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1.
Mikrochim Acta ; 191(6): 322, 2024 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-38730044

RESUMO

The first electrochemical sensor application in the literature is described for the sensitive and selective determination of the selective Janus kinase (JAK)-1 inhibitor abrocitinib (ABR). ABR is approved by the U.S. Food and Drug Administration (FDA) for the treatment of atopic dermatitis. The molecularly imprinted polymer (MIP)-based sensor was designed to incorporate zinc nanoflower (ZnNFs)-graphene oxide (GO) conjugate (ZnNFs@GO), synthesized from the root methanolic extract (RME) of the species Alkanna cappadocica Boiss. et Bal. to improve the porosity and effective surface area of the glassy carbon electrode (GCE). Furthermore, the MIP structure was prepared using ABR as a template molecule, 4-aminobenzoic acid (4-ABA) as a functional monomer, and other additional components. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) were used to characterize the surface and structure of the synthesized nanomaterial and MIP-based surface. Among the electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were preferred for detailed electrochemical characterization, and differential pulse voltammetry (DPV) was preferred for all other electrochemical measurements using 5.0 mM [Fe(CN)6]3-/4- solution as the redox probe. The MIP-based sensor, which was the result of a detailed optimization phase, gave a linear response in the 1.0 × 10-13 - 1.0 × 10-12 M range in standard solution and serum sample. The obtained limit of detection (LOD) and limit of quantification (LOQ) values and recovery studies demonstrated the sensitivity, accuracy, and applicability of the sensor. Selectivity, the most important feature of the MIP-based sensor, was verified by imprinting factor calculations using ibrutinib, ruxolitinib, tofacitinib, zonisamide, and acetazolamide.


Assuntos
Técnicas Eletroquímicas , Limite de Detecção , Polímeros Molecularmente Impressos , Zinco , Polímeros Molecularmente Impressos/química , Técnicas Eletroquímicas/métodos , Técnicas Eletroquímicas/instrumentação , Zinco/química , Grafite/química , Humanos , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/sangue , Aminoimidazol Carboxamida/química , Nanoestruturas/química , Eletrodos
2.
J Environ Sci Health B ; 55(10): 876-888, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32654594

RESUMO

In the present work we have studied photo-induced decomposition of iprodione on silica support with different additions of titanium dioxide. Both the experimental and theoretical (DFT) approaches have been applied. It was found that 16 hours visible light exposure of the samples with 0.1% and 1.0% of TiO2 leads respectively to 48.28% and 21.05% of residual amounts of iprodione in these samples. A number of intermediates and end products were identified by means of GS-MS and LC-MS chromatography. The iprodione isomer (RP 30228) and its decay product 1-(3,5-dichlorophenyl)-5-isopropyl biuret (RP 36221) were identified among them. Our DFT calculations have revealed the detailed mechanisms of formation of the above products and the mechanism of accelerated proton-induced decomposition of iprodione molecules adsorbed on the TiO2 surface. Also, the intra-molecular reasons for iprodione stability in acidic media were clarified together with the mechanism of hydantoin cycle opening under the action of hydroxyl anions.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Fungicidas Industriais/análise , Hidantoínas/análise , Fotólise , Luz Solar , Titânio/análise , Aminoimidazol Carboxamida/análise , Catálise
3.
Artigo em Inglês | MEDLINE | ID: mdl-31535952

RESUMO

In this study, we propose an improved analytical method for the multiresidue analysis of captan (plus its metabolite, tetrahydrophthalimide), folpet (plus its metabolite, phthalimide), captafol, and iprodione in cereals using liquid chromatography tandem mass spectrometry (LC-MS/MS). As captan, captafol, and folpet are easily degraded during homogenisation and extraction, samples were comminuted with liquid nitrogen, and both QuEChERS and ethyl acetate-based extraction workflows provided a satisfactory method performance. The optimised LC-MS/MS procedure with electrospray ionisation did not degrade these compounds, and offered sufficient method selectivity by resolving and minimising co-eluting matrix-derived interferences. The method also resolved the problem of non-specific mass spectra that these compounds usually produce on GC-MS analysis involving electron ionisation. The method performance was satisfactory for all 6 compounds at 0.01 mg kg-1 and higher levels of fortification, and validated as per the SANTE/11813/2017 guidelines of analytical quality control in a wide range of cereals including rice, wheat, sorghum, and corn. The method provides special advantage of simultaneous analysis of captan, and folpet along with their metabolites (tetrahydrophthalimide, and phthalimide, respectively) in combination with captafol, and iprodione in a single chromatographic run. Although iprodione is known to degrade to 3,5-dichloroaniline, since this metabolite is not a part of the residue definition, it was not included in the scope of this method. As the method demonstrates satisfactory selectivity, sensitivity, accuracy, precision, and robustness in a wide range of cereal matrices, it is recommended for regulatory testing of these compounds in cereals.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Captana/análogos & derivados , Captana/análise , Cicloexenos/análise , Contaminação de Alimentos/análise , Hidantoínas/análise , Resíduos de Praguicidas/análise , Ftalimidas/análise , Aminoimidazol Carboxamida/análise , Cromatografia Líquida , Grão Comestível/química , Análise de Alimentos , Espectrometria de Massas em Tandem
4.
Food Chem ; 301: 125216, 2019 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-31404804

RESUMO

An improved liquid chromatography tandem mass spectrometry method is reported for the determination of residues of captan (+tetrahydrophthalimide), captafol, folpet (+phthalimide), and iprodione in fruits and vegetables. The optimized electrospray ionization parameters (high cone gas flow, and a low desolvation temperature) did not result in degradation of target compounds, rather they provided a significant advantage over the conventional GC-MS/MS methods, which lack sensitivity and repeatability. Strategies for minimizing losses in recovery of these compounds during sample preparation included cryogenic comminution, extraction with acidified ethyl acetate or acetonitrile, and dilution of the final extract with acidified water prior to LC-MS/MS analysis. The method performance complied with the SANTE/11813/2017 guidelines, with recoveries in the range of 70-120% at the LOQ of 0.01 mg/kg across the tested matrices at various pHs. The efficiency of the method was reflected in its precision (RSDs < 10%) for incurred residues.


Assuntos
Cromatografia Líquida/métodos , Contaminação de Alimentos/análise , Frutas/química , Resíduos de Praguicidas/análise , Espectrometria de Massas em Tandem/métodos , Verduras/química , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Captana/análogos & derivados , Captana/análise , Cicloexenos/análise , Hidantoínas/análise , Limite de Detecção , Ftalimidas/análise
5.
Food Chem ; 293: 226-232, 2019 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-31151605

RESUMO

Iprodione is a fungicide widely used in viticulture in most agricultural countries. It was banned recently in the European community because of its carcinogenic and endocrine disrupting characters. In this work, a cheap analytical method able to monitor iprodione in a white wine was developed. Molecularly imprinted sol-gel polymers (MIS) specific to iprodione and using green solvents were synthesized. An experimental design having the following factors (solvent volume and crosslinker quantity) was used to prepare an optimal MIS. In terms of selectivity, the optimal MIS showed the best partition coefficient towards iprodione in a white wine containing four other competing fungicides (procymidone, pyrimethanil, azoxystrobin and iprovalicarb). A solid phase extraction method using the optimal MIS was optimized and applied to analyse iprodione in a white wine. Low detection and quantification limits were reached 11.7 and 39.1 µg/L respectively.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Fungicidas Industriais/análise , Hidantoínas/análise , Impressão Molecular , Polímeros/química , Solventes/química , Vinho/análise , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/isolamento & purificação , Cromatografia Líquida de Alta Pressão , Fungicidas Industriais/isolamento & purificação , Géis/química , Química Verde , Hidantoínas/isolamento & purificação , Extração em Fase Sólida/métodos
6.
Environ Monit Assess ; 190(10): 607, 2018 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-30255206

RESUMO

This study reports the optimization of a binary dispersive liquid-liquid microextraction method for the determination of iprodione, procymidone, and chlorflurenol by gas chromatography mass spectrometry. The study was aimed at using two extraction solvents to increase the extraction efficiency of all analytes. The binary solvents recorded results higher than the mono-solvents. After examining the effects of main experimental parameters and their interactions by analysis of variance, 200 µL of binary mixture (dichloromethane and 1,2-dichloroethane), 2.5 mL of ethanol, and 15 s vortex were obtained as optimum parameters. The detection and quantification limits calculated for the analytes were found to be between 0.30-1.6 and 1.0-5.3 ng/mL, respectively. Enhancement in detection power calculated as a ratio of the binary extraction detection limit to the detection limit of direct GC-MS analysis was 105-, 214-, and 233-fold for chlorflurenol, iprodione, and procymidone, respectively. In order to check the accuracy of the developed method, recovery study was performed. Water sampled from a lake and two wastewater samples from treatment facilities were spiked at two concentrations, and the percent recovery calculated for the samples ranged between 87 and 116%. These results confirmed the suitability of the method to real samples for accurate determination of the analytes at trace levels.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Compostos Bicíclicos com Pontes/análise , Monitoramento Ambiental/métodos , Fluorenos/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidantoínas/análise , Águas Residuárias/química , Poluentes Químicos da Água/análise , Aminoimidazol Carboxamida/análise , Lagos/análise , Limite de Detecção , Microextração em Fase Líquida/métodos , Solventes/química
7.
Environ Sci Pollut Res Int ; 25(22): 21440-21450, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-28914414

RESUMO

A biopurification system based on the adsorption and degradation capacity of a biomixture to degrade a mixture of pesticides (atrazine, chlorpyrifos, iprodione; 50 mg kg-1 each) in repeated applications (0, 30, and 60 days) was evaluated. Tanks of 1 m3 packed with a biomixture (ρ 0.29 g mL-1) with and without vegetal cover were used. The biomixture contained soil, peat, and wheat straw in a proportion 1:1:2 by volume, respectively. Pesticide concentrations, biological activities (urease, phenoloxidase, and dehydrogenase), and microbial community changes (DGGE and qPCR) were evaluated periodically. Pesticide dissipation was higher in tanks with vegetal cover (> 95%) and no variation was observed after the three applications; contrarily, pesticide dissipation decreased in the tank without vegetal cover after each application. The presence of vegetal cover decreased the half-life of pesticides by at least twice. Biological activities were in general not affected by the application and reapplication of pesticides in the same treatment; however, they exhibited some differences between tanks containing and lacking the vegetal cover. High similarity between microbial groups (actinobacteria, bacteria, and fungi) was observed, suggesting no influence ascribable to the successive pesticide applications. The number of copies of bacteria and actinobacteria remained almost constant during the assay. However, the number of copies of fungi was significantly higher in the uncontaminated tank without vegetal cover.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Atrazina/metabolismo , Clorpirifos/metabolismo , Poluição Ambiental/prevenção & controle , Hidantoínas/metabolismo , Microbiologia do Solo , Actinobacteria/metabolismo , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/metabolismo , Atrazina/análise , Bactérias/metabolismo , Biodegradação Ambiental , Clorpirifos/análise , Enzimas/análise , Fungos/metabolismo , Hidantoínas/análise , Praguicidas/análise , Praguicidas/metabolismo , Plantas , Solo , Poluentes do Solo/análise , Poluentes do Solo/metabolismo
8.
Drug Test Anal ; 9(11-12): 1704-1712, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-29032594

RESUMO

AICAR (5-aminoimidazole-4-carboxamide-1-ß-D-ribofuranoside), is a naturally occurring substance which is part to the World Anti-Doping Agency (WADA) Prohibited List. It is claimed to improve physical performance when administered as a supplement. As for other endogenous compounds such as steroids, the gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) analysis remains an efficient tool to differentiate endogenous substances from exogenous ones. A protocol was described in the literature for the analysis of AICAR by GC-C-IRMS. The aim of the present study was to implement this protocol in our laboratory and to propose solutions to avoid the difficulties encountered. The first point discussed in this study is the derivatization step. Due to the structure of the AICAR molecule, conventional derivatization for GC-C-IRMS such as acetylation could not be applied and silylation was preferred. The improvement of the derivatives stability was achieved thanks to several derivatization conditions tested. This adjustment led to a reproducible derivatization pattern with the 3-TMS form as major derivative product. The second point discussed in this study is the diminution of extracts' background noise. Indeed, the implementation of the published protocol was not easy due to high performance liquid chromatography (HPLC) problems encountered when concentrated urine was injected into our system. Also, too many interferences in the endogenous reference compound fractions were observed. The addition of both a wash step before the HPLC purification and a HPLC purification step for the endogenous reference compound (ERC) fraction allowed us to increase the robustness of the method. This study presents the modified protocol compared to the original protocol as well as the evaluation of the whole method performances. Copyright © 2017 John Wiley & Sons, Ltd.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Ribonucleotídeos/análise , Esteroides/análise , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/química , Cromatografia Líquida de Alta Pressão , Dopagem Esportivo , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Ribonucleotídeos/química , Esteroides/química
9.
J Environ Sci Health B ; 52(9): 651-657, 2017 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-28594308

RESUMO

The use of biopurification systems can mitigate the effects of pesticide contamination on farms. The primary aim of this study was to evaluate the effect of pesticide dissipation on microbial communities in a pilot biopurification system. The pesticide dissipation of atrazine, chlorpyrifos and iprodione (35 mg kg-1 active ingredient [a.i.]) and biological activity were determined for 40 days. The microbial communities (bacteria, actinomycetes and fungi) were analyzed using denaturing gradient gel electrophoresis (DGGE). In general, pesticide dissipation was the highest by day 5 and reached 95%. The pesticides did not affect biological activity during the experiment. The structure of the actinomycete and bacterial communities in the rhizosphere was more stable during the evaluation than that in the communities in the control without pesticides. The rhizosphere fungal communities, detected using DGGE, showed small and transitory shifts with time. To conclude, rhizosphere microbial communities were not affected during pesticide dissipation in a pilot biopurification system.


Assuntos
Bactérias/efeitos dos fármacos , Fungos/efeitos dos fármacos , Consórcios Microbianos/efeitos dos fármacos , Praguicidas/toxicidade , Eliminação de Resíduos Líquidos/métodos , Actinomyces/efeitos dos fármacos , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/toxicidade , Atrazina/análise , Atrazina/toxicidade , Biodiversidade , Clorpirifos/análise , Clorpirifos/toxicidade , Eletroforese em Gel de Gradiente Desnaturante , Hidantoínas/análise , Hidantoínas/toxicidade , Praguicidas/análise
10.
Drug Test Anal ; 9(9): 1363-1371, 2017 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28407446

RESUMO

Acadesine, 5-aminoimidazole-4-carboxamide-1-ß-D-ribofuranoside, commonly known as AICAR, is a naturally occurring adenosine monophosphate-activated protein kinase (AMPK) activator in many mammals, including humans and horses. AICAR has attracted considerable attention recently in the field of doping control because of a study showing the enhancement of endurance performance in unexercised or untrained mice, resulting in the term 'exercise pill'. Its use has been classified as gene doping by the World Anti-Doping Agency (WADA), and since it is endogenous, it may only be possible to control deliberate administration of AICAR to racehorses after establishment of an appropriate threshold. Herein we report our studies of AICAR in post-race equine urine and plasma samples including statistical studies of AICAR concentrations determined from 1,470 urine samples collected from thoroughbreds and standardbreds and analyzed in Australia, France, and Hong Kong. Quantification methods in equine urine and plasma using liquid chromatography-mass spectrometry were developed by the laboratories in each country. An exchange of spiked urine and plasma samples between the three countries was conducted, confirming no significant differences in the methods. However, the concentration of AICAR in plasma was found to increase upon haemolysis of whole blood samples, impeding the establishment of a suitable threshold in equine plasma. A possible urine screening cut-off at 600 ng/mL for the control of AICAR in racehorses could be considered for adoption. Application of the proposed screening cut-off to urine samples collected after intravenous administration of a small dose (2 g) of AICAR to a mare yielded a short detection time of approximately 4.5 h. Copyright © 2017 John Wiley & Sons, Ltd.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Dopagem Esportivo/prevenção & controle , Ribonucleosídeos/análise , Ribonucleotídeos/análise , Espectrometria de Massas em Tandem/métodos , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/química , Aminoimidazol Carboxamida/metabolismo , Animais , Austrália , Cromatografia Líquida , Cavalos , Humanos , Ribonucleosídeos/química , Ribonucleosídeos/metabolismo , Ribonucleotídeos/química , Ribonucleotídeos/metabolismo , Urinálise
11.
Environ Monit Assess ; 188(1): 64, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26718945

RESUMO

The aim of this study was to determine the behaviour of strobilurin and carbocyamides commonly used in chemical protection of lettuce depending on carefully selected effective microorganisms (EM) and yeast (Y). Additionally, the assessment of the chronic health risk during a 2-week experiment was performed. The statistical method for correlation of physico-chemical parameters and time of degradation for pesticides was applied. In this study, the concentration of azoxystrobin, boscalid, pyraclostrobin and iprodione using liquid chromatography-mass spectrometry (LC-MS/MS) in the matrix of lettuce plants was performed, and there was no case of concentration above maximum residues levels. Before harvest, four fungicides and their mixture with EM (1 % and 10 %) and/or yeast 5 % were applied. In our work, the mixtures of 1%EM + Y and 10%EM + Y both stimulated and inhibited the degradation of the tested active substances. Adding 10%EM to the test substances strongly inhibited the degradation of iprodione, and its concentration decreased by 30 %, and in the case of other test substances, the degradation was approximately 60 %. Moreover, the addition of yeast stimulated the distribution of pyraclostrobin and boscalid in lettuce leaves. The risk assessment for the pesticides ranged from 0.4 to 64.8 % on day 1, but after 14 days, it ranged from 0.0 to 20.9 % for children and adults, respectively. It indicated no risk of adverse effects following exposure to individual pesticides and their mixtures with EM and yeast.


Assuntos
Fungicidas Industriais/análise , Lactuca/química , Resíduos de Praguicidas/análise , Praguicidas/análise , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/química , Aminoimidazol Carboxamida/metabolismo , Aspergillus/metabolismo , Compostos de Bifenilo/análise , Compostos de Bifenilo/química , Compostos de Bifenilo/metabolismo , Carbamatos/análise , Carbamatos/química , Carbamatos/metabolismo , Cromatografia Líquida , Monitoramento Ambiental , Fungicidas Industriais/química , Fungicidas Industriais/metabolismo , Humanos , Hidantoínas/análise , Hidantoínas/química , Hidantoínas/metabolismo , Lactobacillales/metabolismo , Lactuca/microbiologia , Metacrilatos/análise , Metacrilatos/química , Metacrilatos/metabolismo , Mucor/metabolismo , Niacinamida/análogos & derivados , Niacinamida/análise , Niacinamida/química , Niacinamida/metabolismo , Penicillium/metabolismo , Resíduos de Praguicidas/química , Resíduos de Praguicidas/metabolismo , Praguicidas/química , Praguicidas/metabolismo , Pirazóis/análise , Pirazóis/química , Pirazóis/metabolismo , Pirimidinas/análise , Pirimidinas/química , Pirimidinas/metabolismo , Rhodobacteraceae/metabolismo , Medição de Risco , Saccharomyces cerevisiae/metabolismo , Streptomyces/metabolismo , Estrobilurinas , Espectrometria de Massas em Tandem/métodos
12.
J Magn Reson Imaging ; 37(4): 974-80, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23055421

RESUMO

Adenylosuccinate lyase (ADSL) deficiency is a rare inborn error of metabolism resulting in accumulation of metabolites including succinylaminoimidazole carboxamide riboside (SAICAr) and succinyladenosine (S-Ado) in the brain and other tissues. Patients with ADSL have progressive psychomotor retardation, neonatal seizures, global developmental delay, hypotonia, and autistic features, although variable clinical manifestations may make the initial diagnosis challenging. Two cases of the severe form of the disease are reported here: an 18-month-old boy with global developmental delay, intractable neonatal seizures, progressive cerebral atrophy, and marked hypomyelination, and a 3-month-old girl presenting with microcephaly, neonatal seizures, and marked psychomotor retardation. In both patients in vivo proton magnetic resonance spectroscopy (MRS) showed the presence of S-Ado signal at 8.3 ppm, consistent with a prior report. Interestingly, SAICAr signal was also detectable at 7.5 ppm in affected white matter, which has not been reported in vivo before. A novel splice-site mutation, c.IVS12 + 1/G > C, in the ADSL gene was identified in the second patient. Our findings confirm the utility of in vivo proton MRS in suggesting a specific diagnosis of ADSL deficiency, and also demonstrate an additional in vivo resonance (7.5 ppm) of SAICAr in the cases of severe disease.


Assuntos
Encéfalo/enzimologia , Deficiências do Desenvolvimento/diagnóstico , Aumento da Imagem/métodos , Interpretação de Imagem Assistida por Computador/métodos , Espectroscopia de Ressonância Magnética/métodos , Transtornos Psicomotores/diagnóstico , Erros Inatos do Metabolismo da Purina-Pirimidina/diagnóstico , Adenosina/análogos & derivados , Adenosina/análise , Adenilossuccinato Liase/deficiência , Adenilossuccinato Liase/genética , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Transtorno Autístico , Análise Mutacional de DNA , Deficiências do Desenvolvimento/enzimologia , Deficiências do Desenvolvimento/genética , Feminino , Humanos , Lactente , Masculino , Transtornos Psicomotores/enzimologia , Transtornos Psicomotores/genética , Erros Inatos do Metabolismo da Purina-Pirimidina/enzimologia , Erros Inatos do Metabolismo da Purina-Pirimidina/genética , Ribonucleosídeos/análise
13.
Bull Environ Contam Toxicol ; 89(4): 877-81, 2012 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-22893179

RESUMO

Field experiments were conducted in two different locations to determine the residue levels and dissipation rates of iprodione in tobacco leaves and soil. Iprodione 50% wettable powder formulation was sprayed once at 12.50 g/ha to study the dissipation behavior and three to four times at 8.33 g/ha (recommended dose) and 12.50 g/ha (1.5 times the recommended field dose) to determine the residue levels of iprodione in tobacco leaves and soil after repeated applications. Iprodione residues in both green tobacco leaves and soil dissipated to about 50% of the initial deposits after 7 days and then further dissipated to more than 90% after 35 days.The dissipation of iprodione followed first order kinetics and the calculated half-life values (T (1/2)) were 5.64-8.80 days in green tobacco leaves and 7.50-9.93 days in soil, respectively. Iprodione residue levels in flue-cured tobacco leaves 21 days after the third and fourth applications ranged from 7.61 to 40.98 mg/kg. Meanwhile, the residues detected in soil decreased to 0.010-0.117 mg/kg 21 days after the last treatment.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Fungicidas Industriais/análise , Hidantoínas/análise , Nicotiana/química , Resíduos de Praguicidas/análise , Solo/química , Aminoimidazol Carboxamida/análise , Meia-Vida , Folhas de Planta/química , Poluentes do Solo/análise
14.
Pest Manag Sci ; 68(4): 543-7, 2012 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-22102420

RESUMO

BACKGROUND: Greenhouse tomato production is intended exclusively for fresh consumption. Typical greenhouse conditions provide a conducive environment for the development of different fungi, principally late blight and grey mould, that can destroy plants and fruits. For this reason, different fungicides with different sites of action are used in integrated pest management strategies. Famoxadone, fenamidone, fenhexamid and iprodione (fig. 1) are fungicides of difference classes with different actions that could be used to control tomato pests. RESULTS: The QuEChERS method showed good recoveries, and the analytical method allowed good separation of the fungicides selected. Good results were obtained in terms of repeatability and intermediate precision, with a coefficient of variation of < 9.8%. The limits of determination and quantification of the method were far below the maximum residual levels (MRLs) set by the EU for these fungicides in tomatoes. The analysis of fungicide residues showed that cv. Shiren accounted for higher residue levels than cv. Caramba. The dissipation curves were similar in the two cultivars, indicating that the decrease in pesticides was not related to the tomato type. CONCLUSIONS: Care should be taken when using pesticides in greenhouse conditions, because degradation mainly affects fruit growth. The size of the tomato, in particular its surface/weight ratio, is very important for defining pesticide residues. All fungicides used showed residue levels below the MRLs at the preharvest interval.


Assuntos
Amidas/análise , Aminoimidazol Carboxamida/análogos & derivados , Fracionamento Químico/métodos , Cromatografia Gasosa/métodos , Fungicidas Industriais/análise , Hidantoínas/análise , Oxazóis/análise , Resíduos de Praguicidas/análise , Solanum lycopersicum/química , Amidas/isolamento & purificação , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/isolamento & purificação , Fungicidas Industriais/isolamento & purificação , Hidantoínas/isolamento & purificação , Solanum lycopersicum/crescimento & desenvolvimento , Metacrilatos/análise , Metacrilatos/isolamento & purificação , Oxazóis/isolamento & purificação , Resíduos de Praguicidas/isolamento & purificação , Estrobilurinas
15.
J Chromatogr A ; 1218(52): 9375-83, 2011 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-22119674

RESUMO

A new type of low thermal mass (LTM) fast gas chromatograph (GC) was designed and operated in combination with gas chromatography mass spectrometry (GC-MS) with supersonic molecular beams (SMB), including GC-MS-MS with SMB, thereby providing a novel combination with unique capabilities. The LTM fast GC is based on a short capillary column inserted inside a stainless steel tube that is resistively heated. It is located and mounted outside the standard GC oven on its available top detector port, while the capillary column is connected as usual to the standard GC injector and supersonic molecular beam interface transfer line. This new type of fast GC-MS with SMB enables less than 1 min full range temperature programming and cooling down analysis cycle time. The operation of the fast GC-MS with SMB was explored and 1 min full analysis cycle time of a mixture of 16 hydrocarbons in the C(10)H(22) up to C(44)H(90) range was achieved. The use of 35 mL/min high column flow rate enabled the elution of C(44)H(90) in less than 45 s while the SMB interface enabled splitless acceptance of this high flow rate and the provision of dominant molecular ions. A novel compound 9-benzylazidanthracene was analyzed for its purity and a synthetic chemistry process was monitored for the optimization of the chemical reaction yield. Biodiesel was analyzed in jet fuel (by both GC-MS and GC-MS-MS) in under 1 min as 5 ppm fatty acid methyl esters. Authentic iprodion and cypermethrin pesticides were analyzed in grapes extract in both full scan mode and fast GC-MS-MS mode in under 1 min cycle time and explosive mixture including TATP, TNT and RDX was analyzed in under 1 min combined with exhibiting dominant molecular ion for TATP. Fast GC-MS with SMB is based on trading GC separation for speed of analysis while enhancing the separation power of the MS via the enhancement of the molecular ion in the electron ionization of cold molecules in the SMB. This paper further discusses several features of fast GC and fast GC-MS and the various trade-offs involved in having powerful and practical fast GC-MS.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas/instrumentação , Cromatografia Gasosa-Espectrometria de Massas/métodos , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Antracenos/análise , Substâncias Explosivas/análise , Fungicidas Industriais/análise , Temperatura Alta , Hidantoínas/análise , Hidrocarbonetos/análise , Inseticidas/análise , Piretrinas/análise , Fatores de Tempo , Vitis/química
16.
Talanta ; 85(3): 1500-7, 2011 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-21807215

RESUMO

Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L(-1) for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g(-1) and 57.7 ng g(-1) for sediments and regarding fish, were below 1 ng g(-1) for 8 molecules and were determined between 5 and 49 ng g(-1) for the 5 other compounds. This method was finally used as a new routine practice for environmental research.


Assuntos
Sedimentos Geológicos/química , Músculos/química , Resíduos de Praguicidas/análise , Praguicidas/análise , Poluentes Químicos da Água/análise , Acetamidas/análise , Acetamidas/isolamento & purificação , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/isolamento & purificação , Animais , Benzimidazóis/análise , Benzimidazóis/isolamento & purificação , Carbamatos/análise , Carbamatos/isolamento & purificação , Fracionamento Químico/métodos , Cromatografia Líquida/métodos , Monitoramento Ambiental/métodos , Peixes , Hidantoínas/análise , Hidantoínas/isolamento & purificação , Isoxazóis/análise , Isoxazóis/isolamento & purificação , Metacrilatos/análise , Metacrilatos/isolamento & purificação , Naftalenos/análise , Naftalenos/isolamento & purificação , Niacinamida/análogos & derivados , Niacinamida/análise , Niacinamida/isolamento & purificação , Oxazolidinonas/análise , Oxazolidinonas/isolamento & purificação , Resíduos de Praguicidas/isolamento & purificação , Praguicidas/isolamento & purificação , Compostos de Fenilureia/análise , Compostos de Fenilureia/isolamento & purificação , Propionatos , Pirimidinas/análise , Pirimidinas/isolamento & purificação , Quinoxalinas , Reprodutibilidade dos Testes , Extração em Fase Sólida/métodos , Estrobilurinas , Compostos de Sulfonilureia/análise , Compostos de Sulfonilureia/isolamento & purificação , Espectrometria de Massas em Tandem/métodos , Tiofenos , Poluentes Químicos da Água/isolamento & purificação
17.
Drug Test Anal ; 3(5): 331-6, 2011 May.
Artigo em Inglês | MEDLINE | ID: mdl-21538997

RESUMO

Identifying the use of non-approved drugs by cheating athletes has been a great challenge for doping control laboratories. This is due to the additional complexities associated with identifying relatively unknown and uncharacterized compounds and their metabolites as opposed to known and well-studied therapeutics. In 2010, the prohibited drug candidates and gene doping substances AICAR and GW1516, together with the selective androgen receptor modulator (SARM) MK-2866 were obtained by the Cologne Doping Control Laboratory from Internet suppliers and their structure, quantity, and formulation elucidated. All three compounds proved authentic as determined by liquid chromatography-high resolution/high accuracy (tandem) mass spectrometry and comparison to reference material. While AICAR was provided as a colourless powder in 100 mg aliquots, GW1516 was obtained as an orange/yellow suspension in water/glycerol (150 mg/ml), and MK-2866 (25 mg/ml) was shipped dissolved in polyethylene glycol (PEG) 300. In all cases, the quantified amounts were considerably lower than indicated on the label. The substances were delivered via courier, with packaging identifying them as containing 'amino acids' and 'green tea extract', arguably to circumvent customs control. Although all of the substances were declared 'for research only', their potential misuse in illicit performance-enhancement cannot be excluded; moreover sports drug testing authorities should be aware of the facile availability of black market copies of these drug candidates.


Assuntos
Anabolizantes/análise , Dopagem Esportivo/prevenção & controle , Detecção do Abuso de Substâncias/métodos , Amidas/análise , Amidas/química , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/química , Anabolizantes/química , Anilidas , Cromatografia Líquida , Humanos , Drogas Ilícitas/análise , Internet , Espectrometria de Massas , Polietilenoglicóis/química , Ribonucleotídeos/análise , Ribonucleotídeos/química , Solventes/química , Tiazóis/análise , Tiazóis/química
18.
J Chromatogr B Analyt Technol Biomed Life Sci ; 878(21): 1801-8, 2010 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-20627825

RESUMO

The applicability of micellar electrokinetic capillary chromatography (MEKC) for the analysis of temozolomide (TMZ) and its degradants, 3-methyl-(triazen-1-yl)imidazole-4-carboxamide (MTIC) and 5-amino-imidazole-4-carboxamide (AIC) has been studied. Using short-end injection, the analysis of TMZ and its degradants could be performed within 1.2 min. The obtained precision of migration times was better than 1.6 RSD%, and the limit of quantitation (LOQ) was 0.31-0.93 microg/mL. The therapeutic concentration of TMZ in blood samples can be determined after direct sample injection and conventional on-capillary UV detection. The proposed MEKC method was applied to study the stability of TMZ in water and serum at different pH values. It was established that the half-life of the TMZ in vitro serum at room temperature was 33 min, close to the half-life (28 min) obtained in water at pH 7.9.


Assuntos
Cromatografia Capilar Eletrocinética Micelar/métodos , Dacarbazina/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/sangue , Aminoimidazol Carboxamida/química , Antineoplásicos Alquilantes/análise , Antineoplásicos Alquilantes/sangue , Antineoplásicos Alquilantes/química , Dacarbazina/análise , Dacarbazina/sangue , Dacarbazina/química , Estabilidade de Medicamentos , Meia-Vida , Humanos , Concentração de Íons de Hidrogênio , Modelos Lineares , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Temozolomida , Temperatura , Água
19.
J Agric Food Chem ; 58(3): 1416-9, 2010 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-20000573

RESUMO

Iprodione is an agricultural fungicide that is difficult to detect in foods by HPLC because it coelutes with natural compounds in the food. We previously showed that food matrix could be degraded with titanium dioxide powder (TP). Here we describe an improved method for detection of iprodione using silica gel supported titanium dioxide (SGT). To synthesize SGT, titania-sol was mixed with diethanolamine, 2-propanol, and titanium tetraisopropoxide. After titania-sol was infiltrated into the silica gel (particle diameter 4 mm), the mixture was dried and then heated. Crude basil extract containing iprodione was mixed with SGT in a quartz vial, and the vial was irradiated with a UV light to selectively decompose the matrix interfering with the iprodione determination. In HPLC chromatograms of the treated solution, the interference peak decreased 35 times faster with SGT than with TP. When SGT (11 g) was added to the extract (20 mL) of dry basil (2 g), black light irradiation for 30 min was enough to quantify iprodione. The recovery rate of iprodione was 99.1%. Thus, the photocatalytic cleanup method using SGT is effective for analyzing residual iprodione in dry basil.


Assuntos
Aminoimidazol Carboxamida/análogos & derivados , Cromatografia Líquida de Alta Pressão/métodos , Fungicidas Industriais/análise , Hidantoínas/análise , Ocimum basilicum/química , Titânio/química , Aminoimidazol Carboxamida/análise , Cromatografia Líquida de Alta Pressão/instrumentação
20.
J Chromatogr A ; 1216(35): 6326-34, 2009 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-19643423

RESUMO

A combination of fast GC with narrow-bore column and bench top quadrupole mass spectrometer (MS) detector in negative chemical ionization (NCI) mode (with methane as reagent gas) is set up and utilized for the ultratrace analysis of 25 selected pesticides. The observed pesticides, belonging to the endocrine disrupting chemicals (EDCs), were from different chemical classes. A comparative study with electron impact (EI) ionization was also carried out (both techniques in selected ion monitoring (SIM) mode). The programmed temperature vaporizer (PTV) injector in solvent vent mode and narrow-bore column (15mx0.15mm I.D.x0.15microm film of 5% diphenyl 95% dimethylsiloxane stationary phase) were used for effective and fast separation. Heptachlor (HPT) as internal standard (I.S.) was applied for the comparison of results obtained from absolute and normalized peak areas. Non-fatty food matrices were investigated. Fruit (apple - matrix-matched standards; orange, strawberry, plum - real samples) and vegetable (lettuce - real sample) extracts were prepared by a quick and effective QuEChERS sample preparation technique. Very good results were obtained for the characterization of fast GC-NCI-MS method analysing EDCs pesticides. Analyte response was linear from 0.01 to 150microgkg(-1) with the R(2) values in the range from 0.9936 to 1.0000 (calculated from absolute peak areas) and from 0.9956 to 1.0000 (calculated from peak areas normalized to HPT). Instrument limits of detection (LODs) and quantification (LOQs) were found at pgmL(-1) level and for the majority of analytes were up to three orders of magnitude lower for NCI compared to EI mode. In both ionization modes, repeatability of measurements expressed as relative standard deviation (RSDs) was less than 10% which is in very good agreement with the criterion of European Union.


Assuntos
Análise de Alimentos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Resíduos de Praguicidas/análise , Praguicidas/análise , Aminoimidazol Carboxamida/análogos & derivados , Aminoimidazol Carboxamida/análise , Aminoimidazol Carboxamida/isolamento & purificação , Disruptores Endócrinos/análise , Disruptores Endócrinos/isolamento & purificação , União Europeia , Análise de Alimentos/normas , Frutas/química , Hidantoínas/análise , Hidantoínas/isolamento & purificação , Malation/análise , Malation/isolamento & purificação , Resíduos de Praguicidas/isolamento & purificação , Praguicidas/isolamento & purificação , Verduras/química
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