Presence Of Organophosphorus Compounds Research Articles

Photodegradation kinetics of organophosphorous with hydroxyl radicals: Experimental and theoretical study

The presence of organophosphorus compounds (OPs) in the environmental counterparts has become an important problem because of their toxicity. In this study, the photocatalytic degradation reactions of the three OPs with hydroxyl radical were investigated by both experimental and quantum chemical methods. Photocatalytic degradation kinetics of the examined organophosphorus compounds were investigated under UV-A irradiation using TiO2 as the photocatalyst. The effects of the initial concentrations on the degradation rate have been examined. There was an observable loss of OPs in the presence of TiO2 photocatalyst under UV-A at 0.2 g TiO2 per 100 mL. The quantum chemical calculations have been carried out by the density functional theory (DFT) at B3LYP/6-31g(d) level. The reaction pathways were modelled to find the most probable mechanism for OPs with the OH radical and to determine the primary intermediates. The rate constants of the eight reaction paths were calculated by the transition state theory. Conductor-like polarizable continuum model (CPCM) was used as the solvation model with the intention of understanding the water effect. The theoretical results were in agreement with experimental ones.

Prediction of Ligands Binding Acetylcholinesterase with Potential Antidotal Activity: A Virtual Screening Approach.

Intoxications caused by organophosphorus compounds (OPs) are associated with the reversible, and sometimes irreversible interaction with acetylcholinesterase (AChE). OPs are commonly used as pesticides mainly in developing countries, where the associated poisoning is a major health problem related to suicidal attempts, careless manipulation, and chemical warfare. The current antidotes are oxime-based drugs that can regenerate the AChE catalytic activity. Nevertheless, challenges associated with lack of efficiency and difficulties for crossing blood-brain barrier have motivated the design of novel alternatives. We used a validated molecular docking approach for the virtual screening of 579,890 synthetic ligands and 478 drugs against a human AChE in its apo conformation, and a murine AChE conjugated with the OP tabun. After filtering, 7 hits were selected as potential competitors due to the formation of key interactions within the active site gorge of the AChE structure, and potential reactivators based on interactions with amino acids of the catalytic triad in the presence of organophosphorus compounds. The selected candidates will be further evaluated through in vitro and in vivo assays.

Development of a sensitive, generic and easy to use organophosphate skin disclosure kit

Various organophosphorus compounds (OP), primarily the nerve agent VX and other V-agents, are highly toxic to humans after skin exposure. Percutaneous exposure by such OP results in a delayed onset of toxic signs which enables the initiation of specific countermeasures if contamination is detected rapidly. Presently available mobile detection systems can hardly detect skin exposure by low volatile OP. In order to fill this gap an OP skin disclosure kit was developed which should fulfill different requirements, i.e. ▪ a high sensitivity, ▪ coverage of human toxic OP, ▪ easy handling, ▪ rapid results, ▪ small dimension and weight. The kit includes a cotton swab to sample skin, human AChE as target and chemicals for a color reaction based on the Ellman assay which is recorded by visual inspection. OP is dissolved from the sampler in a test tube filled with phosphate buffer (0.1M, pH 7.4) and incubated with lyophilized human AChE for 1min. The reaction with acetylthiocholine and 5,5′-dithio-bis-2-nitrobenzoic acid (1min) results in a rich yellow color in the absence of OP and in contrast, in transparent or pale yellow buffer in the presence of OP. At the recommended conditions, the limit of detection is 100ng VX and Russian VX and 50ng Chinese VX on plain surface and 200ng VX on rat skin. With activated pesticides, paraoxon and malaoxon, a concentration of ∼10μg can be detected on plain surface. The ready-to-use kit has a weight of 16g and a size of 10×12×1cm. In the end, this kit has the potential to fill a major gap and to enable timely detection of OP skin exposure and initiation of life-saving countermeasures.

Residues of organochlorine and organophosphorus pesticides in sugarcane crop soils and river water

The presence of residual organochlorine and organophosphorus pesticides was evaluated at different periods of sugarcane cultivation in agricultural soil and water samples from the town of Tlaltizapan, which is located in the state of Morelos in Mexico, to determine the presence and persistence of these compounds and their possible effects on the region. The compounds p,p′-DDE, p,p′-DDD (metabolites of p,p′-DDT), γ-HCH and heptachlor were found in more of 95% of the sampling zones in the three monitoring periods performed along 2 years. The highest concentration detected (129.6 μg/kg dry soil) was for α-HCH, but its frequency of detection was ∼5%. The low detection frequency of α-HCH and the high concentration values of γ-HCH indicate the repeated use of technical-grade HCH and Lindane (γ-HCH) in the region. Among the organophosphorus pesticides, ethyl parathion was the compound with the highest soil concentration, at ∼2000 μg/kgdry soil, during the initial monitoring. However, this compound was detected in the second monitoring with a concentration of ∼4 μg/kgdry soil, but it was not detected in the third, indicating that is was not accumulated in the environment. The heptachlor was the compound most commonly found in all water samples, within a range of 0.45–1.25 ng/L. The presence of this organochlorine compound in the water samples indicated a possible migration from the soil to water bodies due to soil erosion. The presence of organophosphorus compounds was not detected in the water samples, which could be attributed to the moderate persistence of these compounds and their consequent degradation before arriving at the water bodies.

A thin film electro-acoustic enzyme biosensor allowing the detection of trace organophosphorus pesticides

We report an analytical method using a thin film electro-acoustic resonator for the detection of organophosphorus pesticides. The acetylcholinesterase (AChE) enzyme was immobilized on the surface of the resonator. In the presence of organophosphorus compounds, the degree of inhibitory effect of organophosphorus compounds on the AChE activity and the concentration of pesticides were detected in real time by measuring the frequency shift of the resonator. The proposed device has a remarkably low detection limit of 1.8×10−11M and obvious advantages such as small size, simple operation, and integrated circuit compatibility, providing a promising tool for pesticide analysis.

Layer-by-Layer Films of Chitosan, Organophosphorus Hydrolase and Thioglycolic Acid-Capped CdSe Quantum Dots for the Detection of Paraoxon

A polyelectrolyte architecture was fabricated that was composed of chitosan and organophosphorus hydrolase polycations along with thioglycolic acid-capped CdSe quantum dots (QDs) as the polyanion. This film was imaged by epifluorescence microscopy. UV−vis and emission spectroscopies were used to monitor the growth of the bilayer film due to the enhanced optical property of QDs. Photoluminescence of the functionalized QDs improved when sandwiched between the polycations layers. The presence of organophosphorus compounds was confirmed through photoluminescence spectroscopy.

Layer-by-Layer Biosensor Assembly Incorporating Functionalized Quantum Dots

Layer-by-layer (LbL) assembly has been utilized to fabricate an ultrathin film of polyelectrolytes. The architecture was composed of chitosan and organophosphorus hydrolase polycations along with thioglycolic acid-capped CdSe quantum dots (QDs) as the polyanion. The topography of the films was studied using epifluorescence microscopy imaging. The photoluminescence property of the functionalized QDs improved when sandwiched between the polycation layers. The enhanced optical property of QDs allowed easy monitoring of LbL growth and detection of paraoxon with high sensitivity. The presence of organophosphorus compounds was confirmed through UV−vis and emission spectroscopies.

Kinetics of calcium sulfate formation in aqueous media: effect of organophosphorus compounds

The kinetics of spontaneous precipitation of calcium sulfate dihydrate at pH 7.0, 30°C were investigated in the presence of organophosphorus compounds. The measurement of the kinetics parameters was done at conditions of constant supersaturation probing the conductivity of the supersaturated solutions. Aqueous solutions of 1-hydroxy-ethylidene-1,1-diphosphonic acid (EHDP), nitrilotrimethylene phosphonic acid (NTMP) and N,N,N′,N′-ethylene diaminotetramethylene phosphonic acid (ENTMP) were included in unstable supersaturated solutions of calcium sulfate. NTMP and ENTMP at concentration levels between 0.1 and 1.0 μM increased drastically the induction times preceding precipitation while the rates of precipitation were reduced by 90% at concentrations below 1μM. EHDP was effective in reducing the precipitation rates but at considerably higher concentrations (70% reduction at 0.1 μM). Examination of the morphology of the precipitated crystals suggested that the kinetic results obtained could be attributed to the adsorption of the organophosphorus compounds onto different gypsum crystal faces. EHDP did not inhibit the [0 2 0] face resulting in elongated prismatic crystals, while NTMP and ENTMP favored the development of [0 2 0] resulting in shorter and broader crystallites.

THE REACTIVITY OF ESTERASES AND PROTEASES IN THE PRESENCE OF ORGANOPHOSPHORUS COMPOUNDS

THE REACTIVITY OF ESTERASES AND PROTEASES IN THE PRESENCE OF ORGANOPHOSPHORUS COMPOUNDS