Evaluation of imazalil dissipation/migration in postharvest papaya using low-temperature partition extraction and GC-MS analysis.

Methods involving solid-liquid extraction with low-temperature partition and analysis by gas chromatography coupled to mass spectrometry (GC-MS) were validated to investigate the dissipation/migration of residues of the postharvest fungicide imazalil in papaya skin, pulp, and seeds. The fruits were stored for 23 days (14 °C). Every two days, fruits from the control group and those treated with imazalil had their skin, outer pulp, inner pulp, and seeds separated and then analyzed by GC-MS. After the 23rd day, about 70% of the imazalil had dissipated. Most of the remaining residue was found in the skin; however, the small amount migrating into the pulp was above the maximum residue levels allowed by the regulatory agencies. Imazalil residue was also detected in seeds at concentrations lower than the LOQ (0.025 mg kg-1). Mass loss was the only quality parameter that showed a significant difference between the fruits of the control and study groups.

Cutting agents in cocaine: A temporal study of the period 2015-2017 in the Northern Region of Colombia.

Cocaine is a naturally occurring psychostimulant drug available worldwide. Drug trafficking networks adulterate pure cocaine with cutting agents to increase their earnings. This study presents a descriptive statistical analysis of the cutting agents found in 2118 cocaine samples that were seized in the Northern Region of Colombia (in the period 2015-2017). The data used in this study was drawn from the GC-MS analytical reports of the National Institute of Legal Medicine and Forensic Sciences -Colombia, Northern Region. Results showed diverse cutting agents in seized cocaine samples, from which the most commonly used are caffeine, phenacetin, lidocaine, imidazole and levamisole. In addition, cocaine samples showed different mixtures of the above cutting agents, predominantly caffeine/phenacetin and caffeine/lidocaine/phenacetin mixtures.

Rapid monitoring of pesticides in tomatoes (Solanum lycopersicum L.) during pre-harvest intervals by paper spray ionization mass spectrometry.

A rapid analysis of acephate, chlorpyrifos, and cyazofamid in tomato peels during pre-harvest intervals using paper spray ionization mass spectrometry (PSI-MS) has been demonstrated. LODs of 0.01 ppm and LOQs of 0.03 ppm were achieved. Relative standard deviations were below 9%, and recoveries close to 100%. For pesticides monitoring, samples were separated into stored and field groups. Stored group contained fruits that were harvested and stored at low temperature during the pre-harvest interval, and the field group contained fruits that were on the agricultural field over the pre-harvest interval. The decrease in pesticide amounts was lower for the stored samples. At the end of the pre-harvest intervals, acephate, chlorpyrifos, and cyazofamid were determined at 0.86, 0.96, and 0.23 ppm in the stored group, and at 0.26, 0.37, and 0.09 ppm in the field group, respectively. This work demonstrates the utility of PSI-MS for performing rapid quality control of fruit harvesting.

Influence of hydrodynamic conditions on the degradation of 1-butyl-3-methylimidazolium chloride solutions on boron-doped diamond anodes.

This study assessed the influence of hydrodynamic conditions on the degradation process of 1-butyl-3-methylimidazolium chloride (BMImCl) solution on a boron-doped diamond anode in a filter-type electrochemical reactor configuration. The results show that this parameter did not significantly affect this process when operating in the laminar regime. However, in the transition regime (Re ≥ 2000), higher flow rates resulted in a faster removal of BMImCl and total organic carbon, making the process more efficient. Following BMImCl degradation, nitrates were generated at the cathode, then reduced at the cathode to ammonium; combination with free chloride produced at the anode led to the transformation of chloride into combined chlorine forms instead of more toxic oxianions such as chlorate and perchlorate. Thus, the flow rate can be a key parameter for defining operating conditions in which the target BMImCl is more effectively degraded with reduced generation of undesirable secondary products.

Seasonal change in main alkaloids of jaborandi (Pilocarpus microphyllus Stapf ex Wardleworth), an economically important species from the Brazilian flora.

Pilocarpus microphyllus Stapf ex Wardleworth (jaborandi, Rutaceae) is one of the most important Brazilian medicinal species owing to its content of pilocarpine (PIL), an alkaloid used for treating glaucoma and xerostomia. This species contains another alkaloid, epiisopiloturine (EPI), which has demonstrated effectiveness against schistosomiasis. The aim of this work was to assess seasonal changes of PIL and EPI in three populations of cultivated P. microphyllus from northeastern Brazil over one year, including the dry and rainy seasons. Alkaloid profiles were correlated to phenotypic and genetic patterns in the morphological and molecular characterizations. PIL was the primary alkaloid and its levels differed among populations in all months except September. The S01 population (green line) showed an especially high PIL content compared to populations S02 and S03 (traditional line), which had similar alkaloid contents. PIL content gradually decreased in the three populations in the rainy season.EPI content was significantly different between the green line (S01) and the traditional line (S02 and S03).S01 had a significantly lower EPI content in all months, demonstrating that it was not the best source for EPI extraction. Inter simple sequence repeat (ISSR) markers and morphological analyses clearly separated S01 from S02 and S03, in agreement with the alkaloid results. This study shows the first correlation between the chemical, morphological, and molecular markers of P. microphyllus and highlights the potential benefits of a multidisciplinary research approach aimed at supporting both industry and conservation of natural resources.

Molecularly imprinted solid phase extraction of fluconazole from pharmaceutical formulations.

This work encompasses a direct and coherent strategy to synthesise a molecularly imprinted polymer (MIP) capable of extracting fluconazole from its sample. The MIP was successfully prepared from methacrylic acid (functional monomer), ethyleneglycoldimethacrylate (crosslinker) and acetonitrile (porogenic solvent) in the presence of fluconazole as the template molecule through a non-covalent approach. The non-imprinted polymer (NIP) was prepared following the same synthetic scheme, but in the absence of the template. The data obtained from scanning electronic microscopy, infrared spectroscopy, thermogravimetric and nitrogen Brunauer-Emmett-Teller plot helped to elucidate the structural as well as the morphological characteristics of the MIP and NIP. The application of MIP as a sorbent was demonstrated by packing it in solid phase extraction cartridges to extract fluconazole from commercial capsule samples through an offline analytical procedure. The quantification of fluconazole was accomplished through UPLC-MS, which resulted in LOD≤1.63×10(-10) mM. Furthermore, a high percentage recovery of 91±10% (n=9) was obtained. The ability of the MIP for selective recognition of fluconazole was evaluated by comparison with the structural analogues, miconazole, tioconazole and secnidazole, resulting in percentage recoveries of 51, 35 and 32%, respectively.

A method for determination of imazapic and imazethapyr residues in soil using an ultrasonic assisted extraction and LC-MS/MS.

At least 52 % of the planted rice area in Rio Grande do Sul, a major rice producing state in Brazil, employs Clearfield(®) production system, corresponding to 580,000 ha of cultivated area. To grow rice with Clearfield(®) technology, producers combine imazethapyr and imazapic herbicides. However, these herbicides leave residual activity in soil; consequently, the repeated application of imazethapyr and imazapic on Brazilian Clearfield(®) rice fields has increased these herbicides persistence in treated soils. In this study, a method has been developed for removal and quantification of imazethapyr and imazapic residues in soil through ultrasonic assisted extraction using methanol-phosphoric acid aqueous solution (pH 2.0). The detected response was linear for both herbicides within the range of 0.25-5 ng mL(-1) with correlations coefficients >0.99. The quantification limit was limit of quantification 0.2 µg Kg(-1) for both pesticides. The good recovery rate from all pesticides, which ranges between 70 % and 120 %, demonstrates the method's validity.

Persistence and sorption of imazapyr in three Argentinean soils.

Imazapyr is a herbicide widely used for weed control in imidazolinone-tolerant sunflower. Imazapyr has a high potential for leaching into groundwater because it is highly water-soluble, persistent in soil, and only weakly sorbed by soils. There is a lack of information available in Argentina concerning groundwater leaching of imazapyr. Therefore, the objective of the present study was to determine the persistence and sorption of imazapyr in 3 Argentinean soils (Tandil, Anguil, and Cerro Azul sites). The presence and concentration of imazapyr were determined and quantified by ultra-performance liquid chromatography and tandem mass spectrometry. The persistence in soils followed the order: Cerro Azul > Tandil > Anguil, with half-life values of 121 d, 75 d, and 37 d, respectively. The half-life of imazapyr was negatively associated with soil pH and iron and aluminum content, and was positively related to clay content. Imazapyr sorption was found to be well described by the Freundlich isotherm. Soil pH and clay, iron, and aluminum contents were the main factors affecting the sorption of imazapyr. The sorption had a limiting effect on the degradation rate. Under certain conditions, the weak sorption and high persistence may increase the movement of imazapyr in the soil profile and the risk of groundwater pollution.

Degradation of conazole fungicides in water by electrochemical oxidation.

The electrochemical oxidation (EO) treatment in water of three conazole fungicides, myclobutanil, triadimefon and propiconazole, has been carried out at constant current using a BDD/SS system. First, solutions of each fungicide were electrolyzed to assess the effect of the experimental parameters such as current, pH and fungicide concentration on the decay of each compound and total organic carbon abatement. Then a careful analysis of the degradation by-products was made by high performance liquid chromatography, ion chromatography and gas chromatography coupled with mass spectrometry in order to provide a detailed discussion on the original reaction pathways. Thus, during the degradation of conazole fungicides by the electrochemical oxidation process, aromatic intermediates, aliphatic carboxylic acids and Cl(-) were detected prior to their complete mineralization to CO2 while NO3(-) anions remained in the treated solution. This is an essential preliminary step towards the applicability of the EO processes for the treatment of wastewater containing conazole fungicides.

Evaluation of an analytical methodology using QuEChERS and GC-SQ/MS for the investigation of the level of pesticide residues in Brazilian melons.

A multiresidue method based on the sample preparation by modified QuEChERS and detection by gas chromatography coupled to single quadruple mass spectrometers (GC-SQ/MS) was used for the analysis of 35 multiclass pesticides in melons (Cucumis melo inodorus) produced in Ceara-Brazil. The rates of recovery for pesticides studied were satisfactory (except for the etridiazole), ranging from 85% to 117% with a relative standard deviation (RSD) of less than 15%, at concentrations between 0.05 and 0.20 mg kg(-1). The limit of quantification (LOQ) for most compounds was below the MRLs established in Brazil. The combined relative uncertainty (Uc) and expanded uncertainty (Ue) was determined using repeatability, recovery and calibration curves data for each pesticide. Analysis of commercial melons samples revealed the presence of pesticides bifenthrin and imazalil at levels below the MRLs established by ANVISA, EU and USEPA.

A selenium-based ionic liquid as a recyclable solvent for the catalyst-free synthesis of 3-selenylindoles.

The ionic liquid 1-butyl-3-methylimidazolium methylselenite, [bmim][SeO2(OCH3)], was successfully used as solvent in the catalyst-free preparation of 3-arylselenylindoles by the reaction of indole with ArSeCl at room temperature. The products were obtained selectively in good yields without the need of any additive and the solvent was easily reused for several cycles with good results.

Determination of 2-methylimidazole and 4-methylimidazole in caramel colors by capillary electrophoresis.

The use of chemical preservative compounds is common in the food products industry. Caramel color is the most usual additive used in beverages, desserts, and breads worldwide. During its fabrication process, 2- and 4-methylimidazole (MeI), highly carcinogenic compounds, are generated. In these cases, the development of reliable analytical methods for the monitoring of undesirable compounds is necessary. The primary procedure for the analysis of 2- and 4-MeI is using LC- or GC-MS techniques. These procedures are time-consuming and require large amounts of organic solvents and several pretreatment steps. This prevents the routine use of this procedure. This paper describes a rapid, efficient, and simple method using capillary electrophoresis (CE) for the separation and determination of 2- and 4-MeI in caramel colors. The analyses were performed using a 75 µm i.d. uncoated fused-silica capillary with an effective length of 40 cm and a running electrolyte consisting of 160 mmol L(-1) phosphate plus 30% acetonitrile. The pH was adjusted to 2.5 with triethylamine. The analytes were separated within 6 min at a voltage of 20 kV. Method validation revealed good repeatability of both migration time (<0.8% RSD) and peak area (<2% RSD). Analytical curves for 2- and 4-MeI were linear in the 0.4-40 mg L(-1) concentration interval. Detection limits were 0.16 mg L(-1) for 4-MeI and 0.22 mg L(-1) for 2-MeI. The extraction recoveries were satisfactory. The developed method showed many advantages when compared to the previously used method.

Determination of neonicotinoid insecticides in environmental samples by micellar electrokinetic chromatography using solid-phase treatments.

A sensitive and reliable method based on MEKC has been developed and validated for trace determination of neonicotinoid insecticides (thiamethoxam, acetamiprid, and imidacloprid) and the metabolite 6-chloronicotinic acid in water and soil matrices. Optimum separation of the neonicotinoid insecticides was obtained on a 58 cm long capillary (75 µm id) using as the running electrolyte 40 mM SDS, 5 mM borate (pH 10.4), and 5% (v/v) methanol at a temperature of 25°C, a voltage of 25 kV and with hydrodynamic injection (10 s). The analysis time was less than 7 min. Prior to MEKC determination, the samples were purified and enriched by carrying out extraction-preconcentration steps. For aqueous samples, off-line SPE with a sorptive material such as Strata-X (polymeric hydrophobic sorbent) and octadecylsilane (C18) was carried out to clean up and preconcentrate the insecticides. However, for soil samples, matrix solid-phase dispersion (MSPD) was applied with C18 used as the dispersant. Good linearity, accuracy, and precision were obtained and the detection limits were in the range between 0.01 and 0.07 µg mL⁻¹ for river water and 0.17 and 0.37 µg g⁻¹ for soil samples. Recovery levels reached greater than 92% for all of the assayed neonicotinoids in river water samples with Strata-X. In soil matrices, the best recoveries (63-99%) were obtained with MSPD.

Development and validation of a discriminating in vitro dissolution method for a poorly soluble drug, olmesartan medoxomil: comparison between commercial tablets.

A dissolution test for tablets containing 40 mg of olmesartan medoxomil (OLM) was developed and validated using both LC-UV and UV methods. After evaluation of the sink condition, dissolution medium, and stability of the drug, the method was validated using USP apparatus 2, 50 rpm rotation speed, and 900 ml of deaerated H(2)O + 0.5% sodium lauryl sulfate (w/v) at pH 6.8 (adjusted with 18% phosphoric acid) as the dissolution medium. The model-independent method using difference factor (f(1)) and similarity factor (f(2)), model-dependent method, and dissolution efficiency were employed to compare dissolution profiles. The kinetic parameters of drug release were also investigated. The obtained results provided adequate dissolution profiles. The developed dissolution test was validated according to international guidelines. Since there is no monograph for this drug in tablets, the dissolution method presented here can be used as a quality control test for OLM in this dosage form, especially in a batch to batch evaluation.

HPLC-ESI-MS/MS of imidazole alkaloids in Pilocarpus microphyllus.

Pilocarpine, an important imidazole alkaloid, is extracted from the leaves of Pilocarpus microphyllus (Rutaceae), known in Brazil as jaborandi and used mainly for the treatment of glaucoma. Jaborandi leaves also contain other imidazole alkaloids, whose pharmacological and physiological properties are unknown, and whose biosynthetic pathways are under investigation. In the present study, a HPLC method coupled with ESI-MS(n) was developed for their qualitative and quantitative analysis. This method permits the chromatographic separation of the imidazole alkaloids found in extracts of jaborandi, as well as the MS/MS analysis of the individual compounds. Thus two samples: leaves of P. microphyllus and a paste that is left over after the industrial extraction of pilocarpine; were compared. The paste was found to contain significant amounts of pilocarpine and other imidazole alkaloids, but had a slightly different alkaloid profile than the leaf extract. The method is suitable for the routine analysis of samples containing these alkaloids, as well as for the separation and identification of known and novel alkaloids from this family, and may be applied to further studies of the biosynthetic pathway of pilocarpine in P. microphyllus.

Development and validation of liquid chromatographic and ultraviolet derivative spectrophotometric methods for determination of epinastine hydrochloride in coated tablets.

High-performance liquid chromatographic (LC) and ultraviolet derivative spectrophotometric (UVD) methods were developed and validated for the quantitative determination of epinastine hydrochloride in coated tablets. LC was performed on a reversed-phase RP-18 column with a mobile phase composed of 0.3% triethylamine (pH adjusted to 4.0 with 10% orthophosphoric acid)-methanol (60 + 40, v/v). The first-order derivative method was performed at 243.8 nm using HCI and methanol as the solvent. The methods were validated according to U.S. Pharmacopoeia and International Conference on Harmonization guidelines. The statistical analysis by Student's t-test showed no significant difference between the results obtained by the 2 methods. The proposed methods were found to be simple, rapid, precise, accurate, robust, and sensitive, allowing perfect interchange. The LC and UVD methods can be used in the routine quantitative determination of the epinastine hydrochloride in coated tablets.

Testing MACRO (version 5.1) for pesticide leaching in a Dutch clay soil.

Testing of pesticide leaching models against comprehensive field-scale measurements is necessary to increase confidence in their predictive ability when used as regulatory tools. Version 5.1 of the MACRO model was tested against measurements of water flow and the behaviour of bromide, bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide] and imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] in a cracked clay soil. In keeping with EU (FOCUS) procedures, the model was first calibrated against the measured moisture profiles and bromide concentrations in soil and in drain water. Uncalibrated pesticide simulations based on laboratory measurements of sorption and degradation were then compared with field data on the leaching of bentazone and imidacloprid. Calibrated parameter values indicated that a high degree of physical non-equilibrium (i.e. strong macropore flow) was necessary to describe solute transport in this soil. Comparison of measured and simulated bentazone concentration profiles revealed that the bulk of the bentazone movement in this soil was underestimated by MACRO. Nevertheless, the model simulated the dynamics of the bentazone breakthrough in drain water rather well and, in particular, accurately simulated the timing and the concentration level of the early bentazone breakthrough in drain water. The imidacloprid concentration profiles and its persistence in soil were simulated well. Moreover, the timing of the early imidacloprid breakthrough in the drain water was simulated well, although the simulated concentrations were about 2-3 times larger than measured. Deep groundwater concentrations for all substances were underestimated by MACRO, although it simulated concentrations in the shallow groundwater reasonably well. It is concluded that, in the context of ecotoxicological risk assessments for surface water, MACRO can give reasonably good simulations of pesticide concentrations in water draining from cracking clay soils, but that prior calibration against hydrologic and tracer data is desirable to reduce uncertainty and improve accuracy.

Simultaneous multiresponse optimization applied to epinastine determination in human serum by using capillary electrophoresis.

Experimental design and optimization techniques were implemented for the development of a rapid and simple capillary zone electrophoresis method (CZE) for the determination of epinastine hydrochloride in human serum. The effects of five factors were studied on the resolution between the peaks for the target analyte (epinastine hydrochloride) and lidocaine hydrochloride, used as internal standard, as well as on the analysis time. The factors were the concentration and pH of the buffer, the injection time, the injection voltage and the separation voltage. The separation was carried out by using an uncoated silica capillary with 50 microm i.d. and total length 64.5 cm (150 microm of path length) and UV detection (200 nm). Multiple response simultaneous optimization by using the desirability function was used to find experimental conditions where the system generates desirable results. The optimum conditions were: sodium phosphate buffer solution, 16.0 mmol L(-1); pH 8.50; injection voltage, 20.0 kV; injection time, 30 s; separation voltage, 26.7 kV. The method was confirmed to be linear in the range of 2.0-12 ng mL(-1). The injection repeatability of the method was evaluated by six injections at three concentration levels, while intra-assay precision was assessed by analysing a single concentration level, yielding a CV's of ca. 1% for standard and 2% for serum samples. Accuracy was evaluated by recovery assays and by comparing with an HPLC method, the results being acceptable according to regulatory agencies. The rudgeness was evaluated by means of an experimental Plackett-Burman design, in which the accuracy was assessed when small changes were set in the studied parameters. Clean-up of human serum samples was carried out by means of a liquid-liquid extraction procedure, which gave a high extraction yield for epinastine hydrochloride (93.00%).

Spectrophotometric determination of oxiconazole in topical lotion using methyl orange.

A spectrophotometric method is described for the determination of oxiconazole in raw material and in topical lotion. This method is based on the reaction of the oxiconazole with methyl orange in buffered aqueous solution of citric acid at pH 2.3. The chromogen, being extractable with dichloromethane, could be measured quantitatively with maximum absorption at 427 nm. The Lambert-Beer law was obeyed in the concentration range of 4.0-14.0 microg ml(-1). A prospective validation of the method showed that the method was linear (r=0.9995), precise (intra-day: CV=1.57% and inter-day: CV=1.50%) and accurate (mean recoveries: 99.69%). The results compared favourably with those of the HPLC method.