Biodegradation of monocrotophos by Brucella intermedia Msd2 isolated from cotton plant.

Widespread and inadequate use of Monocrotophos has led to several environmental issues. Biodegradation is an ecofriendly method used for detoxification of toxic monocrotophos. In the present study, Msd2 bacterial strain was isolated from the cotton plant growing in contaminated sites of Sahiwal, Pakistan. Msd2 is capable of utilizing the monocrotophos (MCP) organophosphate pesticide as its sole carbon source for growth. Msd2 was identified as Brucella intermedia on the basis of morphology, biochemical characterization and 16S rRNA sequencing. B. intermedia showed tolerance of MCP up to 100 ppm. The presence of opd candidate gene for pesticide degradation, gives credence to B. intermedia as an effective bacterium to degrade MCP. Screening of the B. intermedia strain Msd2 for plant growth promoting activities revealed its ability to produce ammonia, exopolysaccharides, catalase, amylase and ACC-deaminase, and phosphorus, zinc and potassium solubilization. The optimization of the growth parameters (temperatures, shaking rpm, and pH level) of the MCP-degrading isolate was carried out in minimal salt broth supplemented with MCP. The optimal pH, temperature, and rpm for Msd2 growth were observed as pH 6, 35 °C, and 120 rpm, respectively. Based on optimization results, batch degradation experiment was performed. Biodegradation of MCP by B. intermedia was monitored using HPLC and recorded 78% degradation of MCP at 100 ppm concentration within 7 days of incubation. Degradation of MCP by Msd2 followed the first order reaction kinetics. Plant growth promoting and multi-stress tolerance ability of Msd2 was confirmed by molecular analysis. It is concluded that Brucella intermedia strain Msd2 could be beneficial as potential biological agent for an effective bioremediation for polluted environments.

Encapsulation of water soluble pesticides for extended delivery of pesticides without contaminating water bodies.

The main objective of this study is to develop polymeric encapsulated formulation for the water soluble broad-spectrum pesticides. Pesticides contaminate the environment in different ways but foremost hazards are linked with the contamination of water bodies. Water soluble pesticides are the major deleterious agents and go off into ground water and different water bodies through leaching or surface runoff from the applied places. Besides this some of the water soluble pesticides are broad-spectrum, but proper methods and techniques are not available for their effective and safe usage, all broad-spectrum pesticide are disappearing from the pesticide lists every year. Hence, the present study is based on development of encapsulated formulation for water soluble broad-spectrum pesticide i.e. Monocrotophos. In this study, water soluble pesticide was encapsulated in polyvinyl alcohol (PVA) polymer along with surfactants and cross linker. The developed microspheres were analyzed in HPLC for calculating loading capacity and encapsulation efficacy, these were calculated 0.75 and 90% respectively. The FT-IR data results confirmed that the monocrotophos successfully encapsulated in the PVA polymer with respective bands. The degradation studies show that in encapsulated formulation monocrotophos degradation was found only 10% after 94 hrs. Optical micrographs in aqeous solution indicate spherical shapes with size in the rage of 7-8 µm of encapsulated formulation. XRD data further crystalline nature of polymeric encapsulated formulation. The study may provide a new corridor to save the broad-spectrum water soluble pesticides which are on the verge to be banned.

Establishment of resveratrol and its derivatives as neuroprotectant against monocrotophos-induced alteration in NIPBL and POU4F1 protein through molecular docking studies.

Monocrotophos (MCP) is a broad spectrum organophosphorus insecticide, which is widely used as foliar spray to the different important crops. MCP may reach the soil and the aquatic environment directly or indirectly during and after the application, which leads to the different environmental issues. MCP is found to be associated with neurotoxicity and its toxic effects have been monitored during different stages of neuronal development. Identification of gene expression in MCP-induced neurotoxicity during neuronal developmental stage is a major area of genomic research interest. In accordance with this identification, screening of potential neuroprotective, natural resources are also required as a preventive aspects by targeting the impaired genes. In this current course of work, microarray experiment has been used to identify genes that were expressed in monocrotophos (MCP)-induced mesenchymal stem cells (MSC) and also the neuroprotectant activity of RV on MCP-exposed MSCs. Microarray experiment data have been deposited in NCBI's Gene Expression Omnibus database and are accessible through GEO Series accession number GSE121261. In this paper, we have discussed two important genes NIPBL (nipped-B-like protein) and POU4F1 (POU domain, class 4, transcription factor 1). These genes were found to be significantly expressed in MCP-exposed MSC and show minimum expression in presence of RV. Homology modelling and docking study was done to identify the interaction and binding affinity of resveratrol and its derivatives with NIPBL and POU4F1 protein. Docking analysis shows that RV and its derivatives have strong interaction with NIPBL and POU4F1 protein hence proves the significance of resveratrol as potential neuroprotectant. This paper highlights the hazardous impact of MCP on neuronal development disorders and repairing potentiality of RV and its derivatives on altered genes involved in neuronal diseases. Graphical Abstract.

Molecular characterization of monocrotophos and chlorpyrifos tolerant bacterial strain for enhancing seed germination of vegetable crops.

The main aim of this study is to investigate the toxicity of organophosphate (OPs) insecticides monocrotophos (MCP) and chlorpyrifos (CLS) on plant growth promoting (PGP) properties and seed germination of brinjal, tomato and okra vegetables inoculated by Microbacterium hydrocarbonoxydans (BHUJP-P1), Stenotrophomonas rhizophila (BHUJP-P2), Bacillus licheniformis (BHUJP-P3) and Bacillus cereus (BHUJP-P4). Maximum increase in microbial growth (52.6% & 47.9%) with enhanced EPS production (447.67 mg/ml & 75.00 mg/ml) was showed by BHUJP-P4 and BHUJP-P3 at 10× dose of MCP and CLS over control, BHUJP-2 and BHUJP-P1 respectively. Simultaneously, both strains recorded minimum reduction in PGP activities and seed germination at 3× dose of both insecticides as compared to BHUJP-2 and BHUJP-P1, respectively. Strains BHUJP-P3 and BHUJP-P4 showed 83 and 81% of monocrotophos degradation at 50 mg/kg concentration; 81 and 80% at 150 mg/kg concentration within 5days respectively. Concurrently, these strains BHUJP-P3 and BHUJP-P4 were recorded 53 and 90% of chlorpyrifos degradation at 50 mg/kg concentration; 49% and 87% at 100 mg/kg concentration within 72 h, respectively. The OPs insecticide degrading gene opdA and opd was found in strain BHUJP-P3 and BHUJP-P4, respectively. The multifarious biological activities of strain BHUJP-P3 and BHUJP-P4 showed maximum tolerance against insecticide, and minimum reduction in P-solubilisation, IAA, siderophore and HCN production for plant growth promotion and biological control under insecticide stress. Thus, these novel isolates may be used as biodegradation of organophosphate insecticide and plant growth promoting bacterial (PGPB) inoculum for enhancing seed germination of vegetables under stress insecticide. These novel strains will be environment friendly, socially acceptable and economically viable.

Degradation of monocrotophos by Starkeya novella YW6 isolated from paddy soil.

A bacteria strain, YW6, capable of utilizing monocrotophos (MCP) as the sole carbon and nitrogen sources for growth was isolated from paddy soil and identified as Starkeya novella. Strain YW6 completely degraded 0.2 mM MCP within 36 h without any lag period. Addition of carbon source resulted in slowing down of the initial rate of degradation of MCP, while the presence of a more favorable source of nitrogen enhanced the degradation of MCP. In addition to the degradation of MCP, strain YW6 was also able to degrade a wide range of organophosphorus pesticides (OPs) containing P-O-C bond, but not dimethoate, which has P-S-C bond. A MCP degradation pathway was proposed on the basis of metabolite production patterns and identification of the metabolites. MCP is hydrolyzed at the P-O-C bond to form N-methylacetoacetamide and dimethyl phosphate; N-methylacetoacetamide is transformed to N-methyl-4-oxo-pentanamide, which was subsequently converted to 5-(methylamino)-5-oxo-pentanoic acid, and 5-(methylamino)-5-oxo-pentanoic acid is cleaved to glutaric acid and methylamine. These findings provide new insights into the microbial metabolism of MCP. To the best of our knowledge, this is the first report on the degradation of MCP by Starkeya bacteria.

Molecular Mechanism of Switching of TrkA/p75(NTR) Signaling in Monocrotophos Induced Neurotoxicity.

We demonstrate the role of molecular switching of TrkA/p75(NTR) signaling cascade in organophosphate pesticide-Monocrotophos (MCP) induced neurotoxicity in stem cell derived cholinergic neurons and in rat brain. Our in-silico studies reveal that MCP followed the similar pattern of binding as staurosporine and AG-879 (known inhibitors of TrkA) with TrkA protein (PDB ID: 4AOJ) at the ATP binding sites. This binding of MCP to TrkA led to the conformational change in this protein and triggers the cell death cascades. The in-silico findings are validated by observing the down regulated levels of phosphorylated TrkA and its downstream molecules viz., pERK1/2, pAkt and pCREB in MCP-exposed cells. We observe that these MCP induced alterations in pTrkA and downstream signaling molecules are found to be associated with apoptosis and injury to neurons. The down-regulation of TrkA could be linked to increased p75(NTR). The in-vitro studies could be correlated in the rat model. The switching of TrkA/p75(NTR) signaling plays a central role in MCP-induced neural injury in rBNSCs and behavioral changes in exposed rats. Our studies significantly advance the understanding of the switching of TrkA/p75(NTR) that may pave the way for the application of TrkA inducer/p75(NTR) inhibitor for potential therapeutic intervention in various neurodegenerative disorders.

Cytogenotoxicity assessment of monocrotophos and butachlor at single and combined chronic exposures in the fish Catla catla (Hamilton).

Cytogenotoxic effects in the form of micronuclei and deformed nucleus, nuclear buds, binucleated cells, vacuolated nucleus, vacuolated cytoplasm, echinocytes, and enucleus induced by two compounds belonging to two different chemical classes of agrochemicals (monocrotophos and butachlor) at sublethal concentrations (0.625, 1.3, and 2.3 ppm and 0.016, 0.032, and 0.064 ppm) in single and combined chronic exposures were studied under laboratory conditions for a period of 35 days in the economically important Indian fish Catla catla. Statistically significant duration-dependent increases in the frequencies of micronucleus (MN) and other cytological anomalies were observed. Compared to single exposures, a twofold increase in micronuclei frequency was noted at combined exposures indicating the synergistic phenomenon. Binucleated and enucleated cells appeared only in fishes exposed to sublethal concentrations of butachlor. The present study is the first of its kind in exploring a significant positive correlation between micronuclei and other nuclear anomalies suggesting them as new possible biomarkers of genotoxicity after agrochemical exposures. The study highlights the sensitivity of the assay in exploring various predictive biomarkers of genotoxic and cytotoxic events and also elicits the synergistic effects of agrochemicals in apparently healthy fishes. C. catla can be considered as a suitable aquatic biomonitoring sentinel species of contaminated water bodies.

Effect of an organophosphate pesticide, monocrotophos, on phosphate-solubilizing efficiency of soil fungal isolates.

Soil is a sink of pesticide residues as well as microorganisms. Fungi are well known for solubilization of inorganic phosphates, and this activity of fungal isolates may be affected by the presence of pesticide residues in the soil. In the present study, five generically different fungal isolates, viz. Aspergillus niger JQ660373, Aspergillus flavus, Penicillium aculeatum JQ660374, Fusarium pallidoroseum and Macrophomina sp., were tested and compared for their phosphate-solubilizing ability in the absence and presence of monocrotophos (500 mg L(-1)). After 168 h of incubation, four times high amount of tricalcium phosphate was solubilized by isolates in the growth medium containing monocrotophos in comparison to control (without monocrotophos). Concurrently, 78 % of the applied monocrotophos was degraded by these fungal isolates. Kinetics of phosphate solubilization shifted from logarithmic to power model in the presence of monocrotophos. Similarly, the phosphatase activity was also found significantly high in the presence of monocrotophos. The combined order of phosphate solubilization as well as monocrotophos degradation was found to be A. niger JQ660373 > P. aculeatum JQ660374 > A. flavus > F. pallidoroseum > Macrophomina sp. On the contrary, phosphate solubilization negatively correlated with the pH of the growth medium. Hence, it could be concluded that these fungal species efficiently solubilize inorganic phosphates and monocrotophos poses a positive effect on their ability and in turn degraded by them. To the best of our knowledge, this is the first report on P solubilization by Macrophomina sp. and F. pallidoroseum.

Biophysical aspects of lysozyme adduct with monocrotophos.

The present study on in vitro formation and characterization of lysozyme adduct with monocrotophos (MP) evaluates the potential of lysozyme to be used as a sensitive biomarker to monitor exposure levels to the commonly used organophosphorus pesticide monocrotophos. Crystallization of lysozyme protein adduct with monocrotophos was also undertaken to understand the adduct formation mechanism at a molecular level. The binding of organophosphorus pesticides to lysozyme is one of the key steps in their mutagenicity. The formation and structural characterization of lysozyme adduct with monocrotophos was done using MALDI-TOFMS, fluorescence, UV/Vis spectroscopy, circular dichroism, and X-ray diffraction studies. We report the crystal structure of lysozyme adduct with monocrotophos at 1.9 Å. It crystallized in the P43 space group with two monomers in one asymmetric unit having one molecule of monocrotophos bound to each protein chain. The results proved that the fluorescence quenching of lysozyme by monocrotophos is due to binding of monocrotophos with a tryptophan residue of lysozyme. Monocrotophos interacts most strongly with the Trp-108 and Asp-52 of lysozyme. The interactions of the monocrotophos molecule with the lysozyme suggest the formation of a stable adduct. In addition, the alteration of lysozyme secondary structure in the presence of monocrotophos was confirmed by circular dichroism and fluorescence inhibition of lysozyme by increasing monocrotophos and UV/Vis spectrophotometry. The formation of lysozyme adduct with monocrotophos was confirmed by MALDI-TOFMS.

Enzymatic degradation of monocrotophos by extracellular fungal OP hydrolases.

The present study explores the potential of extracellular fungal organophosphate (OP) hydrolase for the degradation of monocrotophos. Extracellular OP hydrolases were isolated and purified from five different fungal isolates viz. Aspergillus niger (M1), Aspergillus flavus (M2), Penicillium aculeatum (M3), Fusarium pallidoroseum (M4), and Macrophomina sp. (M5) by AmSO4 precipitation, dialysis, and G-100 chromatography. M3 showed highest percentage yield of 68.81 followed by 55.41 % for M1. Each of the purified enzyme fraction constituted of two different subunits of 33- and 67-kDa molecular weight. Optimum enzyme fraction (150 µg ml(-1)) rapidly degraded monocrotophos within 120 h in phosphorus-free liquid culture medium (CZM) with K deg of 0.0368, 0.0138, 0.048, 0.016, 0.0138, and 0.048 day(-1) and half-life of 0.79, 2.11, 0.6, 1.8, and 2.11 days for M1, M2, M3, M4, and M5, respectively. The results were further confirmed by high performance thin layer chromatography and Fourier transform infrared which indicate the disappearance of monocrotophos by hydrolytic cleavage of vinyl phosphate bond. The overall order of enzymatic degradation was found to be P. aculeatum > A. niger > F. pallidoroseum > A. flavus = Macrophomina sp. Hence, the study concludes that extracellular OP hydrolases efficiently degraded monocrotophos and could be used as a potential candidate for the detoxification of this neurotoxin pesticide.

The interaction between natural organic matter in raw waters and pesticide residues: a three dimensional excitation-emission matrix (3DEEM) fluorescence investigation.

This paper examines the interaction between dissolved natural organic matter and pesticide residues, both of which are found in raw water sources, using three dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy. It was observed that pesticide residue at 0.1 mg L(-1) formed a complex with humic-like fluorophores that are commonly found in raw water samples. Applying 3DEEM fluorescence to investigate the humic fractions, it was found that identification of changes in water sources was possible, and, importantly, the presence of a number of pesticides was able to be determined. In addition, the formation of this complex, and the influence of soluble cations and anions upon it, was shown to impact the efficiency of analytical extraction procedures for pesticides; however, 3DEEM fluorescence could be an approach to account for such losses.

Dispersive microextraction based on "magnetic water" coupled to gas chromatography/mass spectrometry for the fast determination of organophosphorus pesticides in cold-pressed vegetable oils.

This article presents a novel application of dispersive microextraction based on "magnetic water" (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe3O4 by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2-100 ng/g with satisfactory correlation coefficients (R) of 0.9997-0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70-1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established "magnetic water" microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils.

Comparative purification and characterization of two distinct extracellular monocrotophos hydrolases secreted by Penicillium aculeatum and Fusarium pallidoroseum isolated from agricultural fields.

The present study aimed at a comparative characterization of two distinct extracellular monocrotophos hydrolases, from Penicillium aculeatum ITCC 7980.10 (M3) and Fusarium pallidoroseum ITCC 7785.10 (M4), isolated from agricultural fields. The MCP hydrolases were purified by Sephadex G-100 column and DEAE-Sepharose CL-6B ion-exchange column followed by SDS-PAGE analysis, which showed the presence of two hydrolases, of 33 and 67 kDa respectively. Both enzymes were most active at alkaline pH and were stable over a wide range of temperatures (60-70 °C). Between the strains, the MCP hydrolases from M3 were 2-fold more active than that from M4. Enzyme kinetic studies showed lowest Km (33.52 mM) and highest Vmax (5.18 U/mg protein) for OPH67 of M3 in comparison to the Km and Vmax of the other hydrolases purified from M3 and M4, suggesting that M3 OPH67 was the most efficient MCP hydrolase. To the best of our knowledge, this is the first report of the purification of two distinct extracellular thermostable MCP hydrolases from fungal strains Penicillium aculeatum ITCC 7980.10 and Fusarium pallidoroseum ITCC 7785.10. Owing to its potential MCP hydrolyzing activity, M3 OPH67 can perhaps used directly or in the encapsulated form for remediation of MCP contaminated sites.

Photocatalytic degradation of monocrotophos pesticide--an endocrine disruptor by magnesium doped titania.

Mg-doped TiO(2) with different Mg concentrations were prepared using sol-gel method and characterized by XRD, UV-visible, XPS, SEM and FT-IR. The XRD results revealed that Mg(2+) goes into the TiO(2) lattice. SEM images of the doped and pure TiO(2) indicated that there is a smaller particle size for the doped catalyst compared to that of the pure TiO(2). UV-visible absorption spectra indicated that upon doping with Mg(2+) ion, the catalyst exhibits absorption in visible region. FT-IR and XPS spectra demonstrated that the presence of Mg(2+) ion in the TiO(2) lattice as substitutional dopant. Photocatalytic activity of doped TiO(2) has been evaluated by degradation of the monocrotophos (MCP) pesticide. The effect of solution pH, catalyst dosage and initial concentration of MCP on the photocatalytic activity of Mg-doped TiO(2) with different loadings was studied. It was observed that the rate of degradation of MCP over Mg-doped TiO(2) is better than Pure TiO(2) and Degussa P-25.

Sonophotocatalytic degradation of monocrotophos using TiO2 and Fe3+.

Monocrotophos (MCP) is an organophosphate insecticide that has been found as a pollutant in aqueous environments. The sonolytic, photocatalytic and sonophotocatalytic degradation of MCP in the presence of homogeneous (Fe(3+)) and heterogeneous photocatalysts (TiO(2)) were studied. The photocatalytic degradation rate using TiO(2) was found to be lower than that of sonolysis alone due to the interference of phosphate ions formed as an intermediate product. On the other hand, a 15 fold enhancement in the degradation rate was found when photolysis was carried out in the presence of Fe(3+) compared to the rate observed with photolysis alone. The combination of sonolysis and photocatalysis (using either TiO(2) or Fe(3+)) showed a detrimental effect. Synergy indices of 0.62 and 0.87 were found for the sonophotocatalytic degradation of MCP in the presence of TiO(2) and Fe(3+), respectively. Total organic carbon (TOC) analysis was carried out to study the extent of mineralization of MCP. It was found that the mineralization process was additive for both TiO(2) and Fe(3+) sonophotocatalysis. HPLC and electrospray mass spectrometry (ESMS) techniques were employed for the identification of the degradation intermediates. The sonication of MCP led to the formation of dimethyl phosphate, dimethylphosphonate, 3-hydroxy 2-buteneamide and N-methyl 3-oxobutanamide as the intermediate products.

Impact of repeated pesticide applications on the binding and release of methyl 14C-monocrotophos and U-ring labelled 14C-carbaryl to soil matrices under field conditions.

The dissipation of (O-methyl-14C) monocrotophos and U-ring labelled 14C-carbaryl was monitored for over two years in absence and presence of other insecticides using in situ soil columns. The dissipation of 14C-monocrotophos from soil treated with methomyl and carbaryl showed a faster rate of downward movement than in a control column tagged with the labelled insecticide alone. The same trend was observed in experiments with 14C-carbaryl that dissipated more readily in soil treated with non-labelled monocrotophos and methomyl. In the presence of other insecticides the percentage of bound residues was generally lower than in control experiments. The bound residues at the top of the column are released at a low rate under conditions prevailing in the field. The overall time required for dissipation of 50% of monocrotophos and carbaryl (t50) as estimated from control experiment was approximately 20 and 24 weeks, respectively. The data indicate that repeated applications of pesticides might enhance the release of 14C-bound residues.

Determination of polar organophosphorus pesticides in water samples by hydrophilic interaction liquid chromatography with tandem mass spectrometry.

A method combining hydrophilic interaction liquid chromatography (HILIC) with tandem mass spectrometry (MS/MS) was developed for the determination of polar organophosphorus pesticides (OPPs; acephate, methamidophos, monocrotophos, omethoate, oxydemeton-methyl, and vamidothion) in water samples. To extract the polar OPPs and minimize matrix effects from the water sample, an activated carbon cartridge was used for pretreatment. After pretreatment of the water sample, the eluate from the activated carbon cartridge was directly injected into the HILIC/MS/MS system. The OPPs were separated on an Atlantis HILIC silica column by isocratic elution with a mixture of acetonitrile, isopropanol, and ammonium formate buffer as a mobile phase, and they were detected by positive electrospray ionization MS/MS in the selected reaction monitoring mode. The method was validated at 0.05, 0.5, and 5 microg/L levels in water samples, and the recoveries of polar OPPs were between 76.4 and 98.6%. The limits of detection were between 0.13 and 1.0 pg on-column, and the limits of quantification were between 0.43 and 3.4 pg on-column. The method can be applied to the determination of trace amounts of OPPs in environmental water samples.

Films coated with molecular imprinted polymers for the selective stir bar sorption extraction of monocrotophos.

The flexibility and simplicity of stir bar sorption extraction (SBSE) have been combined with the selectivity of molecularly imprinted polymers (MIP). Stir bars were coated reproducible with a 180 microm film formed from a formic acid solution of nylon-6 polymer either nonimprinted or imprinted with monocrotophos. Time sorption profiles were measured for the extraction of monocrotophos from dichloromethane at the concentration of 10-200 micromol/L levels with both types of films in order to compare extraction characteristics. The results indicated that the MIP coated layer showed remarkable high affinity toward monocrotophos and equilibrium adsorption was attained rapidly (60 min) in contrast to free standing molecularly imprinted polymer in which equilibrium adsorption was normally attained after several hours. The stir bars coated with MIP films were capable of extracting four structural analogues of monocrotophos from dichloromethane solution, which suggests that both the amino group and PO part of these molecules is responsible for interaction with the imprinted polymer. Evidence was also presented by FT-IR analysis that the amide-hydrogen-bonding interaction between the MIP-coated films and monocrotophos was originated for monocrotophos recognition. To achieve selective extraction of monocrotophos from sample, stir bars coated with MIP films were washed with 10% (v/v) acetic acid/methanol and methanol. Clean extracts and yields of 95% were obtained, demonstrating the suitability of stir bar coated with MIP films for the analysis of environmental and biological samples. Compared with traditional MIP and SBSE, the MIP-coated film showed not only the high selectivity but also the rapid equilibrium adsorption.

Dissipation and leaching of (14)C-monocrotophos in Soil Columns under subtropical climate.

Dissipation and leaching behavior of 14C-monocrotophos was studied for 365 days under field conditions using PVC cylinders. The first set (24 cylinders) was spiked with 1.0 microCi 14C-labeled monocrotophos along with 1.06 mg unlabeled monocrotophos to give a concentration of 2 mg kg -1 in the soil up to 15 cm depth. The second set (24 cylinders) received 14C-labeled monocrotophos along with other non-labeled insecticides viz., dimethoate @ 300 g a.i ha-1, deltamethrin @ 12.5 g a.i ha-1, endosulfan @ 750 g a.i ha-1, cypermethrin @ 60 g a.i ha-1, and triazophos @ 600 g a.i ha-1 at an interval of 15 days each as recommended for the cotton crop. 14C-monocrotophos dissipated faster, up to 45% in first 90 days in columns treated with only monocrotophos compared to 25% in columns that received monocrotophos along with other insecticides. However, both the columns showed similar residues 180 days onward. After 180 days of treatment, 46% radiolabeled residues were observed, which reduced up to 39.6% after 365 days. Leaching of 14C-monocrotophos to 15-30 cm soil layer was observed in both the experimental setups. In the 15-30 cm soil layer of both soil columns, up to 0.19 mg 14C-monocrotophos kg-1d. wt. soil was detected after 270 days.

Molecularly imprinted polymer for monocrotophos and its binding characteristics for organophosphorus pesticides.

In this study, molecular imprinting was used to develop a method based on noncovalent interaction for the synthesis of a monocrotophos-specific polymer. The selective binding characteristics of the template polymer were evaluated by 1H NMR study. The result was consistent with the existence of multi-molecular complexes formed by hydrogen-bonding interactions. Batch rebinding studies in acetonitrile were undertaken to quantitatively evaluate the affinity of the polymer for monocrotophos. The experimental binding isotherms were fitted to the Freundlich isotherm and the total number of binding sites of the polymer can be calculated to be 4.046 micromol g(-1). The induced affinity and selectivity by imprinting were examined chromatographically. The polymer gave more than 15 times longer retention for monocrotophos than the nonimprinted polymer with the same chemical composition. Other organophosphorus pesticides under study were eluted close to the void volume on the polymer column.