⁴C. Although 5 % of the applied radiolabel remained in the soil at potato harvest the potato tubers contained only a very small residue (0.007 mg/kg).     

Effect of Neurotoxic Pesticides on the Feeding Rate of Marine Mussels (Mytilus edulis)

The effects of selected neurotoxic pesticides on the feeding rate of marine mussels (Mytilus edulis) were determined. Two organochlorine pesticides, lindane and endrin, two acetylcholinesterase-inhibiting compounds, dichlorvos and carbaryl and two pyrethroids, flucythrinate and permethrin, were studied. No evidence was found for any specific neurotoxic effect of the organochlorines and pyrethroids on feeding efficiency. In contrast, dichlorvos and carbaryl inhibited the enzyme acetylcholinesterase in mussel gills and were more toxic to feeding efficiency than could be explained by a narcotic mechanism of toxicity alone. Dichlorvos also caused clear behavioural changes in the mussels. The significance of these observations for the application of mussels to impact assessment in the marine environment is discussed. © 1997 SCI.     

Photolysis of organophosphorus insecticides on soil surfaces

Photolysis on soil surfaces of the organophosphorus insecticides diazinon, methidathion and profenofos was studied under artificial sunlight conditions. All three compounds were readily degraded under the conditions used. The rate of degradation decreased in the order diazinon, profenofos, methidathion and was always greater in moist than in dry soil. The same order of stability was also observed from photolysis studies in aqueous solution. The major photolysis products identified were 2-isopropyl-6-methylpyrimidin-4-ol from diazinon, 5-methoxy-3H-1,3,4-thiadiazol-2-one from methidathion and 4-bromo-2-chlorophenol and 4-bromo-2-chlorophenyl ethyl hydrogen phosphate from profenofos. The same compounds were formed in hydrolysis studies and also upon photodecomposition in aqueous solutions of diazinon and methidathion. Profenofos, however, showed a different photolytic reaction in aqueous systems, forming O-(2-chlorophenyl) O-ethyl S-propyl phosphorothioate. Soil photolysis studies together with hydrolysis experiments could be a useful quick method for obtaining early information on the chemical breakdown products which are to be expected in the soil environment.     

Degradation of Diuron Photoinduced by Iron(III) in Aqueous Solution

The degradation of diuron photoinduced by iron(III) in aqueous solution has been investigated with different iron(III) species (monomeric species Fe(OH)²⁺, dimeric species Fe₂(OH)₂⁴⁺ and water-soluble oligomeric species) under monochromatic excitation at 365 nm and under sunlight. The rate of degradation depends on the concentration in Fe(OH)²⁺, the most reactive species in terms of ^•OH radical formation. The major photoproduct is 3-(3,4-dichlorophenyl)-1-formyl-1-methylurea which represents more than 60% of diuron disappearance. The mechanism only involves the attack by ^•OH radicals arising from iron(III) excited species. The half-lives of diuron when submitted to such a process in the environment were estimated to be 1–2 h and a few days according to the concentration of Fe(OH)²⁺ (respectively 70% and <10% of total iron(III) concentration).     

Assessment of the suitability of Tinopal as an enhancing adjuvant in formulations of the insect pathogenic fungus Beauveria bassiana (Bals.) Vuillemin

BACKGROUND: Biopesticides based on Beauveria bassiana (Bals.) Vuillemin hold great promise for the management of a wide range of insect pests. The conidia in the biopesticide formulation require an adjuvant to protect them from photoinactivation by sunlight. The suitability of Tinopal, an optical brightener used as sunscreen for baculovirus formulations, for use with B. bassiana was assessed. The aim was to study the effect of Tinopal on the growth and photoprotection of B. bassiana, and its effect on the susceptibility of insects to B. bassiana. RESULTS: Tinopal was found to have no adverse effect on the growth of B. bassiana. It was found to confer total protection (approximately 95% conidial germination at 10 g Tinopal L(-1)) from sunlight up to 3 h of exposure, and a better survival rate than controls even up to 4 h. Helicoverpa armigera Hübner larvae fed on diet with 5 g kg(-1) Tinopal were found to have reduced growth. The duration of the larval stage increased by 3-4 days in 1 and 5 g kg(-1) Tinopal treatments. Among the moths that emerged from larvae fed on diet with 5 g kg(-1) Tinopal, a significantly high number were malformed compared with controls. The larvae that were fed diet with Tinopal showed quicker and higher mortality and required a lower effective lethal dose (LC(50)) than the controls. Tinopal was found to have a synergistic effect with B. bassiana in causing insect mortality. CONCLUSIONS: Tinopal was found to be a suitable adjuvant for B. bassiana-based biopesticide formulations. It conferred tolerance to sunlight and caused stress in the insect, leading to a synergistic effect with B. bassiana.     

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.