Sensitive and selective detection of amitrole based on molecularly imprinted nanosensor.

SPR sensor used for amitrole detection was prepared without using any modification. Molecularly imprinted SPR sensor enabled high selectivity for amitrole pesticide. Amino acid-based functional monomer MATrp was integrated as a recognition element. Tailor-made SPR sensor enables real-time monitoring of amitrole pesticide. Synthetic recognition sites provided by MATrp were prepared without labeling.

Colorimetric aminotriazole assay based on catalase deactivation-dependent longitudinal etching of gold nanorods.

A colorimetric and visual assay is described for the herbicide aminotriazole (ATZ). It is based on the etching of gold nanorods (AuNRs) by iodine which is formed on oxidation of iodide via H2O2. Longitudinal etching of the AuNRs occurs quickly and is accompanied by a color change from dark blue to red. In the absence of ATZ and the presence of active catalase (CAT), H2O2 is quickly decomposed into water, and the AuNRs will not be etched. In the presence of ATZ, CAT is partially deactivated, and this affects the amount of available H2O2 and, consequently, of the iodine. Hence, the color is significantly changed. The color changes can be easily detected with bare eyes. The assay has a linear response in the 5 to 70 µM concentration range, with a detection limit of 1.3 µM and high selectivity for ATZ. It was applied to the determination of ATZ in water and food samples. Graphical abstract A multicolor colorimetric method is developed for aminotriazole (ATZ) detection based on catalase (CAT) deactivation-dependent longitudinal etching of gold nanorods (AuNRs). The color signals can be visually identified. Good detection performances and capability for evaluating ATZ level in water and food samples is demonstrated.

Plastic antibody based surface plasmon resonance nanosensors for selective atrazine detection.

This study reports a surface plasmon resonance (SPR) based affinity sensor system with the use of molecular imprinted nanoparticles (plastic antibodies) to enhance the pesticide detection. Molecular imprinting based affinity sensor is prepared by the attachment of atrazine (chosen as model pesticide) imprinted nanoparticles onto the gold surface of SPR chip. Recognition element of the affinity sensor is polymerizable form of aspartic acid. The imprinted nanoparticles were characterized via FTIR and zeta-sizer measurements. SPR sensors are characterized with atomic force microscopy (AFM), scanning electron microscopy (SEM), Fourier transform infrared spectrophotometry (FTIR) and contact angle measurements. The imprinted nanoparticles showed more sensitivity to atrazine than the non-imprinted ones. Different concentrations of atrazine solutions are applied to SPR system to determine the adsorption kinetics. Langmuir adsorption model is found as the most suitable model for this affinity nanosensor system. In order to show the selectivity of the atrazine-imprinted nanoparticles, competitive adsorption of atrazine, simazine and amitrole is investigated. The results showed that the imprinted nanosensor has high selectivity and sensitivity for atrazine.

A simple electrochemical platform based on pectin stabilized gold nanoparticles for picomolar detection of biologically toxic amitrole.

Amitrole is a biologically toxic nonselective herbicide which contaminates surface and ground waters at unprecedented rates. All reported modified electrodes that detect amitrole within sub-micromolar to nanomolar levels were based on the electro-oxidation of amitrole. Herein, we developed a new conceptual idea to detect picomolar concentrations of amitrole based on calcium cross linked pectin stabilized gold nanoparticle (CCLP-GNP) film modified electrode which was prepared by electrodeposition. When the electrochemical behavior of amitrole was investigated at the CCLP-GNP film, the reduction peak current of the GNPs linearly decreased as the concentration of amitrole increases. We have designed a determination platform based on the amitrole dependent decrease of the GNP cathodic peak. The described concept and high sensitivity of square wave voltammetry together facilitate the great sensing ability; as a result the described approach is able to reach a low detection limit of 36 pM which surpassed the detection limits of existing protocols. The sensor presents a good ability to determine amitrole in two linear concentration ranges: (1) 100 pM-1500 pM with a detection limit of 36 pM; (2) 100 nM-1500 nM with a detection limit of 20 nM. The preparation of CCLP-GNPs is simple, rapid and does not require any reducing agents.

Biosensor based on ds-DNA decorated chitosan modified multiwall carbon nanotubes for voltammetric biodetection of herbicide amitrole.

The interaction of amitrole and salmon sperm ds-DNA was studied using UV-vis and differential pulse voltammetry (DPV) at both bare and DNA-modified electrodes. Amitrole showed an oxidation peak at 0.445 V at a bare pencil graphite electrode (PGE). When ds-DNA was added into the amitrole solution, the peak current of amitrole decreased and the peak potential underwent a shift. UV-vis spectra showed that the absorption intensity of the ds-DNA at 260 nm decreased with increasing amitrole concentration, proving the interaction between amitrole and the ds-DNA. The results also showed that amitrole could interact with the ds-DNA molecules via the intercalative binding mode. Finally, a pretreated pencil graphite electrode (PGE) modified with multiwall carbon nanotubes (MWCNTs) and chitosan (CHIT) decorated with the ds-DNA were tested in order to determine amitrole content in solution. Electrochemical oxidation of amitrole bonded on DNA/MWCNTs-CHIT/PGE was used to obtain an analytical signal. A linear dependence was observed to exist between the peak current and 0.025-2.4 ng mL(-1) amitrole with a detection limit of 0.017 ng mL(-1). The sensor showed a good selectivity and precision for the determination of amitrole. Finally, applicability of the biosensor was evaluated by measuring the analyte in soil and water samples with good selectivity.

Calibration and field application of Chemcatcher® passive samplers for detecting amitrole residues in agricultural drain waters.

A passive sampler device suitable for monitoring of residues of the hydrophilic ionic herbicide amitrole in irrigation waterways was developed. Uptake of amitrole on styrenedivinylbenzene-reverse phase sulfonated Empore™ disks was linear and proportional to its water concentration over the range of 1-10 µg/L with a sampling rate of 23.1 mL/day under laboratory flow-through conditions. Performance of the sampler was evaluated by deployment in an agricultural irrigation drain for 10 days. The amount of amitrole adsorbed by the passive samplers compared well with the cumulative mean water concentrations calculated from daily spot samplings of the drain water.

Ion-pairing high-performance liquid chromatography determination of amitrole in apple after solid-phase extraction and precolumn derivatization.

A novel method based on solid-phase extraction was studied for the extraction of amitrole (3-amino-1,2,4-triazole), and its residue determination in apples has been developed. The samples were derivatized with 4-chloro-3,5-dinitrobenzotrifluoride (CNBF). The derivatization conditions and the influence of elution composition on the separation were investigated. In pH 9.5 H(3)BO(3)-Na(2)B(4)O(7) media, the reaction of amitrole with CNBF was complete at 60 degrees C after 30 min. The separation of derivatized amitrole was achieved at room temperature within 13 min by gradient elution mode with cetyltrimethylammonium bromide in mobile phase as ion-pair reagent. The method correlation coefficient was 0.9996, in concentrations ranging from 1.66 to 415 mg L(-1). The calculated recoveries of the proposed method were from 94.17% to 105.67%, and relative standard deviations were 1.57% to 6.44% in the application to the quantitative determination of amitrole in apples. The detection limit of amitrole was 0.10 mg L(-1) with a signal-to-noise ratio of 3.

Determination of amitrole in environmental water samples with precolumn derivatization by high-performance liquid chromatography.

Amitrole is a nonselective polar herbicide that can easily pollute ground and surface waters because of its high solubility in water. A precolumn derivatization high-performance liquid chromatographic method for amitrole analysis has been developed. Derivatization of amitrole was performed with 4-chloro-3,5-dinitrobenzotrifluoride (CNBF). The derivatization conditions and the influence of elution composition on the separation were investigated. In pH 9.5 H(3)BO(3)-Na(2)B(4)O(7) media, the reaction of amitrole with CNBF was complete at 60 degrees C after 30 min. The stability of the derivative under light irradiation and room temperature in methanol-water samples was demonstrated. The derivatized amitrole was separated on a K C(18) column (250 mm x 4.6 mm, 5 microm) at room temperature, and UV detection was applied at 360 nm. The separation of derivatized amitrole was achieved within 18 min by gradient elution mode. The method correlation coefficient was 0.9995, in concentrations ranging from 1.59 to 318 mg L(-1). The detection limit of amitrole was 0.16 mg L(-1) with a signal-to-noise ratio of 3. The proposed method was applied to the quantitative determination of amitrole in environmental water with recoveries of 92.0-103.0% and RSDs of 2.22-6.26, depending on the sample investigated. This method has good accuracy and repeatability that can be used to quantify amitrole in environmental water.

Analysis of amitrole by normal-phase liquid chromatography and tandem mass spectrometry using a sheath liquid electrospray interface.

The coupling of normal-phase liquid chromatography to tandem mass spectrometry, previously developed in our laboratory, has been applied to the analysis of amitrole. This coupling utilizes an electrospray interface modified to accommodate the introduction of a make-up solution at the tip of the electrospray probe. A methanolic solution containing 3 mM ammonium acetate delivered at a flow rate of 10 microL . min(-1) was found to be the optimal sheath liquid to promote successful ionization of the amitrole. Protonated molecules, arising from in-source dissociation of ammonium adducts, were subjected to tandem mass spectrometric experiments in a triple-quadrupole instrument. The main fragmentation reactions were characterized and selected to acquire chromatographic data in the multiple reaction monitoring mode. The limit of detection for amitrole was in the ppm range without any preconcentration step. Enhanced efficiency of ion transmission achievable nowadays in mass spectrometers (this analytical configuration was developed with a 15-year-old instrument) is reasonably expected to further improve this detection level.

Determination of amitrole and urazole in water samples by capillary zone electrophoresis using simultaneous UV and amperometrical detection.

In this paper, capillary zone electrophoresis with amperometric detection (CZE-AD) was first applied to the simultaneous separation and determination of amitrole and urazole in water samples. A simple end-column electrochemical detector was used in combination with a commercially available capillary electrophoresis instrument with UV detection. The effects of several important factors were investigated to find optimum conditions. A carbon disk electrode was used as working electrode. Separation and determination of these compounds in water samples were performed in 0.030 mol l(-1) acetate buffers at pH 4.5, 25 kV as separation voltage and the samples were introduced by hydrodynamic mode for 1.5 s. Most of the studies realized showed that the direct electrochemical detection is more sensitive and selective than UV detection. Under the optimum conditions, excellent linearity was observed between peak amperometric signal and analyte concentrations in the range of 0.19-1.35 mg l(-1) for amitrole and 0.20-1.62 mg l(-1) for urazole. The detection limits were 63 and 68 microg l(-1) for amitrole and urazole, respectively. The utility of this method was demonstrated by monitoring water samples, and the assay results were satisfactory. The detection limits using a previous preconcentration step for amitrole and urazole in spiked mineral water samples were 0.6 and 1.0 microg l(-1) for amitrole and urazole, respectively.

Simultaneous separation and on-line concentration of amitrole and benzimidazole pesticides by capillary electrophoresis with a volatile migration buffer applicable to mass spectrometric detection.

This study used capillary electrophoresis (CE) to investigate the simultaneous separation and on-line concentration of five pesticides: amitrole (AMT), carbendazim (MBC), 2-aminobenzimidazole (ABI), thiabendazole (TBZ) and 1,2-diaminobenzene (DAB). A volatile migration buffer was used for the investigation because of the applicability to mass spectrometric (MS) detection. They were separated completely at pH 4.0 as a result of changing pH using formic acid-ammonium formate buffer. Values of the dissociation constant for MBC and DAB estimated from the changes in the mobility with pH showed good agreement with values in the literature. Dissociation constants for AMT and TBZ were estimated. Limits of detection (LODs) for the analytes were on the ppm level with UV detection under the optimized separation condition. On-line concentration by simple stacking mode was not effective except to 2-aminobenzimidazole because of the peak tailing. The addition of formic acid to sample matrix improved the peak shapes. That improvement may be attributed to transient isotachophoretic effect. The concentration factors obtained from the comparison of the LODs were in the range of 7.6-27-fold. This concentration method was applied preliminarily to CE with MS detection.

Electrocatalytic amperometric determination of amitrole using a cobalt-phthalocyanine-modified carbon paste electrode.

Cobalt-phthalocyanine-modified carbon paste electrodes are shown to be excellent indicators for electrocatalytic amperometric measurements of triazolic herbicides such as amitrole, at low oxidation potentials (+0.40 V). The detection and determination of amitrole in flow injection analysis with a modified carbon paste electrode with Co-phthalocyanine is described. The concentrations of amitrole in 0.1 M NaOH solutions were determined using the electrocatalytic oxidation signal corresponding to the Co(II)/Co(III) redox process. A detection limit of 0.04 microg mL(-1) (4 ng amitrole) was obtained for a sample loop of 100 microL at a fixed potential of +0.55 V (vs. Ag/AgCl) in 0.1 M NaOH and a flow rate of 4.0 mL min(-1). Furthermore, the modified carbon paste electrodes offers reproducible responses in such a system, and the relative standard deviation was 3.3% using the same surface, 5.1% using different surface, and 6.9% using different pastes. The performance of the cobalt-phthalocyanine-modified carbon paste electrodes is illustrated here for the determination of amitrole in commercial formulations. The response of the electrodes is stable, with more than 80% of the initial retained activity after 50 min of continuous use.

Determination of the herbicide amitrole in water with pre-column derivatization, liquid chromatography and tandem mass spectrometry.

Amitrole is a widely used polar herbicide, difficult to isolate from water. Due to its persistence, it can easily pollute ground and surface waters used in drinking water production. A fully automated on-line SPE-HPLC (solid-phase extraction-high-performance liquid chromatography) method with atmospheric pressure chemical ionisation-tandem mass spectrometry detection is described for the determination of amitrole. A pre-column derivatization with 9-fluorenylmethoxycarbonyl chloride directly in the native aqueous sample allows an enrichment step by SPE and HPLC separation. Due to the sensitivity of tandem mass spectrometric detection, a limit of detection and quantification as low as 0.025 microg/l was achieved in drinking water and ground and surface water. Based on the constant ratio of two selected product ions together with the retention time, the identification is very selective and quantitation is very reliable. The performance characteristics of the described method fully meet the requirements set by the EU Drinking Water Directive: recoveries of >95% in drinking water and >75% in surface water were achieved, as well as RSD values for repeatability of <9% in drinking water and <12% in surface water (determined at a spiking level of 0.1 microg/l). The method was successfully applied to real samples of ground and surface water with actual concentration up to 1.1 microg/l.

Herbicide: fatal ammonium thiocyanate and aminotriazole poisoning.

OBJECTIVE: To describe fatal herbicide poisoning with Radoxone TL composed of aminotriazole and ammonium thiocyanate. CASE REPORT: A 54-year-old man was hospitalized because of unexplained coma with myoclonic jerks and vascular collapse. Despite symptomatic treatment with mechanical ventilation and vascular filling, life-threatening shock occurred with oliguria, profound metabolic acidosis and cardiac arrest. Hyperchloremia (141 mmol/L) with reversed anion gap (-19) suggested interference with chloride measurement caused by halogens (Br,F,I) or other anions such as thiocyanate. Eventually a weed killer, Radoxone TL containing ammonium thiocyanate, was found at the patient's house. Thiocyanate and aminotriazole blood levels were 750 mg/L and 138 mg/L respectively more than 12 hours after ingestion. After prolonged cardiopulmonary resuscitation, continuous venovenous hemodiafiltration was performed. Despite hemodynamic recovery the patient died 48 hours later of postanoxic coma. CONCLUSION: Aminotriazole, a systemic nonselective herbicide, is often associated with ammonium thiocyanate which enhances its activity. Experimental studies and previous fatal cases suggest a predominant toxicity of thiocyanate. Early diagnosis is important.