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[Studies on metabolism of a fungicide yekuling in rat].

The metabolism of a fungicide Yekuling was studied in rat after oral administration. Four metabolites were isolated and purified by means of reverse-phase HPLC and TLC. They were identified to be acetic acid, 1,3-dithiolan-2-ylidenehydrazide; pyruvic acid, 1,3-dithiolan-2-ylidenehydrazide; benzoic acid and hippuric acid with UV and MS. The latter was further confirmed by chemical synthesis. The experimental results showed that Yekuling was metabolized extensively in rat. Yekuling was hydrolyzed by amidase to produce benzoic acid and 1,3-dithiolan-2-ylidenehydrazide. The latter was further acetylated by N-acetyltransferase to form acetic acid, 1,3-dithiolan-2-ylidenehydrazide, or condensed spontaneously to form pyruvic acid, 1,3-dithiolan-2-ylidenehydrazide. Benzoic acid was further conjugated with glycine to produce hippuric acid.

Acetates↗

Organic viticulture: efficacy evaluation of different fungicides against Plasmopara viticola.

The restriction on the use of copper salt fixed by the European Community (Reg. EC n. 473/2002) owing to the environment problems due to the copper accumulation in the soil, has stimulated the research to evaluate the possibility to reduce the copper use. This field experiment was carried out to estimate, in an organic vineyard, the effectiveness, against Plasmopara viticola (Berk. et Curt) Berl. et De Toni, of copper compounds at a low rate or alternative copper products. Guideline EPPO/OEPP PP 1/3 (2) has been used. Plots of 18 plants each, repeated 4 times in a randomized design, have been arranged. The obtained results, even if related to circumscribed and extremely favorable field for the development of the grapevine downy mildew, evidenced the impossibility to practice a defense to fixed cadence, succeeding, at the same time, to respect the limits of European Community for copper metal. The reference product, that has guaranteed the best results, determined a total contribution of copper metal of 25.7 Kg/ha that leaves very little possibilities of copper use in the following years, like previewed from the Reg. EC n. 473/2002; therefore a strategy of defense of this type turns out as not usable. The two cupric products characterized by the low metallic content were not completely satisfactory in our operating conditions with high pressure of grapevine downy mildew, but they determined a contribution of copper metal under the limits established by the European Community. Therefore new experiments, using differentiated strategies, should be carried out to improve the effectiveness of these fungicides. About biofungicide, it gave total absence of biological activity against P. viticola. The limits of the used formulations regarding the operating protocol applied, are evidenced, for some of them, by epidemiological results, for the others by the high amount of distributed copper, that causes an accumulation of residual in soil and leaves. Through the examination of the results and considering the particular climatic condition that characterized 2002, we can conclude that the trial must be considerate valid for the stressful situations that affected the vineyard.

Copper↗

[Azoles. 34. Nitroimidazole derivatives and their antibacterial and fungicidal action].

Nitroimidazole derivatives 4a-4c, 5a-5c, 8a-8c and 9a-9c were synthesized by treating 4,5-dinitro- and 2-methyl-4,5-dinitroimidazole (1,2) or their silver salts [1.Ag,, 2.Ag) with chlorosubtituted phenacyl bromides 3a-3c, diethyl sulphate or ethyl iodide, allyl iodide and ethyl chloro-, azo- or bromoacetate. 2,4(5)-dinitroimidazole (10) has been converted to the 2,4-dinitroimidazole derivative 10a by the action of ethyl bromoacetate in the presence of sodium ethylate. A modified method for the synthesis of 6a and 6b has been described. 7a and 7b have been obtained by a known method. Some of the newly synthesized nitroimidazole derivatives show antibacterial and fungicidal activity.

Anti-Bacterial Agents↗

Evaluation of a method based on liquid chromatography/electrospray tandem mass spectrometry for analyzing eight triazolic and pyrimidine fungicides in extracts of processed fruits and vegetables.

The feasibility of using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) for determining 8 fungicides (triadimenol, penconazole, propiconazole, hexaconazole, cyproconazole, myclobutanil, fenarimol, and bitertanol) in extracts of tomato puree and lemon juice concentrate has been evaluated. A miniaturized extraction-partition procedure requiring small amounts of nonchlorinated solvents has been used. The extracts (5 microL) were analyzed by LC/ESI-MS/MS without any previous cleanup step. Chromatographic determination has been performed using a C18 column and isocratic elution. Seventeen MS/MS transitions of precursor ions were monitored simultaneously (2 or 3 for each pesticide). The excellent selectivity and good linearity of the LC/MS/MS method allowed quantitation and identification at low levels (limits of quantitation <0.010 mg/kg), even in difficult matrixes, with a run time of only 1.5 min.

Chromatography, Liquid↗

Fungicidal properties of Pinus sylvestris L. for improvement of air quality.

Sick building syndrome is a term commonly used to describe the consequences of poor indoor air quality. It is well documented that first of all air quality depends on the chemical composition, and until now negligible attention has been paid to air pollution by microorganisms. Some species of fungi (Aspergillus flavus, A. fumigatus, A. niger, A. parasiticus, A. oryzea and other) and their toxins cause difficulty in breathing, allergic rhinitis, watery eyes, headaches, and flu-like symptoms. Over recent years considerable interest has been developed for plant extracts that would be of great use for the improvement of air quality. The biological activity of Pinus sylvestris L. has been investigated in order to find out its fungicidal activity against airborne microorganisms. It was determined, that fungi from Aspergillus and Penicillium genera dominated indoors. Antimicrobial activity of pine oil was evaluated by technique of oil diffusion to Czapek agar (for fungi), malt extract agar (for yeast and yeast-like fungi) and nutrient agar (for bacteria). Minimum inhibitory concentrations of pine oil to 13 species (8 fungi, 2 yeast-like fungi, yeast and 2 bacteria,) were determined: 1.0-2.5, 1.0-1.2, 0.5-0.75, and 0.75-1.2% (v/v), respectively. According to resistance to pine oil action, microorganisms grouped themselves as following: fungi, spore bacteria, yeast-like fungi, yeast, and bacteria (fungi being the most resistive and bacteria being the least resistive). The most active concentration of pine oil against all tested microorganisms was 2.5%, and the most sensitive fungus to volatiles was Ulocladium oudemansii.

Air Microbiology↗

Responses of two ladybeetles to eight fungicides used in Florida citrus: implications for biological control.

Two ladybeetles, Cycloneda sanguinea and Harmonia axyridis, were exposed in the laboratory to eight fungicide formulations commonly used in citrus production in Florida. Both benomyl and the combination of copper and petroleum oil proved toxic to larvae of C. sanguinea that were exposed to concentrations corresponding to recommended field rates, either as leaf residues or in topical spray applications. Larvae of C. sanguinea also suffered significant mortality when exposed to neem oil as a leaf residue, but not after topical application. Larvae of H. axyridis exposed to these compounds completed development with the same success as control larvae in all trials. However, H. axyridis larvae exhibited slower development following exposure to leaf residues of ferbam applied at twice the recommended rate. Exposure to azoxystrobin as a leaf residue at twice the recommended concentration resulted in accelerated larval development in both species. No compounds appeared repellent to adult beetles of either species. Adult beetles of both species were observed resting on portions of filter paper treated with fosetyl-Al more often than on untreated, control portions. Azoxystrobin, ferbam and mefenoxam similarly arrested the movement of adult C. sanguinea, whereas benomyl and the copper and petroleum oil combination arrested the movement of adult H. axyridis. The differential sensitivity of the two coccinellid species is discussed in the context of the potential displacement of the indigenous C. sanguinea by the invasive H. axyridis.

Aerosols↗

Assessment of deposition of MEMC (seed dressing fungicide) in exposed rice grain through study of seedling growth parameters.

Rice seed grains exposed to 240 ppm of seed dressing fungicide, MEMC showed increase in deposition of mercury with increase in period of observation (0h to 48h) in 765+/-5 mg of intact endosperm. The gradual increase in mercury deposition in intact endosperm caused simultaneous decrease in mercury content of the seed coat. Exposure periods of 5 to 20 min with 240 ppm of MEMC showed 5.5 to 8.72 microg of mercury deposition in 765+/-5 mg of intact endosperm. Increase in period of exposure (3 to 20 min) to 240 ppm of MEMC and also increase in chronic treatment to lower concentrations (1.5 ppm to 24 ppm) to seed grains have shown similar results in seedling growth parameters. Lower period of exposure or exposure to lower concentrations, both showed a significant inhibition of root growth, however the shoot growth showed stimulation. But higher exposure period or exposure to higher concentrations brought inhibition of both root and shoot growth. The exposure period showing 50% of root growth inhibition of 72h old seedling was calculated to be 10 min So also the chronic treatment showing the 50% of root growth inhibition was calculated to be 9 ppm. Ten min exposure of rice grain to 240 ppm of MEMC showed deposition of 7.11 microg of mercury in 765+/-5 mg of intact endosperm at 48h of observation (optimal phase of germinating process). Regression analysis indicated that by the time of 72h the intact endosperm and developing seedling might have acquired with a minimum amount of 10.23 microg of mercury from the seed coat. Finally it can be said that 10.23 microg of MEMC might be bringing 50% root growth inhibition in 72h old seedlings and 16.71 microg of mercury causing 50% inhibition of both root and shoot growth of 120h old seedlings.

Fungicides, Industrial↗

Residue analysis and dissipation of a new fungicide 2-allylphenol in tomato.

The method of residue analysis of a new synthesized fungicide 2-allylphenol was studied by simulating the active compound structure in Gingko tree (Gingko biloba L.) and its dissipation rate and terminal residue levels in tomato under field condition. Residues of 2-allylphenol were extracted from tomato matrix with acetone, purified by liquid-liquid extraction and Florisil cartrieges, and then determined by HPLC with UV-detector. The minimum detectable amount of 2-allylphenol was 3 x 10(-9) g, the minimum detectable concentration of 2-allylphenol in the samples of tomato were 0.01 mg/kg. The ranges of average recoveries and coefficient variation of the method were 87.7%-90.2% and 1.25%-2.06%, respectively. The dissipation rate and terminal residue levels in tomato were determined with the method described above. The results showed that the half-life of 2-allylphenol in tomato was 6.37 d, and 2-allylphenol declined with 82.6% of the initial deposit remaining in tomato at harvest. The terminal residue levels in tomato were 0.15 mg/kg and 0.20 mg/kg following the recommended doses and time intervals.

Acetone↗

Fungicide residues in pears and apples after post harvest treatments by drencher.

Aim of this trial was to verify the residues of two fungicides, already authorised for the use in field (the admitted maximum limit of residues have been fixed), after post harvest treatments on pears and apples for defence against main post harvest rots. The use of formulation in post harvest must consider also the technique of product application. In fact there are different systems to carry out the treatments for the protection of the commodities during cold storage. In this trial two formulations of pyrimethanil and imazalil were applied by drencher on pome fruit.

Consumer Product Safety↗

Use of fungicides against powdery mildew during an artificial scab inoculation test in an apple breeding programme focused on partial resistance.

Our project aimed to develop an effective selection methodology for partial disease resistance. One of its objectives was to define the optimal selection threshold for discarding individual seedlings after artificial scab inoculation tests. Working with large populations of seedlings, it was necessary to conduct the scab tests at intervals throughout the season, with the risk of powdery mildew infection of the young plantlets during the summer. Because Podosphaera leucotricha symptoms prevent breeders from properly evaluating scab symptoms, a trial was conducted to assess the effect of specific anti-mildew fungicides on the results of the scab inoculation test. The results allowed the active ingredient and the optimum time for application in relation to the inoculation date to be determined.

Breeding↗

Persistence and degradation of metalaxyl, mancozeb fungicides and its metabolite ethylenethiourea in soils.

The degradation pattern of metalaxyl, mancozeb and its metabolite ethylenethiourea (ETU) residues indicated a close correspondence to first order exponential degradation kinetics in soils. Degradation of fungicides in soils was predominantly biological as well as chemical in nature. Slower degradation ofmetalaxyl was noticed in the soils and their half-life values were higher than mancozeb and ETU as evident by wide range of half-life values from 41.24 to 165.11 days. In case of metalaxyl, Hiriyur soil was found to be superior in degrading the metalaxyl. Lower persistence of mancozeb and ETU was observed in soils resulting in rapid rate of degradation at smaller half-life values as compared to metalaxyl indicating the faster degradation of mancozeb and ETU. In mancozeb applied soils, the ETU formation was increased up to 30 days of incubation and thereafter it declined. Amongsoils, degradation of either mancozeb or ETU is not influenced by soil types. However, mancozeb persistence was higher in Hiriyur soils than Chettalli and Bangalore soils.

Agriculture↗

Interaction of potassium phosphonate fungicide in laterite soil.

Potassium phosphonate is a fungicide widely used to control Phytophthora fungi species in many crops all over the world. In this paper, an attempt has been made to study the interaction of potassium phosphonate with soil under varying pH and calcium level. Several reports available in literature indicate that the phosphonate in organic form adsorb strongly on almost all mineral surfaces and natural materials like soil and sediments. The present study conducted on laterite soil of Kerala using 2 mm sieved sample indicated that phosphonate obeys Freundlich adsorption isotherm. Though at lower concentrations, Langmuir model equally fits well, deviation was observed at higher concentrations. pH and calcium content of the soil had striking influence on the interaction of the chemical with the soil. The calcium source also appeared to influence the adsorption phenomenon. Since potassium phosphonate is extensively used to control Phytophthora fungi species in black pepper (Piper nigrum) plantations in India and liming is a standard practice followed as soil amendment in acid soils to increase the soil pH, this study may help to maintain good soil quality.

Computer Simulation↗

[The systemic fungicide tridermorph as an inhibitor of the respiratory chain of electron transfer particles from beef heart mitochondria].

Tridemorph (N-tridecyl-2,6-dimethylmorpholine) inhibits both the NADH-oxidase and the succinate-cytochrome c oxydoreductase system of non-phosphorylating electron transfer particles from beef heart. The concentration required for half-inhibition amounted to 3,4 muM and 24 muM respectively. Two different sites of action in the respiratory chain could be localized by means of difference spectroscopy and measurements of enzymic activities in various partial systems. The inhibition of the NADH-ubiquinone oxydoreductase activity as well as the suppression of the NADH-induced reduction of all cytochromes on the one hand and the insensitivity of the NADH-ferricyanide oxydoreductase system on the other argue in favour of a site of action similar to rotenone. The partial suppression of the succinate-induced reduction of cytochrome b with simultaneous complete inhibition of the reduction of the other cytochromes indicate an additional site of action analogous to antimycin A. Both inhibitory actions appeared instantaneously after the addition of tridemorph and were counteracted by serum albumin. Furthermore, tridemorph inhibited the oxydation of external ferrocytochrome c but not that of ascorbate/tetra-methyl-p-phenylene-diamine-HCI (TMPID) showing that it is not a true inhibitor of the cytochrome oxidase. The TMPD-induced bypass of the succinate oxidation was inhibited as well. The possible role of the inhibition of the main pathway of the respiratory chain for the fungicidal action of tridemorph is discussed.

Animals↗

[A comparative evaluation of acute action thresholds during the isolated and combined effects of boricid fungicide and its components (polycarbacin+sulphur)].

The article contains a comparative analysis of the acute action thresholds in isolated and combined actions of boricide fungicide and its components when inhaled. To determine the predominant type of the combined action, a correlation analysis technique of dosage (concentration) dependences was used with regard both to mixtures and isolated components, as it was done in case with the lethality curves studies involving calculation of the combined action coefficient. The coefficient calculation technique used for the lethality levels can be adequately applied to the calculations of acute action thresholds of a permanent composition mixture by CE50 degrees and CE50 min.

Animals↗

[The hygienic validation of the MPEL for the fungicide tekto in reservoir water].

Fungicide tecto (thiabendazol) is a low-toxic compound, produces a weak skin-resorptive and local irritating effect. Cumulation coefficient is 3.96. Threshold and subthreshold doses for tecto were determined as a result of 12-months chronic experiment on white rats--3.7 and 0.37 mg/kg, respectively. The allowable 24-hours dose for human exposure to the chemical is 0.6 mg. The threshold tecto concentration according to the effect on the general sanitary regimen of water reservoirs appeared to be 1 mg/l. According to the limiting toxicological index 0.05 mg/l was recommended as tecto MAC for the water of reservoirs.

Animals↗

[The estrogenic effect of the fungicide Novozír MN 80 on the uterus in neonatal rats].

The estrogenic effect of the ethylenebisdithiocarbamate fungicide Novozír MN 80 (Duslo, Sal') was studied by means of the screening method determining the reproductive risk of chemical substances, recommended by the Environmental Protection Agency. Compared to intact controls, a significant increase in relative uterine weight was recorded in the group of animals which received 1/25 of the maximal tolerable concentration of Novozír MN 80. Compared to negative controls (Tween 80), the relative uterine weight was increased significantly after administration of 1/25 and 1/50 of the maximal tolerable concentration of Novozír MN 80. On histologic examination the cuboidal epithelium of the mucous membrane was found to be changed into columnar epithelium, with uneven distribution of enlarged nuclei in the vacuolized cytoplasm. At 1/25 maximal tolerable concentration thickening of the uterine wall was observed.

Animals↗

Circadian rhythms of RNA, DNA and protein content in the rat thyroid, adrenal and testis in chronic pesticide exposure. I. Effects of a fungicide (Mancozeb).

Ninety days of exposure to the fungicide Mancozeb, 100 ppm/day, affects the circadian rhythms of RNA, DNA and proteins in the thyroid and adrenal and slightly but statistically significantly, the testicular RNA content in the rat. The thyroid RNA rhythm shows an almost 12-hour phase advance without change in mesor, but with a decrease in amplitude and in the percent of total variability of RNA in the group, attributable to the circadian rhythm (PR). In the adrenal, the circadian rhythm of RNA and DNA is lost as a group phenomenon and the mesor of the circadian rhythm of protein content is elevated. The testicular RNA rhythm shows multiple peaks, suggesting frequency demultiplication and a loss of the circadian rhythm as a group phenomenon. Chronotoxicology appears to be essential in detecting the adverse effects of pesticides.

Adrenal Glands↗