zineb and propineb

We propose a modification of lanthanide-sensitized luminescence (LSL) to increase the selectivity and sensitivity of analytical methods based on this detection. LSL consists in the formation of complexes of lanthanide ions and organic compounds. Then, an intramolecular energy transfer occurs from the excited state of the ligand (organic analyte) to the emitting level of the lanthanide. The utilization of luminescent nanoparticles (carbon quantum dots, CQDs) in LSL systems can enhance their sensitivity and selectivity. CQDs can react with lanthanide ions through their carboxylic groups. These systems can thus be used as time-resolved luminescent probes. Propineb (PPN), a well-known dithiocarbamate fungicide, has been selected as the target analyte to show the advantages of using CQDs in LSL systems. The method proposed is based on the quenching produced by PPN in europium-CQDs luminescence, obtaining a detection limit of 0.03 μg mL

Topics: Carbon; Europium; Fungicides, Industrial; Ions; Luminescence; Luminescent Measurements; Quantum Dots; Zineb

In the presented work, a coprecipitation method was developed for separation-preconcentration, and determination of trace quantities of propineb in vegetable samples. Propineb was coprecipitated by using Al(OH)

Topics: Spectrophotometry, Atomic; Vegetables; Zinc; Zineb

In cadmium (Cd) contaminated farmland soil, antagonism between elements can be used to control the absorption and accumulation of Cd in crops through the external application of zinc (Zn) and manganese (Mn). Dithiocarbamates (DTCs) are highly effective fungicides commonly used in farmlands, and DTCs are rich in Zn and Mn. We selected three representative DTCs (propineb, mancozeb, and zineb) for a field experiment in Henan province, China. The effects of DTC on Cd absorption and accumulation in wheat and the interaction of Zn, Mn, and Cd in wheat after spraying of DTC were studied using different application times at the heading stage. The results showed that after foliar spraying of DTCs according to pesticide application requirements, wheat yield was not affected. The Zn and Mn contents in grains increased, with the highest increases being 19.2% and 12.4%, respectively. Zn and Cd as well as Mn and Cd were antagonistic in wheat, and the transport of Cd from soil to root and from husk to grain was inhibited. The bioconcentration factor (grains/soil) decreased from 1.3 to 0.68 and the translocation factor (grains/husks) decreased from 0.76 to 0.35. The Cd content in grains decreased by 60.4%, 52.8%, and 25.6% with mancozeb, propineb, and zineb applications, respectively, and the Cd reduction effect of spraying DTCs twice was better than that of spraying DTCs once and thrice. The results show that DTCs application could reduce the Cd content in wheat grains and realize the dual effects of crop disease prevention and Cd reduction.

Topics: Cadmium; Edible Grain; Manganese; Soil; Soil Pollutants; Triticum; Zinc; Zineb

A dithiocarbamate (DTC) fungicide, propineb, affects thyroid function and exerts immunotoxicity, cytotoxicity, and neurotoxicity in humans. Long-term exposure to propineb is associated with carcinogenicity, teratogenicity, malfunction of the reproductive system, and abnormalities in vital signs during organ development. However, there is no evidence of acute toxicity attributable to propineb in zebrafish. Therefore, in the present study, we assessed the toxicity of propineb in zebrafish by studying its adverse effects on embryo development, angiogenesis, and notochord development. Embryos with propineb exposure developed morphological and physiological defects and in larvae, apoptosis and notochord defects were induced in the early development stage. Transgenic fli1:eGFP zebrafish exposed to propineb showed abnormal larval development with defects in angiogenesis and deformed vasculature. Propineb induced irreversible damage to the neural development of embryos and neurogenic defects in developing zebrafish in transgenic olig2:dsRED zebrafish. These results show that exposure to propineb triggers abnormalities in different organ systems of zebrafish and suggests the physiological complexity of the response to propineb.

Topics: Animals; Embryo, Nonmammalian; Embryonic Development; Fungicides, Industrial; Neovascularization, Physiologic; Neurogenesis; Notochord; Zebrafish; Zineb

To establish a method for determination of thiram, propineb and metiram in mushroom samples by gas chromatography-mass spectrometry(GC-MS).. Insoluble heavy metal salts were converted into water-soluble sodium salts by alkaline buffer with strong chelating agents. Dithiocarbamates can be converted into different methyl ester compounds with ion pair methylation. The GC separation was performed on a DB-5 MS capillary column(30 m×0. 25 mm, 0. 25 μm). The pesticides were detected by GC-MS with selective ion monitoring(SIM) and quantified by external standard of working curve method. Methodsological verification was carried out based on optimized sample pretreatment and GC-MS condition.. The concentrations of dithiocarbamates exhibited a good linear relationship with GC-MS within a certain range. The limits of detection of thiram, propineb and metiram were 0. 01, 0. 05 and 0. 05 mg/kg, respectively. Furthermore, the average recoveries were from 76. 98% to 93. 52%, and the maximum relative standard deviation was 11. 54%(n=6).. This method is simple, sensitive, accurate and reliable. All the indices meet the requirements of pesticide residue detection.

Topics: Agaricales; Ditiocarb; Gas Chromatography-Mass Spectrometry; Pesticide Residues; Thiram; Zineb

A sensitive and specific method for the determination of propineb and its metabolites, propylenethiourea (PTU) and propylenediamine (PDA), using gas chromatography with flame photometric detection (GC-FPD) and LC-MS/MS was developed and validated. Propineb and its metabolite residue dynamics in supervised field trials under Good Agricultural Practice (GAP) conditions in banana and soil were studied. Recovery of propineb (as CS

Topics: Agriculture; Chromatography, Gas; Chromatography, Liquid; Diamines; Food Analysis; Food Contamination; Fungicides, Industrial; Half-Life; Limit of Detection; Musa; Pesticide Residues; Reproducibility of Results; Soil Pollutants; Tandem Mass Spectrometry; Thiourea; Zineb

Dithiocarbamates have emerged as potent carbonic anhydrase (CA) inhibitors in recent years. Given that CAs are important players in cellular metabolism, the objective of this work was to exploit the CA-inhibitory property of dithiocarbamates as a chemotherapeutic weapon against the Leishmania parasite. We report here strong antileishmanial activity of three hitherto unexplored metal dithiocarbamates, maneb, zineb, and propineb. They inhibited CA activity in Leishmania major promastigotes at submicromolar concentrations and resulted in a dose-dependent inhibition of parasite growth. Treatment with maneb, zineb, and propineb caused morphological deformities of the parasite and Leishmania cell death with 50% lethal dose (LD50) values of 0.56 μM, 0.61 μM, and 0.27 μM, respectively. These compounds were even more effective against parasites growing in acidic medium, in which their LD50 values were severalfold lower. Intracellular acidosis leading to apoptotic and necrotic death of L. major promastigotes was found to be the basis of their leishmanicidal activity. Maneb, zineb, and propineb also efficiently reduced the intracellular parasite burden, suggesting that amastigote forms of the parasite are also susceptible to these metal dithiocarbamates. Interestingly, mammalian cells were unaffected by these compounds even at concentrations which are severalfold higher than their antileishmanial LD50s). Our data thus establish maneb, zineb, and propineb as a new class of antileishmanial compounds having broad therapeutic indices.

Topics: Animals; Antiprotozoal Agents; Apoptosis; Body Burden; Carbonic Anhydrase Inhibitors; Cell Line; Cell Survival; Leishmania major; Maneb; Mice; RNA, Protozoan; Thiocarbamates; Zineb

The determination of transition metal containing dithiocarbamate fungicides represents a challenging aspect of analytical object. They have a low stability, low solubility and stabilize versatile coordination monomers, dimers, disulfides and/or S-oxidized derivatives. Their diverse biological activities and agricultural implementation encompass plant prevention and crop protection against a variety of plants containing fungi and diseases of 400 pathogens and 70 cultures. Nonetheless, those dithiocarbamates (DTCs) are banned for agricultural use in Europe or have expiration at years 2016-2017 because of their highly toxic degradation products and/or metabolites, in particular ethylene thiourea; they found large-scale implementations in materials research and medicine. Despite the broad interdisciplinary of DTC application, due to the above reasons, they have received little attention in the rapidly growing field of analytical chemistry, and in particular, the analytical mass spectrometry. Therefore, the study reported on qualitative, quantitative and structural analysis of ten DTCs (1-10), using the matrix assisted laser desorption/ionization (UV-MALDI)-Orbitrap-mass spectrometry (MS) contributed considerably to the implementation of the method for environmental and foodstuffs monitoring. Its ultrahigh resolving power and capacity for direct solid-state analysis, at limited number of sample pretreatment steps, at concentration levels of analytes of up to femtogram per gram resulted to achievement of a highly precise analytical information for these non-trivial objects. The presented fully validated method and technique is based on the successful ionization of DTCs embedded in three novel organic salts (M1-M3). In this regard, the reported MS and the single-crystal X-ray diffraction data as well as the quantum chemical one are able to correlate the molecular structures in condense and in the gas phase. Despite the novelty of the fundamental methodological character of the research reported, the promising metrology contributed to the applied aspect of the UV-MALDI-MS as a robust analytical method for environmental and foodstuffs monitoring, which is tested on two commercially available crop protecting products such as Mancozeb® and Antracol®, respectively.

Topics: Environmental Monitoring; Europe; Fungicides, Industrial; Maneb; Mass Spectrometry; Metals; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Thiocarbamates; Transition Elements; X-Ray Diffraction; Zineb

Pesticides are one of the most potent environmental contaminants, which accumulate in biotic and abiotic components of ecosystems. Acetamiprid (Acm), a neonicotinoid insecticide, and Propineb (Pro), a dithiocarbamate fungicide, are widely used to control sucking insects and fungal infections on crops, respectively. The present study was undertaken to investigate the genotoxic effects of these compounds, individually and in mixtures, in mouse germ cells by using the sperm morphology assay. Mice were injected intraperitoneally with 0.625, 1.25, and 2.50 μg mL⁻¹ of Acm, 12.5, 25, and 50 μg mL⁻¹ of Pro, and their mixture at the same concentrations over 24 and 48 h. Acm did not significantly increase the percentage of abnormal sperm at any concentration. The frequency of abnormal sperm significantly increased after 24 and 48 h of exposure to 50 μg mL⁻¹ of Pro. The mixtures of 2.50 μg mL⁻¹ of Acm and 50 μg mL⁻¹ of Pro induced sperm abnormalities antagonistically both after 24 and 48 h of exposure. Results suggest that Acm was non-genotoxic for mouse germ cells, while Pro may have been a germ cell mutagen due to the observed increase in the frequency of sperm abnormalities. However, to gain better insight into the mutagenicity and DNA damaging potential of both of these pesticides, further studies at molecular level should be done.

Topics: Animals; Male; Mice; Mutagenicity Tests; Mutagens; Neonicotinoids; Pesticides; Pyridines; Spermatozoa; Zineb

Cyanobacteria are a diverse group of Gram-negative bacteria that produce an array of secondary compounds with selective bioactivity against vertebrates, invertebrates, fungi, bacteria and cell lines. Recently the main methods of controlling cyanobacteria are using chemicals, medicinal plants and microorganism but fewer involved the safety research in hydrophytic ecosystems. In search of an environmentally safe compound, 53 chemicals were screened against the developed heavy cyanobacteria bloom Microcystis aeruginosa using coexistence culture system assay. The results of the coexistence assay showed that 9 chemicals inhibited M. aeruginosa effectively at 20 mg L(-1) after 7 days of exposure. Among them dimethomorph, propineb, and paraquat were identified that they are safe for Chlorella vulgaris, Scenedesmus obliquus, Carassius auratus (Goldfish) and Bacillus subtilis within half maximal effective concentration (EC50) values 5.2, 4.2 and 0.06 mg L(-1) after 7 days, respectively. Paraquat as the positive control observed to be more efficient than the other compounds with the inhibitory rate (IR) of 92% at 0.5 mg L(-1). For the potential inhibition mechanism, the chemicals could destroy the cell ultrastructure in different speed. The safety assay proved dimethomorph, propineb and paraquat as harmless formulations or products having potential value in M. aeruginosa controlling, with the advantage of its cell morphology degrading ability.

Topics: Animals; Bacillus subtilis; Chlorella vulgaris; Eutrophication; Goldfish; Microcystis; Morpholines; Paraquat; Scenedesmus; Toxicity Tests; Zineb

To study the persistence of propineb in/on onion a field experiment was conducted during 2007 at Agricultural Research Station, Durgapura, Jaipur Propineb70WP @ 1,225 and 2,450 g a. i. ha(-1) dose was applied as foliar spray to the crop thrice at an interval of 10 days. After third spray, onion samples comprising of green leaves and immature bulb were collected at 0,1,3,5,7,10 and 15 days. The initial deposit was 2.32 and 4.89 ppm of propineb (on CS(2) basis) which persisted up to the 10 and 15 days at normal 1,225 g a.i. ha(-1) and higher 2,450 g a.i. ha(-1) dose of fungicide application. The half life values of propineb ranged from 3.27 to 4.60 days.

Topics: Environmental Monitoring; Fungicides, Industrial; Onions; Soil; Soil Pollutants; Zineb

A supervised field trial was conducted on tea with propineb at 1,750 and 3,500 g a.i./ha at two locations (Assam and Darjeeling), applied thrice at an interval of 10 days during the year 2006-2007. Propineb residue was measured spectrophotometrically at 435 nm in terms of CS2. The initial deposit of propineb in green tea leaves were found to be in the range of 16.26-35.96 mg/kg and the residue persisted up to 10 days irrespective of doses and locations with half-life value ranging from 2.24 to 2.43 days and preharvest interval of 17.17-21.37 days. Made tea residues ranged from 9.27 to 20.86 mg kg(-1) on 7 days and no residues could be detected on 14 days. Infusion study indicated that propineb did not infuse into tea liquor from made tea. The limit of determination was found to be 0.1 mg kg(-1) in terms of propineb for green tea leaves, made tea, and tea liquor. The tea applied with the recommended dose of propineb is safe for consumption as liquor.

Topics: Beverages; Environmental Monitoring; Environmental Pollutants; Fungicides, Industrial; India; Plant Leaves; Risk Assessment; Tea; Zineb

Two of the most important categories of pesticides used in agricultural practice are organophosphates and dithiocarbamates. Their extensive and inappropriate use has rendered their reliable monitoring at trace levels more and more necessary. This study presents the construction of a rapid and sensitive cellular biosensor test based on the measurement of changes of the cell membrane potential of immobilized cells, according to the working principle of the Bioelectric Recognition Assay (BERA). The cells were immobilized by entrapment in a sodium alginate bead and directly applied in different pesticide dilutions and agricultural samples. The pesticides used were the organophosphate insecticide diazinon and the dithiocarbamate fungicide propineb. Two different cell types, N2a (neuroblastoma) and Vero (fibroblast) were used as the biosensory elements in order to investigate their differential response against the pesticides. In this way, we hoped to increase the selectivity of the assay. Based on the observed patterns of response, we demonstrate that the sensor can be used for the qualitative and, in some concentrations, quantitative detection of the pesticides with a high degree of reproducibility. The lowest detected concentration was 3nM. Finally, for the investigation of the effects of different pesticides on the accumulation of cytosolic Ca(2+), we conducted a fluorescent assay on N2a cells treated with tomato sample extracts, which were replicates of the E.U. proficiency test sample. The tomato samples were either organically grown or contained 14 different pesticides. The experimental results showed a higher increase of the intracellular Ca(2+) concentration in cells treated with non-organic samples compared to the cells treated with organic samples.

Topics: Animals; Biosensing Techniques; Calcium; Cells, Immobilized; Chlorocebus aethiops; Diazinon; Fluorescence; Insecticides; Membrane Potentials; Pesticide Residues; Pesticides; Solanum lycopersicum; Vero Cells; Zineb

Gill, trunk kidney, spleen, and liver of rainbow trout (Oncorhynchus mykiss) were examined after exposure to different sublethal concentrations of carbosulfan (25, 50 and 200 μgL(-1)), propineb (3, 6 and 24 mgL(-1)), and benomyl (2, 5 and 20 mgL(-1)) for 14 days. Lesions were observed in gill, trunk kidney, spleen, and liver of rainbow trout exposed to either concentration of pesticides. The most important lesions were determined in the highest concentrations of pesticides. Lamellar fusion, lamellar hyperplasia, epithelial lifting, vacuolization of epithelial tissue, epithelial necrosis, hypertrophy and sloughing of epithelium were observed on fish exposed to carbosulfan, propineb and benomyl. Fish had cell necrosis, degeneration and oedemas in liver, trunk kidney and spleen. None of these lesions were seen in control fish.

Topics: Animals; Benomyl; Carbamates; Case-Control Studies; Dose-Response Relationship, Drug; Gills; Kidney; Liver; Oncorhynchus mykiss; Organ Specificity; Pesticides; Spleen; Time Factors; Zineb

A gas chromatographic method with flame photometric detection (FPD (sulfur filter)) for analyzing the residues of 4 dithiocarbamates in 22 matrices in a heated closed vial has been established. The dithiocarbamate residues were decomposed to carbon disulfide (CS2) by SnCl2-HCl solution. The liberated CS2 was absorbed by hexane in the vial, and then determined by gas chromatography with FPD (sulfur filter). The results were expressed as the residues of dithiocabamates. The residue analysis method was validated by mancozeb, metiram, propineb and thiram in 22 matrices (apple, grape, etc). The average recovery ranges were from 72% to 110% with the relative standard deviations (RSD) between 0.8% and 22.0% when the fortified concentrations were between 0.06 and 3.0 mg/kg, and the quantitative analysis was performed by using external standard method. The limits of detection were in the range of 0.01-0.1 mg/kg (S/N = 3), and the limits of quantification were between 0.02 and 0.2 mg/kg (S/N = 10) for the 4 dithiocarbamate residues in the 22 matrices. This method is simple, fast, accurate, reproducible, and suitable for the determination of the 4 dithiocarbamate residues in the matrices mentioned in this paper.

Topics: Chromatography, Gas; Ditiocarb; Food Contamination; Fruit; Fungicides, Industrial; Maneb; Pesticide Residues; Thiocarbamates; Vegetables; Zineb

Neurological complications as well as movement disorders are relevant symptoms in animals and humans chronically exposed to dithiocarbamates. Using rat pheochromocytoma cells differentiated by NGF (PC12), we investigated whether propineb affects acetylcholine (Ach) release and the molecular mechanisms involved. Propineb (0.001-100 nM) dose-dependently increased Ach release from PC12. Thus, 0.001-1 nM propineb-induced Ach release, reaching a maximal effect ( approximately 50%) at 0.1-1 nM. Higher concentrations of propineb (10-100 nM) caused a progressive disappearance of the effect. Chelation of extra- and intracellular Ca(2+) did not affect Ach release by propineb, which was prevented by the actin stabilizer jasplakinolide (500 nM). Accordingly, actin depolymerization was observed after exposure of differentiated PC12 to 0.1-1 nM propineb, a loss of effect was evident at higher concentrations (100 nM), and the effect was Ca(2+)-independent. Disulfiram, a related dithiocarbamate not coordinated with Zn(2+), also depolymerized actin, suggesting the involvement of the organic structure of dithiocarbamates rather than the leakage of Zn(2+). Nevertheless, propineb did not depolymerize actin in a cell-free system. These data suggest that dithiocarbamates, through the activation of intracellular cascade(s), impair cytoskeletal actin. This effect may contribute to affect synaptic vesicles processing resulting in an impaired cholinergic transmission.

Topics: Acetylcholine; Actins; Alcohol Deterrents; Animals; Calcium; Cell Differentiation; Cell-Free System; Cytoskeleton; Depsipeptides; Disulfiram; Fungicides, Industrial; PC12 Cells; Rats; Zinc; Zineb

A simple, rapid and sensitive GC-MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS(2)), under acidic conditions in the presence of stannous chloride, extraction of the generated CS(2) into a layer of isooctane which is then analyzed for CS(2) content by GC-MS in SIM mode. Under the optimum conditions, the retention time of CS(2) was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86+/-7 (n=9) and 89+/-4 (n=9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8-1.0 ng m(-3) in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100+/-1 (n=3) and 98+/-2 (n=3), respectively, while for propylenethiourea were 102+/-1 (n=3) and 98+/-1 (n=3), respectively. The detection limits are about 36-43 and 40-49 ng m(-3) in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at -4 degrees C.

Topics: Air Pollutants; Environmental Monitoring; Molecular Structure; Thiourea; Zineb

A rapid and very sensitive high-performance liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) method for the simultaneous determination of dithiocarbamate (DTC) fungicide residues in fruits and vegetables was developed. The surface extraction of samples used an alkaline buffer consisting of sodium hydrogen carbonate and DL-penicillamine. The three DTC subclasses, i.e. dimethyldithiocarbamates (DMDs), ethylenebis(dithiocarbamates) (EBDs), and propylenebis(dithiocarbamates) (PBDs), were separated on a Sequant ZIC-pHILIC column using an acetonitrile/10 mM ammonia gradient. Because of the instability of DTC residues extracted from plant samples, a stable isotope dilution assay was applied. For each DTC subclass, the limits of detection and quantification were approximately 0.03 mg kg(-1) and 0.05 mg kg(-1), respectively. Recoveries from grapes, cucumbers, tomatoes, and rucola, spiked in the range of 0.01-0.9 mg kg(-1), averaged between 90 and 100%.

Topics: Chromatography, High Pressure Liquid; Food Contamination; Fruit; Fungicides, Industrial; Indicator Dilution Techniques; Isotopes; Pesticide Residues; Spectrometry, Mass, Electrospray Ionization; Thiocarbamates; Vegetables; Zineb; Ziram

We report on headache caused by the pesticide Antracol Combi WP 76. A headache caused by handling of pesticides should be distinguishable from migraine and headaches from other causes. This 29-year-old woman, who handled pesticides, presented with very strong headache with nausea and vomiting. Poisoning by this pesticide cannot be proven toxicologically, and there is no antidote. Following isolation from the pesticide and abundant hydration, the pain gradually decreased. History, clinical signs and neuroradiological examinations excluded other possible causes of the headache. In treatment of patients in rural areas, attention should also be paid to the pesticide Antracol Combi WP 76 as a possible cause of headaches.

Topics: Adult; Female; Headache; Humans; Nausea; Pesticides; Ultrasonography, Doppler, Transcranial; Vomiting; Zineb

Chitosan, (Biochikol 020 PC) a potential elicitor of plant defence and also an active inhibitor of fungal growth was used in experiments. The compound was used at concentrations 0.01 to 0.2% as a plant spray for rose protection against Sphaerotheca pannosa var. rosae, Peronospora sparsa and Diplocarpon rosae, Oidium chrysanthemi and Puccinia horiana on chrysanthemum, against Melampsora epitea on willow. Myrothecium roridum on dieffenbachia and against Lophodermium spp on Scots pine. Effectiveness of this product, applied curatively 2-times at 7-day-intervals after appearance of rose powdery mildew symptoms on most of plant parts, was about 32%. When compound was applied just after the first disease symptoms appearance, after 2-week-protection its effectiveness was about 43-60%. After 4 weeks, effectiveness of chitosan (Biochikol 020 PC) increased and ranged from 67 to 77%. In the control of P. sparsa on rose shrubs, growing in plastic tunnel, chitosan at conc. 0.025% was applied 4 times at weekly intervals. Effectiveness of chitosan against this pathogen was over 72%, similar as standard fungicide. Increase of chitosan (Biochikol 020 PC) concentration resulted in decrease of its effectiveness. In case of D. rosae control, chitosan used 9 times at weekly intervals was applied after first disease symptoms. After 3-week-protection effectiveness of the compound varied from 18 to 60% according to used concentration. After 9 weeks of protection effectiveness of tested product ranged from 16 to 23% and was connected with used concentration. Increase of chitosan concentration resulted in better protection of rose shrubs. Effectiveness of chitosan (Biochikol 020 PC) used 4-times at conc. 0.01 to 0.05% as chrysanthemum spray in the control of Oidium chrysanthemi ranged from 69 to 79%, whereas against Puccinia horiana from 54-97%. Two-time-spraying of willow with rust symptoms (Melampsora epitea) with chitosan at conc. 01-0.04% caused decrease of disease severity from 26 to 47%. Additionally about 10 to 25% of uredinia were dried up. Chitosan (Biochikol 020 PC) applied for leaf spraying inhibited the development of Myrothecium leaf spot on dieffenbachia more than 85%. Curative application of the compound controlled Myrotecium leaf spot at about 40%. Chitosan efficacy was also tested against one-year-old Pinus sylvestris seedlings growing in field conditions. Plants were sprayed fortnightly 14-times (long programme) or 5-times (short programme) against Lophodermium s

Topics: Ascomycota; Chitosan; Fungicides, Industrial; Mycoses; Pest Control, Biological; Plant Diseases; Plant Leaves; Rosa; Rosaceae; Zineb

This article addresses results from repeated 1- and 4-wk inhalation exposure studies in Wistar rats with solid aerosol (dust) atmospheres of propineb, a zinc bisdithiocarbamate homopolymer that is used as an agrochemical fungicide. Groups of 10 rats/sex were exposed nose-only to mean concentrations of 3.97, 11.24, and 21.95 mg propineb/m(3) using an exposure regimen of 6 h/day, 5 days/wk for 4 wk. Concentrations were selected based on results from a pilot study in which rats were exposed under identical conditions on 5 consecutive days for 6 h/day to mean concentrations of 10.1, 19.9, 38.1, and 78.7 mg/m(3). Both studies demonstrated that with respect to muscular effects female rats were remarkably more susceptible as compared to males. Female rats exposed to 11.24 mg/m(3) and above displayed characteristic signs of toxicity that included weakness and flaccid paralysis of hindlegs and ensuing immobilization that was considered to be the cause of emaciation and ensuing mortality in some rats. There was an apparent reciprocal relationship of concentration and the manifestation of clinical evidence of muscular dysfunction; that is, the onset in female rats exposed to 11.24, 21.95, 38.1, and 78.7 mg/m(3) was on days 15, 8, 4, and 3, respectively. In contrast, none of the male rats elaborated comparable effects up to 38.1 mg/m(3). Neuromuscular measures included leg grip strength and supplemented the clinical findings, whereas the landing foot splay was only minimally affected. Hematology and clinical pathology endpoints, including those addressing thyroidal function, were unobtrusive up to and including 78.7 mg/m(3). Lung weights were significantly increased in groups exposed to 21.95 mg/m(3) and above, especially in male rats. The microscopic examinations made in the 4-wk study demonstrated an increased incidence of intraalveolar material and enlarged, foamy alveolar macrophages at 3.97 mg/m(3) and above. Especially in female rats an atrophy of thigh muscle fibers, including increased nuclei and focal degeneration, occurred at 11.24 mg/m(3) and above. TTCA (2-thiazolidinethione-4-carboxylic acid) in urine, a metabolite and biomarker of exposure to CS(2), which is a putative breakdown product of propineb, was proportionally higher in the female rats exposed to 11.24 mg/m(3) and above. This biomarker appears to accumulate with time. This finding provides indirect evidence that the etiopathologic cause of neuromuscular changes is related to intermediary levels

Topics: Administration, Inhalation; Animals; Dose-Response Relationship, Drug; Female; Lung; Male; Muscle, Skeletal; Rats; Rats, Wistar; Zineb

Previous repeated inhalation exposure studies revealed two independent organotropic effects of inhaled propineb dust: One was restricted to the lung, the other to muscle weakness of hindlimbs. These effects were believed to be causally related to the principle decomposition products of this type of dithiocarbamate in the biological milieu and related to zinc and carbon disulfide. Two mechanistic 1-wk inhalation studies were performed, each focusing on one of these findings. The 7 x 6-h/day repeated-exposure inhalation study analyzed whether the nature of the response occurring at the alveolar level is "adaptive" or "early adverse" and whether soluble zinc is the causative agent. Groups of 18 female rats were exposed nose-only to mean concentrations of 0, 1.1, 5.5, and 25.8 mg propineb/m(3) and 6.9 mg ZnO/m(3). On postexposure days 1, 3, and 15 the time course of responses was analyzed by bronchoalveolar lavage (BAL), including quantification of Zn and metallothionein (MT) in BAL cells. Clinical evidence of muscular weakness was investigated separately in 20 female Wistar rats exposed to 70 mg propineb/m(3) on 5 consecutive days (6 h/day), followed by a 2-wk postexposure period. Clinical signs, body weights, and feed and water consumption were recorded as frequently as technically feasible. Fifty percent of rats received an oral cysteine supplementation to verify/refute the hypothesis that the incapacitation observed in previous studies is the cause of emaciation and associated impairment of CS(2) detoxification. The findings of the first study are consistent with this hypothesis, namely, that soluble Zn triggers a series of pulmonary events that is consistent with the homeostasis of this essential metal. It is concluded, accordingly, that the adjusted maximal workplace level for ZnO is also valid for propineb to preclude Zn-mediated responses to occur in the lung. With respect to muscular effects, this mechanistic study demonstrates further that the increased detoxification capacity afforded by oral supplementation of cysteine mitigates markedly the toxic potency of propineb. Procedural variables specific to the inhalation bioassay appear to be decisive for the elicitation of muscular effects. The major variable is considered to be the large drop in body weights associated with each exposure session and the concomitantly decreased uptake of essential nutritional factors (e.g., cysteine) involved in the detoxification of this compound. Accordingly, the mus

Topics: Administration, Inhalation; Animals; Dose-Response Relationship, Drug; Female; Lung; Muscle, Skeletal; Rats; Rats, Wistar; Zinc Oxide; Zineb

After repeated-dose toxicity studies with the fungicide propineb, reversible effects on muscle functions were found. Therefore, mechanistic investigations should contribute to clarification of its mode of action in relation to disulfiram and diethyldithiocarbamate neurotoxicity or direct effects on muscle cells. In principle, besides the dithiocarbamate effects, two different mechanisms have been discussed for this fungicide. One mechanism is the degradation to carbon disulfide (CS(2)) and propylenthiourea (PTU) and the other are direct effects of zinc. Primary neuronal cell cultures of the rat are a well established model to identify neurotoxic compounds like n-hexane or acrylamide. In this cell culture model, endpoints such as viability, energy supply, glucose consumption and cytoskeleton elements were determined. Additionally, skeletal muscle cells were used for comparison. Propineb and its metabolite PTU were investigated in comparison to CS(2), disulfiram and diethyldithiocarbamate. The toxicity of zinc was tested using zinc chloride (ZnCl(2)). It was clearly shown that propineb exerted strong effects on the cytoskeleton of neuronal and non-neuronal cell cultures (astrocytes, muscle cells). This was similar to ZnCl(2,) but not to CS(2). With CS(2) and disulfiram effects on the energy supply were more prominent. In conclusion, the toxicity of propineb is not comparable to disulfiram, diethyldithiocarbamate or CS(2) neurotoxicity. In regard to these findings, a direct reversible effect of propineb on skeletal muscle cells seems to be more likely.

Topics: Animals; Carbon Disulfide; Cell Survival; Cells, Cultured; Cerebral Cortex; Chlorides; Cytoskeleton; Disulfiram; Ditiocarb; Dose-Response Relationship, Drug; Enzyme-Linked Immunosorbent Assay; Fungicides, Industrial; Glucose; Muscle, Skeletal; Neurons; Rats; Thiourea; Zinc Compounds; Zineb

Dithiocarbamates (DTCs) are used mainly in agriculture as pesticides and as alcohol deterrent drugs. Neurological complications as well as movement disorders characterized by plastic rigidity, muscle twitch and paralysis are the prevailing symptoms in chronically exposed animals and humans. We investigated whether propineb interfered with peripheral cholinergic transmission in various isolated model systems. In electrically stimulated longitudinal muscle-myenteric plexus preparations (LMMPs), propineb (0.01-1000 nM) concentration-dependently enhanced the amplitude of both neurogenic twitch contractions and tritiated acetylcholine ([3H]ACh) release. The maximum percent increase was achieved by 10 nM propineb and was 19% and 14%, respectively. The effect on twitch contractions was partially antagonized by hexamethonium, a ganglionic nicotinic receptor blocker. In unstimulated LMMPs, propineb (10 pM, 10 nM, 10 microM) did not affect contractions to applied acetylcholine (ACh; 1 nM-10 microM), a finding indicating that propineb has no anticholinesterase activity. In human neuroblastoma cells (SH-SY5Y), propineb facilitated ACh release evoked by KCl depolarization. The increase in ACh release was not associated with detectable alterations of intracellular Ca2+([Ca2+]i) homeostasis. Binding studies carried out with alpha-bungarotoxin in striated muscle cells (L6) failed to demonstrate any influence of propineb on both affinity and capacity of skeletal muscle nicotinic receptors. In conclusion, propineb was found to interfere with cholinergic transmission in LMMPs and SH-SY5Y cells. In LMMPs, the potentiation of cholinergic transmission is partly dependent on the activation of ganglionic nicotinic receptors. Other targets relevant to cholinergic transmission seem not to be affected by propineb.

Topics: Acetylcholine; Animals; Bungarotoxins; Cholinergic Fibers; Dose-Response Relationship, Drug; Electric Stimulation; Fungicides, Industrial; Guinea Pigs; Hexamethonium; Humans; Ileum; Male; Muscle Contraction; Muscle, Skeletal; Muscle, Smooth; Myenteric Plexus; Neuroblastoma; Neuromuscular Junction; Signal Transduction; Tumor Cells, Cultured; Zineb

Topics: Agricultural Workers' Diseases; Dermatitis, Allergic Contact; Facial Dermatoses; Follow-Up Studies; Fungicides, Industrial; Hand Dermatoses; Humans; Male; Middle Aged; Patch Tests; Zineb

The dithiocarbamates are known to cause dermatitis, conjunctivitis, rhinitis, pharyngitis and bronchitis in humans. The experimental group received Propineb (obtained from Bayer) concentrations of 400 ppm in distilled water five days a week (treatment time three weeks) administered orally by gasric pit. Acute oral LD50 for male rats has been found to be 8,500 mg/kg (Worthing, 1983). The control group (n = 10) received only distilled water. At ultrasonographical examination, there were no resorbed fetuses or stillborns during or after propineb administration. It can be clearly seen that the body weights of the experimental group of litters are lower than those of the control group (p < 0.001). However, the mean length of the experimental litters was identical to the control group of litters (p > 0.05). Under microscopical examination, increased keratinization and hyperplasia were observed in the epidermal cells.

Topics: Animals; Animals, Newborn; Biopsy; Body Weight; Epidermis; Female; Fungicides, Industrial; Hyperplasia; Keratins; Male; Maternal-Fetal Exchange; Pregnancy; Rats; Rats, Wistar; Skin; Teratogens; Ultrasonography, Prenatal; Zineb

Dithiocarbamate propineb and maneb are organometal fungicides, which are widely used for the control of diseases in plants. Female Wistar rats were exposed orally to 200 and 400 ppm propineb (Zn-containing dithiocarbamate) and 250 ppm maneb (Mn-containing dithiocarbamate), from the 6th day of gestation up to birth. We found that the body weights of both newborn litters and their fungicide-treated mothers were lower than those of controls. Histological examination of the livers of fungicide-treated pregnant females and the offspring showed a variety of histopathological effects. Moreover, the analysis of Zn and Mn concentrations in the livers of pregnant females exposed to organometallic fungicides during pregnancy demonstrated that the metal concentrations in the liver were higher than those of controls. Similarly, the hepatic metal concentrations were significantly increased in the litters, indicating the transplacental passage of the organometallic fungicides.

Topics: Animals; Animals, Newborn; Female; Fungicides, Industrial; Histocytochemistry; Liver; Maneb; Manganese; Pregnancy; Pregnancy, Animal; Rats; Rats, Wistar; Zinc; Zineb

Dithiocarbamate propineb and maneb are organometal fungicides, which are widely used for the control of diseases in plants. Female Wistar rats were exposed orally to 200 and 400 ppm propineb and 250 ppm maneb, from the sixth day of gestation up to birth. We found that the body weights of both one-day old litters and their fungicide-treated mothers were lower than those of controls. Histological examination of the kidneys of fetus and fungicide-treated pregnant females showed a variety of histopathological effects. Moreover, the analysis of zinc (Zn) and manganese (Mn) concentrations (using inductively coupled plasma-atomic emission spectrometry) in the kidneys of pregnant females exposed to organometallic fungicides during pregnancy demonstrated that the metal concentrations in the kidney were higher than those of controls. However, the renal metal concentrations were significantly increased in the litters subjected to the fungicides during gestation, indicating that high levels of the trace metals in the organ of fetus may well be due to the fungicides easily passing the placental barrier.

Topics: Animals; Animals, Newborn; Body Weight; Female; Fetus; Fungicides, Industrial; Kidney; Male; Maneb; Manganese; Maternal-Fetal Exchange; Pregnancy; Prenatal Exposure Delayed Effects; Rats; Rats, Wistar; Zinc; Zineb

The carcinogenic potential of 5 pesticides was analyzed using a medium-term multi-organ bioassay for carcinogenicity. Male F344 rats were initially treated with 3 known carcinogens (diethylnitrosamine, N-methyl-N-nitrosourea and N-bis(2-hydroxypropyl)nitrosamine) during a period of 4 weeks to induce neoplastic changes in a variety of organs, and then given one of 5 pesticides in the diet for a further 16 weeks. Neoplastic and pre-neoplastic lesions were found in the thyroid, kidney and urinary bladder with propineb, in the forestomach, kidney and thyroid with captan and folpet. The number of glutathione S-transferase placental-form-positive liver-cell foci was significantly increased in the captan- and phosmet-treated groups. Based on these findings, captan and propineb can be considered as carcinogens and carcinogenicity is suspected for folpet and phosmet. These results are in concordance with reported long-term carcinogenicity for captan, folpet and propineb. Daminozide was considered not to be carcinogenic. Thus, the present assay of 20 weeks' duration is useful for the prediction of potential carcinogens.

Topics: Animals; Body Weight; Captan; Carcinogenicity Tests; Carcinogens; Cocarcinogenesis; Diethylnitrosamine; Liver; Liver Neoplasms, Experimental; Male; Methylnitrosourea; Models, Biological; Nitrosamines; Organ Size; Pesticides; Precancerous Conditions; Rats; Rats, Inbred F344; Zineb

This experiment was performed in Wistar rats of both sexes exposed subchronically to 1:100, 1:500, 1:1000 and 1:1500 LD50. The evaluation was based on endpoints measured on the 30th and 90th after starting exposure and after a recovery period of 30 days: these included clinical signs, functional changes, hematological parameters, urine analysis, biochemical, histochemical, immunomorphological endpoints, electron microscopy of internal organs, chromosome examination of bone marrow. A high lethality was shown to occur with a characteristic clinical picture: interruption of weight gain, behavioural changes, leucopenia mainly involving neutrophil leucocytes, biochemical changes characteristic of liver, cardio-vascular system (myocardium and aorta) together with pathologic, biochemical, histochemical and ultrastructural changes in liver, brain, thyroid gland, myocardium, spleen and bone marrow. Endpoints were shown to be clearly dose-dependently related with small variations with the low dose, i.e. 1:1500 LD50 (5 mg/kg-1 bw).

Topics: Animals; Female; Fungicides, Industrial; Lethal Dose 50; Male; Rats; Rats, Wistar; Zineb

The teratogenic and goitrogenic effects of Propineb, dithiocarbamate pesticide and Propylenthiourea (PLTU), its metabolite and degradation product have been studied. The aim of this study was to show the possible correlation between the two activities. Female Sprague-Dawley rats were treated with Propineb and PLTU starting from 6th to 16th day of pregnancy. The functional state of maternal and foetal thyroid, the toxicity of products versus dams and embryotoxic and teratogenic effects were examined. The observed goitrogenic effect may be compared to that reported in the previous studies of the authors, if considering time of sacrifice. In fact, the lesion quickly rises and as rapidly regresses when treatment is stopped. The foetal thyroid has not been affected by the product administered to the dams. PLTU showed a clear teratogenic activity at doses that did not show any maternal toxicity (45 and 90 mg/k).

Topics: Animals; Antithyroid Agents; Female; Fungicides, Industrial; Pregnancy; Pregnancy Complications; Rats; Rats, Inbred Strains; Teratogens; Thiocarbamates; Thiourea; Zineb

The possible clastogenic activity of Propineb, Propineb technical grade and of its main metabolite, propylene-thiourea (PLTU), was investigated by the micronucleus test in mice according to Schmid. No statistically significant increase in the percentage of micronuclei was observed at any of the tested doses of the above compounds. As positive controls, dose-effect curves were constructed for methyl methanesulfonate (MMS) and mitomycin C (MMC).

Topics: Animals; Antibiotics, Antineoplastic; Cell Nucleus; Erythrocytes; Female; Male; Methyl Methanesulfonate; Mice; Mitomycin; Mitomycins; Mutagenicity Tests; Mutagens; Mutation; Thiocarbamates; Thiourea; Zineb

Propineb, a dithiocarbamate fungicide, was studied by using the sperm morphology assay in (C57BL6 male X C3H female) F1 mice. At all dose levels, no statistically significant increase in the percentage of sperm abnormalities was observed. Methyl methanesulfonate (MMS) and 2-acetylaminofluorene (2-AAF), which were tested as positive controls, induced a dose-effect-related increase in teratospermia.

Topics: 2-Acetylaminofluorene; Animals; Crosses, Genetic; Drug Evaluation, Preclinical; Female; Male; Methyl Methanesulfonate; Mice; Mice, Inbred Strains; Organ Size; Spermatozoa; Teratogens; Testis; Thiocarbamates; Zineb

Oral administration of high dosages of the dithiocarbamate pesticides maneb and mancozeb was teratogenic in rats but not in mice. The malformations, severe limb and craniofacial defects, were pronounced after maneb treatment but less so after mancozeb and propineb, zinc-containing compounds. The teratogenic effect of maneb was progressively reduced by simultaneously administering increasing amounts of zinc acetate. The mechanism of the teratogenic effect may involve the compounds being chelating agents, trapping zinc required for many important enzyme systems.

Topics: Abnormalities, Drug-Induced; Acetates; Animals; Female; Fetal Resorption; Maneb; Mice; Pregnancy; Rats; Thiocarbamates; Zinc; Zineb