O-ethyl S-propyl Phosphorothioate Research Articles

An efficient electrochemical sensing platform for profenofos detection

Profenofos is classified by the WHO as a moderately toxic pesticide (category II pesticide) for humans as it inhibits the acetylcholinesterase enzyme and causes respiratory distress. In this study, -NaCl-complexed crown ether was used to modify the Glassy Carbon Electrode (GCE) to detect the presence of profenofos in water at ultra-low level concentration. Differential pulse voltammetry was used to detect the target analyte at lower concentration with higher sensitivity. Suppression of charge transfer due to the ionic interaction between the positively charged sodium ion in NaCl-complexed crown ether and the negatively charged oxygen ion in O-ethyl S-propyl phosphorothioate results in the formation of NaCl•15-crown-5-O-ethyl S-propyl phosphorothioate. This in-turn inhibits the charge transfer process of [Fe(CN)6]3-/4-redox couple to the GCE, hence reducing the current density as a function of profenofos concentration. The profenofos sensor exhibits a wide linear range of 1.025–153.645 nM with a low detection limit of 0.341 nM and a sensitivity of 0.05 µA nM−1. And also, the developed sensor showed RSD, % of inhibition, and stability of <2.27%, <5%, 7 days, respectively. Owing to its stability, the sensor can be utilized for real-time testing of water quality.

COMPARISON BETWEEN CUSTOMS PREPARATIONS AND WORKOUT PREPARATIONS FOR PESTICIDE PROFENOFOS FROM DIFFERENT SOURCES AND UNDER SPECIFIC ENVIRONMENTAL CONDITIONS

Four generic profenfos formulations under trade name Camkron and Tiliton 72% EC (customs, workout) for each of those, which currently applied in Egypt from different companies were studied for the effects of sunlight exposure, UV-light, PH and storage on the stability of profenofos, its respective impurity 4-bromo-2-chlorophenol content and water as a relevant impurity. Exposure to sunlight, UV-light at 16 hours and storage for 14 days at 54±2o C indicated various degradation effects on profenofos content and increase the formation of its impurity 4-bromo-2-chlorophenol and the change in PH in long period cause breakdown of the active substance instability of some component. The storage of profenofos at intervals of 3, 7 and 14 days at 54 ± 2o C from the results obtained showed serious effects on the rate of degradation of profenofos and the increase in the rate of formation of 4-bromo-2-chlorophenol, as well as on sunlight, UV-light exposure, for all of the profenofos formulations under study. It found that the Camkron (workout) is invalid for use it may be due to several factors affecting the consistency of the formulation of profenofos in the manufacturing process, the origins of technical materials, the use of various forms of adjuvants and the long storage time in poor conditions. Analysis before and after storage, sunlight exposure, UV-light using GC-MS identified four degradation products: 4-bromo-2-chlorophenol, O-(4-bromophenyl) O-ethyl S-propyl phosphorothioate, O-(2-chlorophenyl) O-ethyl S-propyl phosphorothioate and O-(4-bromo-2-chlorophenyl) S-propyl hydrogen phosphorothioate and also used IR spectra.

Thermal and photolysis degradation of three profenofos formulations

Three commercial profenofos emulsifiable concentrate (EC) formulations 720 g/l (72% w/v) currently applied in Egypt from three different companies were studied for the effect of sunlight exposure and storage on the stability of profenofos and its relevant impurity 4-bromo-2-chlorophenol content. Exposure to sunlight and storage for more than 14 days at 54 ±2 oC indicated various degradation effects on profenofos content and increase the formation of its impurity 4-bromo-2-chlorophenol. Identification of profenofos content and degradation products were determined using GC–FID and GC-MS. From the obtained results the storage of profenofos at 54 ±2 oC at intervals 28, 42, 56 and 70 days showed serious effects on the degradation rate of profenofos and increase the rate of formation of 4-bromo-2-chlorophenol compared to exposure to sunlight for all profenofos formulations under study. The results showed variable rate of degradation of profenofos and the amount of its relevant impurity 4-bromo-2-chlorophenol for all samples sources under investigation. Analysis after storage using GC-MS identified three degradation products: 4-bromo-2-chlorophenol, O-ethyl-O-(2-chloro-4-bromo-phenyl)-phosphate and O-(4-bromophenyl) O-ethyl S-propyl phosphorothioate.

Profenofos, an Acetylcholinesterase-Inhibiting Organophosphorus Pesticide: A Short Review of Its Usage, Toxicity, and Biodegradation.

Pesticides play an important role in the protection of different crops. Among the diverse sets of pesticides used all over the world, the organophosphates are the most widely used group. Profenofos [O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate] is one of the most largely used organophosphate insecticides on field crops, vegetables, and fruit crops. The World Health Organization classifies this compound as moderately hazardous (Toxicity Class II), and its residues have been found in vegetables like okra [ (L.) Moench], gooseberries ( sp.), green chilies [ (L.)], curry leaves [ (L.) Spreng], mint leaves [ (L.)], and coriander leaves [ (L.)]. Dietary intake of profenofos (PFF) is the major exposure pathway for humans. When applied to agricultural fields, PFF residues spread into every part of the environment: ambient air, surface water, and soil. In this review, we discuss the worldwide usage of PFF pesticide, its toxic effects on humans and other living organisms in the environment, and biodegradation of this chemical by various microbial strains. To date, no complete biodegradation pathway has been established for PFF pesticide, calling for a study of this nature.

14C-Prothiofos Residues in the Presence of Deltamethrin and Dimilin Pesticides in Cotton Seeds and Oils, Removal of Prothiofos Residues in Oils and Bioavailability of its Bound Residues to Rats

Ethyl-1-14C-prothiofos and some of its degradation products have been prepared for the present investigation. Cotton plants were treated with 14C-prohiofos alone and in presence of deltamethrin and dimilin pesticides under conditions simulating local agricultural practice. 14C-residues in seeds were determined at harvest time about 75% of 14C-activity was associated with oil. The ethanol soluble 14C-residues accounted for 6% of the total seed residues after further seeds extraction, while the cake contained about 18.5% of the total residues in case of prothiofos only. The bound residues increased in presence of deltamethrin and dimilin pesticides and amounted to 30% and 34% of the total residues, respectively. About 89% of the 14C-activity in the crude oil could be eliminated by simulated commercial processes locally used for oil refining. Chromatographic analysis of cotton oil extracts (acetonitrile layer) revealed the presence prothiofos oxon, O-ethyl phosphorothioate, O-ethyl S-propyl phosphorothioate, des-propylthio prothiofos, O-ethyl phosphoric acid as the main degradation products, besides to one unknown compound in addition to the parent compound, in case of prothiofos alone. The same degradation products are found in case of prothiofos and deltamethrin and prohiofos and dimilin except compounds O-ethyl S-propyl phosphorothioate and des-propylthio prothiofos. Chromatographic analysis of ethanol extract revealed the presence of O-ethyl phosphorothioate, despropylthio prothiofos and O-ethyl phosphoric acid as free metabolites. The conjugated metabolite was liberated by acid hydrolysis and identified as 2,4-dichlorophenole which was detected by color. When rats were fed the extracted cake for 72 hours, the bound residues were found to be bioavailable. The main excretion route was via the expired air (49%), while the 14C-residues excreted in urine and feces were (34% and 9.7%), respectively. The radioactivity detected among various organs accounted to 6.1%. Chromatographic analysis of urine was determined.

Fate of 14C-ethyl prothiofos insecticide in canola seeds and oils

Canola plants were treated with 14C- prohiofos under conditions simulating local agricultural practices. 14C-residues in seeds were determined at different time intervals. At harvest time about 32 % of 14C-activity was associated with oil. The methanol soluble 14C-residues accounted for 12 % of the total seed residues after further seeds extraction, while the cake contained about 49 % of the total residues. About 69 % of the 14C-activity in the crude oil could be eliminated by simulated commercial processes locally used for oil refining. Chromatographic analysis of crude and refined oil revealed the presence of the parent compound together with three metabolites which were identified as prothiofos oxon, O-ethyl phosphorothioate and O-ethyl S-propyl phosphorothioate, besides one unknown compound. While methanol extract revealed the presence of despropylthio prothiofos and O-ethyl phosphoric acid as free metabolites acid hydrolysis of the conjugated metabolites in the methanol extract yielded 2, 4-dichlorophenole which was detected by color. When rats were fed the extracted cake for 72 hours, the bound residues were found to be bioavailable. The main excretion route was via the expired air (42 %), while the 14C-residues excreted in urine and feces were 30 % and 11 %, respectively. The radioactivity detected among various organs accounted to 7.5 %.Chromatographic analysis of urine indicated the presence of prothiofos oxon, O-ethyl phosphoric acid and 2, 4-dichlorophenole as main degradation products of prothiofos in free and conjugated form.

Effects of insecticide profenophos on germination, early growth, meiotic behavior and chlorophyll mutation of barley (Hordeum vulgare L.)

The genotoxicity of different concentrations of insecticide, profenophos (O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate) was evaluated at various stages of cell cycle (G1, S and G2) by using the seeds of barley (Hordeum vulgare L.). The aim of this work was to investigate the effects of insecticide profenophos at various stages of cell cycle on germination, seedling height and meiotic behavior in M1 and chlorophyll mutations in M2 generation. From the present study, it can be concluded that the stages of cell cycle were sensitive for the treatments of chemicals and it also showed that the S-phase of cell cycle is more sensitive than other phases of cell cycle.

Quantitative nuclear magnetic resonance spectrometry: II. Purity of phosphorus-based agrochemicals glyphosate ( N-(phosphonomethyl)-glycine) and profenofos ( O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate) measured by 1H and 31P QNMR spectrometry

The purities of the widely-used herbicide glyphosate ( N-(phosphonomethyl)glycine), and the insecticide profenofos ( O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate) were determined by 1 H and 31 P quantitative nuclear magnetic resonance (QNMR) spectrometry using an internal standard. QNMR does not need a standard reference of the same target analyte, in contrast to chromatographic methods, but only a compound containing the nucleus of interest. Sodium acetate and sodium phosphate of known purity were chosen as internal standards for 1 H NMR and 31 P NMR), respectively for the water soluble glyphosate and a single internal standard, trimethyl phosphate for both 1 H and 31 P NMR quantitative analysis of the organic soluble profenofos. These standards have NMR peaks that do not interfere with those of the analyte, they are chemically inert and are soluble in the deuterated solvent. The average purity of glyphosate obtained by 1 H NMR (97.07%, σ=0.68) agreed with that by 31 P NMR (96.53%, σ=0.90; ANOVA, P=0.074) for the five batches provided by the manufacturer according to the procedures for chemical registration in Australia. The standard deviations of seven independent analyses of a single batch by 1 H NMR and 31 P NMR were σ=0.24% and σ=0.33%, respectively, values which confirm the exceptional precision of the method. The purity of profenofos by 1 H NMR (94.63%, σ=0.14) also agreed with that by 31 P NMR (94.62%, σ=0.59; ANOVA, P=0.97). Uncertainty budgets for the measured purities of glyphosate and profenofos show that the uncertainty in the purity of the internal standard is a major contributor to the uncertainty of the result. NMR was also used to establish the impurity profile of both compounds, and quantify the impurities present.

Profenofos residues in wild fish from cotton-growing areas of New South Wales, Australia.

The organophosphorus (OP) pesticide profenofos (O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate) is used heavily in cotton-growing areas of eastern Australia toward the end of the growing season. European carp (Cyprinus carpio), bony bream (Nematalosa erebi), and mosquitofish (Gambusia holbrooki) were collected from the cotton-growing areas around Wee Waa, New South Wales, to determine the relationship between profenofos residues and acetyl-cholinesterase (AChE) activity in wild fish. Profenofos concentrations in water, sediment, and fish tissue reflected its general level of use; levels in March 1994 were significantly higher than in 1993 and generally decreased in May, 6 wk after cessation of spraying. Residues in carp and bony bream generally correlated with concentrations in water and sediment, although residues in fish tend to persist longer at some sites. Acetylcholinesterase inhibition was a useful indicator of profenofos exposure within a season, particularly if linked with residue measurements. Bony bream and gravid female mosquitofish recovered AChE levels more slowly than carp or nongravid mosquitofish. Recovery in creeks was generally more rapid than in lagoons.

Identification of 4‐bromo‐2‐chlorophenol as a contaminant responsible for organoleptic taint in melons

An off-odour, described by the growers as similar to profenofos, occurred in melons in which this pesticide had been used in crop treatment. However, profenofos, O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate, could not be detected in the melons using GC/MS although a component with a shorter retention time was found. Concentration of melon volatiles by steam distillation yielded a product identical to that obtained by hydrolysis of profenofos, identified as 4-bromo-2-chlorophenol. A solution of this compound in water had similar organoleptic properties to that of the contaminated fruits. It was concluded that 4-bromo-2-chlorophenol was responsible for the taint detected in melons.

Fate and Efficacy of O-[4-[(4-Chlorophenyl)thio]phenyl]O-Ethyl S-Propyl Phosphorothioate (RH-0994) after Application to the Tobacco Budworm (Lepidoptera: Noctuidae) and the Boll Weevil (Coleoptera: Curculionidae)

Studies with the 14C-labeled experimental insecticide RH-0994 (O-[-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate) demonstrated that adult boll weevils (BWv). Amthonomus grandis Boheman, absorbed topical doses of the compound at a significantly slower rate than 3rd-instar, insecticide-susceptible (S-TBW) or field-collected (F-TBW) tobacco budworms, Heliothis virescens (F.), and that absorption by F-TBW was significantly slower than for S-TBW. In tests of the topical toxicity of RH-0994 against third-stage TBW and adult BWv, the order of susceptibility was S-TBW > F-TBW > BWv. Comparative studies of the metabolism of [14C]RH-0994 by fifth stage S- and F-TBW larvae indicated the insects metabolized oral doses of the compound rapidly at about equivalent rates and produced the same array of metabolites. Field tests of RH-0994 (0.84 and 1.12 kg/ha) against natural populations of Heliothis spp. in cotton indicated that control was comparable to that afforded by sulprofos (1.12 kg/hal and flucythrinate (28.0 and 44.8 g/ha).

Resolution and biological activity of the chiral isomers of O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate (profenofos insecticide)

Resolution and biological activity of the chiral isomers of O-(4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate (profenofos insecticide)

Fate of O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in soil

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTFate of O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in soilDon L. Bull and G. Wayne IvieCite this: J. Agric. Food Chem. 1982, 30, 1, 150–155Publication Date (Print):January 1, 1982Publication History Published online1 May 2002Published inissue 1 January 1982https://doi.org/10.1021/jf00109a033RIGHTS & PERMISSIONSArticle Views29Altmetric-Citations3LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (746 KB) Get e-Alerts Get e-Alerts

Fate of the insecticide O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in water

Fate of the insecticide O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in water

Fate of O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in cotton

Fate of O-[4-[(4-chlorophenyl)thio]phenyl] O-ethyl S-propyl phosphorothioate (RH-0994) in cotton