Death by chumbinho: aldicarb intoxication-regarding a corpse in decomposition.

Chumbinho is the popular name given to carbamate aldicarb (Temik), an insecticide commonly used in agriculture and highly toxic (LD50 = 0.9 mg/kg oral in rats) that has been sold clandestinely in several regions of Brazil. Chumbinho is sold illegally as raticide and is available in a formulation of small black granules which are easily mixed with food for criminal purposes, its use often being attributed to accidents and suicides, hence the importance of its inclusion in the toxicology studies of suspicious deaths. With the corpse putrefaction, many pathological and toxicological anatomical parameters are damaged or lost. This study emphasizes the importance of the gastric content observation, which in this case has, despite the advanced putrefaction, recognized the presence of chumbinho and guide its toxicological confirmation.

Effect of ammonium on liquid- and gas-phase protonation and deprotonation in electrospray ionization mass spectrometry.

The electrospray ionization (ESI) is a complex process and there has been a long debate regarding the gas-phase effect on ion generation in the process. In this paper we investigated the effect of liquid chromatographic mobile phase additives (formic acid, aqueous ammonia and their combination) on the ESI signal intensities for a wide variety of compounds. The addition of a trace amount of aqueous ammonia to the common formic acid-methanol mobile phase significantly enhances the ESI signals of protonated molecules and suppresses the formation of sodium adduct ions. This effect is well observed for the compounds containing the -N-C=O group but not for those without N or O atoms. The ESI signal intensity of deprotonated molecules increases with increase in pH of the mobile phase for neutral compounds, such as substituted urea, whereas this trend is not observed for acidic compounds such as phenoxy acids. The mechanistic analysis regarding liquid- and gas-phase protonation and deprotonation is discussed.

Fluorescence and electrochemical sensing of pesticides methomyl, aldicarb and prometryne by the luminescent europium-3-carboxycoumarin probe.

This work describes the application of time resolved fluorescence in microtiterplates and electrochemical methods on glassy carbon electrode for investigating the interactions of europium-3-carboxycoumarin with pesticides aldicarb, methomyl and prometryne. Stern-volmer studies at different temperatures indicate that static quenching dominates for methomyl, aldicarb and prometryne. By using Lineweaver-Burk equation binding constants were determined at 303 K, 308 K and 313 K. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy ΔH and the entropy ΔS of reactions were all determined. A time-resolved (gated) luminescence-based method for determination of pesticides in microtiterplate format using the long-lived europium-3-carboxycoumarin has been developed. The limit of detection is 4.80, 5.06 and 8.01 µmol L(-1) for methomyl, prometryne and aldicarb, respectively. This is the lowest limit of detection achieved so far for luminescent lanthanide-based probes for pesticides. The interaction of the probe with the pesticides has been investigated using cyclic voltammetry (CV), differential pulse polarography (DPP), square wave voltammetry (SWV) and linear sweep voltammetry (LSV) on a glassy carbon electrode in I = 0.1 mol L(-1) p-toluenesulfonate at 25 °C. The diffusion coefficients of the reduced species are calculated. The main properties of the electrode reaction occurring in a finite diffusion space are the quasireversible maximum and the splitting of the net SWV peak for Eu(III) ions in the ternary complex formed . It was observed that the increase of the cathodic peak currents using LSV is linear with the increase of pesticides concentration in the range 5 × 10(-7) to 1 × 10(-5) mol L(-1). The detection limit (DL) were about 1.01, 2.23 and 1.89 µmol L(-1) for aldicarb, methomyl and prometryne, respectively. In order to assess the analytical applicability of the method, the influence of various potentially interfering species was examined. Influence of interfering species on the recovery of 10 µmol L(-1) pesticides has been investigated.

Interaction of Human Alpha-2-Macroglobulin with Pesticide Aldicarb Using Spectroscopy and Molecular Docking.

BACKGROUND: Aldicarb is a carbamate pesticide commercially used in potato crop production. Once it enters human body, it interacts with diverse proteins and other substances. OBJECTIVE: Aldicarb is toxic to human health and it is also a cholinesterase inhibitor, which prevents the breakdown of acetylcholine in synapse. Human alpha-2-macroglobulin (α2M), is a large tetrameric glycoprotein of 720 kDa with antiproteinase activity, found abundantly in plasma. METHODS: In the present study, the interaction of aldicarb with alpha-2-macroglobulin was explored utilizing various spectroscopic techniques and molecular docking studies. RESULTS: UV-vis and fluorescence spectroscopy suggests the formation of a complex between aldicarb and α2M apparent by increased absorbance and decreased fluorescence with static quenching mode. CD spectroscopy indicates a slight change in the structure of alpha-2-macroglobulin. Docking studies confirm the interaction of aldicarb with Pro- 1391, Leu-1392, Lys-1393, Val-1396, Lys- 1397, Thr-1408, Glu-1409, Val-1410, Asp-282 and Glu-281 in the receptor binding domain at the C-terminal of the alpha 2 macroglobulin. DISCUSSION: In this work, aldicarb is shown to bind with alpha 2-macroglobulin at receptor binding domain which is the binding site for various extracellular and intracellular ligand too. Also, affecting the functional activity of the protein may lead to further physiological consequences. CONCLUSION: It is possible that aldicarb binds and compromises antiproteinase activity of α2M and binding properties by inducing changes in the secondary structure of the protein.

Fluorescence tuning behavior of carbon quantum dots with gold nanoparticles via novel intercalation effect of aldicarb.

A simple, sensitive and rapid fluorometric system has been developed for the detection of aldicarb (ALD) based on inner filter effect (IFE) of gold nanoparticles (AuNPs) on fluorescence (FL) intensity of carbon quantum dots (CQDs). Addition of CQDs into AuNPs, gets them aggregated due to electrostatic interaction resulting in quenching the FL intensity of CQDs. With addition of ALD into AuNPs, an intercalated layer was formed between them through Au-N and Au-S bond which reduced IFE of AuNPs. Hence, CQDs FL intensity recovered along with ALD concentration varying between 3.8 and 76 µg L-1 with lower detection limit of 3.02 µg L-1. The spiked real samples study in fruits, vegetables and soft drinks revealed that this sensing platform was repeatable and effective for real samples. The validation of proposed method indicates that the ALD sensor is promising and adaptable for everyday on spot environment and food safety monitoring.

In vivo efficacy of the Reactive Skin Decontamination Lotion (RSDL®) kit against organophosphate and carbamate pesticides.

In this study, we assessed the efficacy of the Reactive Skin Decontamination Lotion (RSDL®) Kit against parathion and aldicarb pesticide dermal exposure in a guinea pig model. The pesticides inhibit acetylcholinesterase (AChE) leading to signs and symptoms of hyperactivity of organs due to accumulation of acetylcholine. The RSDL Kit has been shown to physically remove and chemically degrade chemical warfare agents. Degradation occurs from a nucleophilic substitution reaction between an active ingredient in the RSDL lotion, potassium 2,3-butanedione monoximate (KBDO), with susceptible sites in these compounds. In the present study, guinea pigs dermally exposed to parathion and aldicarb were decontaminated with RSDL to mitigate the toxic effects of the pesticides. It is observed that animals exposed to 749 mg/kg of parathion (n = 3) died within 24 h without RSDL decontamination; however, RSDL-treated animals (n = 3) showed only mild signs of neurotoxicity. The RSDL-treated animals had an AChE inhibition of 0-58% while the untreated animals had up to 86% inhibition. Similarly, RSDL has been demostrated to prevent aldicarb neurotoxicity effects. The percent inhibition of AChE activity during the 24 h post challenge of 9 mg aldicarb/kg of animal weight ranged from 25% to 61% with severe signs of intoxication while only up to 5% with mild or no signs of intoxication in the case of RSDL-decontaminated animals. Generally, it has been shown that the toxic effects of the organophosphate and carbamate pesticides can be prevented via decontamination using the RSDL Kit.

Photocatalytic degradation of organic pollutant aldicarb by non-metal-doped nanotitania: synthesis and characterization.

The current study focused on pollution control by titania through photocatalytic degradation of aldicarb pesticide in aqueous medium. Titania, which is an efficient photocatalyst, can bring about degradation of aqueous organic pollutants under UV and visible light irradiation. Here, we prepared titania by sol-gel method from titanium tetraisopropoxide and doped non-metals like N and S from sources such as urea and thiourea, respectively. The prepared catalyst was characterized by XRD, UV-Vis.DRS, TEM, XPS, etc. Photocatalytic activity of the catalyst was evaluated from extend of degradation of aldicarb pesticide by measuring its concentration with the help of HPLC. It was found that the modified catalyst showed better photocatalytic degradation than pure titania in visible light.

[Dynamic behavior of aldicarb and its metabolites in cabbage by liquid chromatography-tandem mass spectrometry].

A liquid chromatography-tandem mass spectrometry ( LC-MS/MS ) method was developed for the study of dynamic behavior of aldicarb and its metabolite residues in cabbage. Aldicarb was applied onto cultivated cabbages. The pesticides concentrations were measured periodically (between application and harvest) , and modeled to illustrate the dynamic behavior. The results showed that the liner ranges of aldicarb and its metabolites were from 0. 005 to 0. 2 mg/L, and the recoveries ranged from 78. 9% to 108. 5% with the relative standard deviations of 2. 03%- 8. 91% (n = 8). The aldicarb in cabbage increased at first with the first-order kinetic equation model of c = 0. 020(0.136t) with the correlation coefficient (r2) of 0. 888, and then decreased with the equation of c = 0. 65e(-059t) with the r2 of 0. 979 and the half-life of 29. 1 d. The reducing processes of aldicarb-sulfone and aldicarb-sulfoxide both matched the first-order kinetic equations (c = 23. 4e(-0.044t) and c = 4. 54e(-0.027t) with r2 of 0. 916 and 0. 972 respectively. To meet the limitation requirement of 0. 01 mg/kg, 70. 7, 226. 6 and 176. 3 d were respectively necessary for aldicarb, aldicarb-sulfone and aldicarb-sulfoxide. Final residues of aldicarb-sulfone and aldicarb-sulfoxide were still more than the limitation requirements, indicating that aldicarb should not be used in vegetables of growth cycle shorter than 120 d. This study provided theoretical basis for dynamic behavior of aldicarb residue and its safe use in vegetables.

Adsorption kinetics and isotherms of pesticides onto activated carbon-cloth.

Adsorption of pesticides ametryn, aldicarb, dinoseb and diuron from aqueous solution onto high specific area activated carbon-cloth was studied. Kinetics of adsorption was followed by in situ UV-spectroscopy and the data were treated according to various rate models. The extent of adsorption was determined at the end of 125 min adsorption period. Rate constants and the extent of adsorption for the four pesticides were found to follow the order: dinoseb > ametryn > diuron > aldicarb. Adsorption isotherms were derived at 25 degrees C on the basis of batch analysis. Isotherm data were treated according to Langmuir and Freundlich models. The fits of experimental data to these equations were examined. The types of interactions between the surface and pesticide molecules were discussed.

An enzyme-linked chemiluminescent immunoassay developed for detection of Butocarboxim from agricultural products based on monoclonal antibody.

In this study, four different haptens around the oxime moiety of Butocarboxim were designed and synthesised. Two of the haptens were conjugated with bovine serum albumin (BSA) to serve as the immunogen and all the haptens were conjugated with ovalbumin (OVA) for the coating antigen. The anti-Butocarboxim monoclonal antibody (Mab) was selected based on eight immunogen/coating antigen combinations. The first enzyme-linked chemiluminescent immunoassay (ELCIA) for determining Butocarboxim in agricultural products was developed. Under the optimised conditions, the detection limit for the ELCIA was 20 ng·mL(-1) and the linear range was 27-2700 ng·mL(-1). Analyte recoveries for extracts of spiked agricultural (apple and greengrocery) products and tap water ranged from 97.18% to 107.00%. The developed immunoassay has great potential to be developed as a test kit offering a simple and cost-effective approach (such as lateral flow test strip) for screening purposes and evaluating environmental exposure to Butocarboxim.

Acetylcholinesterase biosensor for inhibitor measurements based on glassy carbon electrode modified with carbon black and pillar[5]arene.

New acetylcholinesterase (AChE) biosensor based on unsubstituted pillar[5]arene (P[5]A) as electron mediator was developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. The AChE from electric eel was immobilized by carbodiimide binding on carbon black (CB) placed on glassy carbon electrode. The working potential of 200mV was obtained in chronoamperometric mode with the measurement time of 180 s providing best inter-biosensors precision of the results. The AChE biosensor developed made it possible to detect 1×10(-11)-1×10(-6) M of malaoxon, 1×10(-8)-7×10(-6) M of methyl-paraoxon, 1×10(-10)-2×10(-6) M of carbofuran and 7×10(-9)-1×10(-5) M of aldicarb with 10 min incubation. The limits of detection were 4×10(-12), 5×10(-9), 2×10(-11) and 6×10(-10) M, respectively. The AChE biosensor was tested in the analysis of pesticide residuals in spiked samples of peanut and beetroot. The protecting effect of P[5]A derivative bearing quaternary ammonia groups on malaoxon inhibition was shown.

A carbamate insecticide: a case study of aldicarb.

Aldicarb, the active ingredient in the insecticide TEMIK, was introduced to the agricultural community over 25 years ago. It has been registered worldwide to control a wide variety of insect, mite, and nematode pests in agriculture. The toxicological research database supporting the registration and use of aldicarb was generated over more than 25 years and contains more than 280 animal studies on 12 species of animals, 2 clinical human trials, and over 20 human monitoring studies. This database, which includes biochemical aspects (metabolism and mode-of-action studies), acute toxicity and special short-term toxicity studies, long-term toxicity studies, and epidemiological observations in humans, serves as the starting point for the evaluation of the risks associated with the acceptance of levels of aldicarb residues in food and drinking water and for the more direct occupational exposure. This article highlights the available toxicological data and reviews worldwide regulation of aldicarb. Included in these discussions is a brief description of the toxicological end point upon which regulatory decisions have been based, namely acetylcholinesterase depression. Aldicarb, the N-methylcarbamic acid ester of 2-methyl-2-(methylthio) propionaldehyde oxime, was the first of a limited group of insecticidal oxime N-methylcarbamates that have properties distinct from N-methylcarbamates which have a phenolic constituent, instead of the oxime moiety. Aldicarb is highly water-soluble (approximately 6000 ppm), nonvolatile, relatively stable under acidic conditions, and is easily degraded under alkaline conditions. These properties are important determinants of its systemic action in plants and of its problematic environmental behavior. Possible environmental hazards involving the chemical include groundwater contamination and (more recently) excessive terminal residues in certain foods.

In vivo acetylcholinesterase inhibition, metabolism, and toxicokinetics of aldicarb in channel catfish: role of biotransformation in acute toxicity.

The carbamate pesticide, aldicarb, demonstrates significant acute toxicity in mammals, birds, and fish through the inhibition of acetylcholinesterase (AChE), and may present high potential for exposure of aquatic organisms during periods of runoff. Toxicity studies have shown that channel catfish are less sensitive to the acute toxic effects of aldicarb than are rainbow trout or bluegill. An earlier in vitro study suggests that the aldicarb resistance in catfish may be related to a low level of bioactivation to the potent aldicarb sulfoxide. The current study examines the toxicity, AChE inhibition, plasma kinetics, and in vivo metabolism of aldicarb in channel catfish. A 48-h LC50 of 9.7 mg/l was determined for juvenile channel catfish. Mortality was accompanied by dramatic loss of brain AChE. Further characterization of tissue-level effects suggests that muscle AChE plays a causal role in mortality. Aldicarb was metabolized in channel catfish to aldicarb sulfoxide, along with the formation of minor hydrolytic products. The toxicokinetics of aldicarb in catfish are bi-compartmental with rapid elimination (t1/2 = 1.9 h). Plasma AChE was inhibited in a pattern similar to that of the elimination of total aldicarb-derived compounds. A comparison of aldicarb uptake between catfish and rainbow trout showed no difference in compound absorbed in 24 h. The pattern of in vivo metabolism, however, was quite different between these species. Rainbow trout produce significantly more hydrolytic derivatives and have a 3-fold higher aldicarb sulfoxide to aldicarb ratio at 3 h. These data give strength to the hypothesis that a slower rate of bioactivation in the catfish (vs. rainbow trout) is acting as a protective mechanism against the acute toxicity of aldicarb.

In vitro sulfoxidation of aldicarb by hepatic microsomes of channel catfish, Ictalurus punctatus.

The carbamate pesticide, aldicarb, demonstrates significant acute toxicity in mammals, birds, and fish, and is readily biotransformed by most organisms studied. Metabolic products of aldicarb include the more toxic sulfoxide and the less toxic sulfone as two of the major products. Both the cytochrome P450 (CYP) and the flavin monooxygenase systems (FMO) are involved in this process. This study examined the capacities of liver microsomes of male channel catfish (Ictalurus punctatus), which lack FMO, to biotransform aldicarb in vitro. In addition, the acetylcholinesterase inhibitory potencies of aldicarb and its sulfoxide and sulfone derivatives were determined. For metabolism studies, incubations of [14C]-aldicarb (0.1mM) were carried out for up to 15-90 min using 1.0 mg/mL of hepatic microsomal protein. Total NADPH- dependent biotransformation was low (< 3.0% conversion to polar metabolites), and was inhibited by carbon monoxide. The only metabolite detected was aldicarb sulfoxide (Kmapp = 53.8 +/- 25.3 microM; Vmaxapp = 0.040 +/- 0.007 nmol/min/mg). Treatment of fish with the CYP modulators beta-naphthoflavone (BNF, 50 mg/kg) and ethanol (EtOH, 1.0% aqueous) had no effect on sulfoxide production. No correlation existed between CYP isoform expression (determined by western blot) and aldicarb sulfoxidation rates, suggesting the involvement of an unmeasured CYP isoform or involvement of several isoforms with low specificity. This study indicates that a low rate of bioactivation of aldicarb to aldicarb sulfoxide may be responsible for the resistance of channel catfish to aldicarb toxicity relative to that of other piscine species.

Construction of an acetylcholinesterase-choline oxidase biosensor for aldicarb determination.

In this study, acetylcholinesterase and choline oxidase were co-immobilized on poly(2-hydroxyethyl methacrylate) membranes and the change in oxygen consumption upon aldicarb introduction was measured. Immobilization of the enzymes was achieved either by entrapment or by surface attachment via a hybrid immobilization method including epichlorohydrin and Cibacron Blue F36A activation. Immobilized enzymes had a long-storage stability (only 15% activity decrease in 2 months in wet storage and no activity loss in dry storage). Aldicarb detection studies showed that a linear working range of 10-500 and 10-250 ppb aldicarb could be achieved by entrapped and surface immobilized enzymes, respectively. Enzymes immobilized on membrane surfaces responded to aldicarb presence more quickly than entrapped enzymes. Aldicarb concentrations as low as 23 and 12 ppb could be detected by entrapped and surface immobilized enzymes, respectively, in 25 min.

Determination of aldicarb, aldicarb sulfoxide and aldicarb sulfone in some fruits and vegetables using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74]+ and the protonated molecular [M+H]+ ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts.

Solid-phase extraction of polar pesticides from environmental water samples on graphitized carbon and Empore-activated carbon disks and on-line coupling to octadecyl-bonded silica analytical columns.

The suitability of Empore-activated carbon disks (EACD), Envi-Carb graphitized carbon black (GCB) and CPP-50 graphitized carbon for the trace enrichment of polar pesticides from water samples was studied by means of off-line and on-line solid-phase extraction (SPE). In the off-line procedure, 0.5-2 l samples spiked with a test mixture of oxamyl, methomyl and aldicarb sulfoxide were enriched on EnviCarb SPE cartridges or 47 mm diameter EACD and eluted with dichloromethane-methanol. After evaporation, a sample was injected onto a C18-bonded silica column and analysed by liquid chromatography with ultraviolet (LC-UV) detection. EACD performed better than EnviCarb cartridges in terms of breakthrough volumes (> 2 l for all test analytes), reproducibility (R.S.D. of recoveries, 4-8%, n = 3) and sampling speed (100 ml/min); detection limits in drinking water were 0.05-0.16 microgram/l. In the on-line experiments, 4.6 mm diameter pieces cut from original EACD and stacked onto each other in a 9 mm long precolumn, and EnviCarb and CPP-50 packed in 10 x 2.0 mm I.D. precolumn, were tested, and 50-200 ml spiked water samples were preconcentrated. Because of the peak broadening caused by the strong sorption of the analytes on carbon, the carbon-packed precolumns were eluted by a separate stream of 0.1 ml/min acetonitrile which was mixed with the gradient LC eluent in front of the C18 analytical column. The final on-line procedure was also applied for the less polar propoxur, carbaryl and methiocarb. EnviCarb could not be used due to its poor pressure resistance. CPP-50 provided less peak broadening than EACD: peak widths were 0.1-0.3 min and R.S.D. of peak heights 4-14% (n = 3). In terms of analyte trapping efficiency on-line SPE-LC-UV with a CPP-50 precolumn also showed better performance than when Bondesil C18/OH or polymeric PLRP-S was used, but chromatographic resolution was similar. With the CPP-50-based system, detection limits of the test compounds were 0.05-1 microgram/l in surface water.

Determination of aldicarb, carbofuran and some of their main metabolites in groundwater by application of micellar electrokinetic capillary chromatography with diode-array detection and solid-phase extraction.

This paper describes a UV detection method for the pesticides aldicarb and carbofuran, and some of their main metabolites, aldicarb-sulfoxide, aldicarb-sulfone and 3-hydroxy-carbofuran, in ground waters. Micellar electrokinetic chromatography (MEKC) with diode-array detection was developed for their determination at 210 nm. The experimental study was performed using sodium dodecyl sulfate (SDS) at a concentration level of 140 mM, and a buffer of borax/HCl 20 mM at pH 8 which gives the best resolution with an analysis time of less than 20 min. Different instrumental parameters such as voltage (23 kV), injection time (12 s) and temperature (25 degrees C) were optimized. The detection limits were in the range 2-7.4 microg glitre(-1) by solid-phase extraction (SPE) with a subsequent evaporation step. Groundwater spiked samples were pre-concentrated off-line with graphite carbon and subsequently analyzed by MEKC with diode-array detection yielding average recoveries between 77 and 97% (n = 4) with RSD between 2-7%.

Assessment of leaching potential of aldicarb and its metabolites using laboratory studies.

The metabolites of pesticides can contaminate groundwater and pose a risk to human health when this water is used for drinking. This paper reports the results of a laboratory study on aldicarb and its main metabolites, aldicarb sulfone and aldicarb sulfoxide. Aldicarb and its metabolites showed Koc values (6-31) which were lower than that of atrazine (55), indicating that they are very mobile in soil. They are less persistent than atrazine (DT50 = 25 days), with DT50 values from less than 1 day and up to 12 days. Aldicarb behaved as a non-leacher, whereas its metabolites clearly showed the characteristics of leachers. Aged residue leaching experiments showed that aldicarb can occur at high concentrations in the leachate, together with its two metabolites. The leachate composition depends on the incubation time of the parent compound. Aldicarb and its metabolites can form various mixtures in groundwater on the basis of the time elapsing between the application of the insecticide and the first significant rainfall. This study confirms the characteristics of contaminants of aldicarb and especially its metabolites, as reported in the literature.

Cholinesterase sensor based on glassy carbon electrode modified with Ag nanoparticles decorated with macrocyclic ligands.

New acetylcholinesterase (AChE) sensor based on Ag nanoparticles decorated with macrocyclic ligand has been developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. AChE was immobilized by carbodiimide binding on carbon black (CB) layer deposited on a glassy carbon electrode. The addition of Ag nanoparticles decreased the working potential of the biosensor from 350 to 50 mV. The AChE sensor made it possible to detect 0.4 nM-0.2 µM of malaoxon, 0.2 nM-0.2 µM of paraoxon, 0.2 nM-2.0 µM of carbofuran and 10 nM-0.20 µM of aldicarb (limits of detection 0.1, 0.05, 0.1 and 10 nM, respectively) with 10 min incubation. The AChE sensor was tested for the detection of residual amounts of pesticides in spiked samples of peanut and grape juice. The protecting effect of new macrocyclic compounds bearing quaternary ammonia fragments was shown on the example of malaoxon inhibition.