Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi
Autor(a) principal: | |
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Data de Publicação: | 2014 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/21635 |
Resumo: | In this study, a method for determination of diquat and paraquat in Cowpea was optimized and validated. In order to obtain a good homogeneous sample, the Cowpea were milled and then prepared a slurry of matrix and water (ratio 1:1.5; m/m). The extraction procedure was based on the QuPPe-Method and modifications of the method were developed. As extraction solution, it was used methanol containing hydrochloric acid 5 mol L-1 (6:4 v/v) plus isotopically labeled (IL) analogues of the targets analytes, which were used as internal standards (ISTDs). In order to promote a better extraction, the mixture between slurry plus extraction solvent was manually shaked for 2 min, vigorously, and then taken to a water bath, at 80°C, for 15 min. After, the mixture was cooled down to room temperature and then centrifuged for 4 min at 4000 rpm. The supernatant was used for the analysis. All analytical solutions of diquat and paraquat have been prepared and stored in polypropylene vessels. The determination of diquat and paraquat was done into a liquid chromatographic system coupled to a tandem mass spectrometer (UPLC-MS/MS). The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with seven replicates (n = 7) for each concentration. Assessed, both as to diquat and paraquat, was determined the linearity (r) of analytical curves, accuracy (as recovery %), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD %) and matrix effects (%). In the recovery study of Diquat, the average recovery obtained was between 77 and 85% with RSD% values ≤ 20%, for all 3 spike concentrations. On the other hand, paraquat presented averages between 68-103% and averages of RSD between 14.4-25.4 %. The LOQ of the method was 10 and 20 μg kg-1 for diquat and paraquat, respectively. The matrix effect was present for both pesticides even using isotopically labeled (IL) analogues of the target analytes, which were used as internal standard (ISTD), therefore requiring matrix-matched calibration standards for application in routine analysis. This study was applied for samples from EMBRAPA study. |
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Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupiOptimization and validation of single residue method for determination of diquat and paraquat for UPLC-MS/MS in cowpeaFeijão-caupiHerbicidasUPLC-MS/MSMétodo individualDiquateParaquateCowpeaHerbicidesSingle residue methodDiquatParaquatCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAIn this study, a method for determination of diquat and paraquat in Cowpea was optimized and validated. In order to obtain a good homogeneous sample, the Cowpea were milled and then prepared a slurry of matrix and water (ratio 1:1.5; m/m). The extraction procedure was based on the QuPPe-Method and modifications of the method were developed. As extraction solution, it was used methanol containing hydrochloric acid 5 mol L-1 (6:4 v/v) plus isotopically labeled (IL) analogues of the targets analytes, which were used as internal standards (ISTDs). In order to promote a better extraction, the mixture between slurry plus extraction solvent was manually shaked for 2 min, vigorously, and then taken to a water bath, at 80°C, for 15 min. After, the mixture was cooled down to room temperature and then centrifuged for 4 min at 4000 rpm. The supernatant was used for the analysis. All analytical solutions of diquat and paraquat have been prepared and stored in polypropylene vessels. The determination of diquat and paraquat was done into a liquid chromatographic system coupled to a tandem mass spectrometer (UPLC-MS/MS). The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with seven replicates (n = 7) for each concentration. Assessed, both as to diquat and paraquat, was determined the linearity (r) of analytical curves, accuracy (as recovery %), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD %) and matrix effects (%). In the recovery study of Diquat, the average recovery obtained was between 77 and 85% with RSD% values ≤ 20%, for all 3 spike concentrations. On the other hand, paraquat presented averages between 68-103% and averages of RSD between 14.4-25.4 %. The LOQ of the method was 10 and 20 μg kg-1 for diquat and paraquat, respectively. The matrix effect was present for both pesticides even using isotopically labeled (IL) analogues of the target analytes, which were used as internal standard (ISTD), therefore requiring matrix-matched calibration standards for application in routine analysis. This study was applied for samples from EMBRAPA study.Organização dos Estados Americanos - OEAGrupo Coimbra de Universidades Brasileiras - GCUBNeste estudo, foi otimizado e validado um método para determinação de diquate e paraquate em feijão-caupi. Para se obter uma amostra bem homogênea, o feijão-caupi foi moído e em seguida preparou-se um slurry de matriz e água (razão 1:1,5; m/m). O procedimento de extração baseou-se no método QuPPe, no qual foram feitas modificações. Como solvente extrator, utilizaram-se metanol contendo ácido clorídrico 5 mol L-1 (6:4 v/v) e utilizou-se padrões internos deuterados de diquate e paraquate. Após a adição do solvente extrator, para promover uma melhor extração, agitou-se vigorosamente de maneira manual por 2 minutos e logo levou-se por 15 minutos para banho de água à 80 °C. Deixou-se resfriar à temperatura ambiente e centrifugou-se por 5 minutos a 4000 rpm. O sobrenadante foi utilizado para as análises. Todas as soluções analíticas de diquate e paraquate foram preparadas e armazenadas em frascos de polipropileno. A determinação de diquate e paraquate foi feita em um sistema de cromatografia líquida acoplado a um espectrômetro de massas tandem (UPLC-MS/MS). A validação foi realizada pela análise de amostras de feijão-caupi fortificado em três concentrações (10, 20 e 50 μg kg-1), com 7 replicatas (n=7) para cada concentração. Avaliou-se, para ambos herbicidas, a linearidade da curva analítica (r), exatidão (recuperação%), limite de detecção e de quantificação (LOD e LOQ) do instrumento e do método, precisão (RSD%) e efeito matriz (%). No estudo de recuperação o diquate obteve médias entre 77-85% e apresentou RSD ≤ 20% para as amostras fortificadas, nas três concentrações de estudo. Por outro lado, paraquate apresentou médias entre 68-103% na recuperação e médias de RSD entre 14,4-25,4%. O LOQ do método foi 10 e 20 μg kg-1 para diquate e paraquate, respetivamente. Mesmo após a adição de padrões deuterados antes da etapa de fortificação o efeito matriz manteve-se presente tanto para diquate como para o paraquate. Dessa forma, para que o método possa ser implantado em análises de rotina, a confecção das curvas analíticas deve ser realizada a partir de soluções em extrato de matriz (matrix-matched calibration). Este método foi aplicado para amostras provenientes de um estudo da EMBRAPA.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasPizzutti, Ionara Reginahttp://lattes.cnpq.br/3883506164936996Carvalho, Leandro Machado deCorbellini, Valeriano AntonioVela, Giovana Milagros Espinoza2021-07-29T13:55:37Z2021-07-29T13:55:37Z2014-02-03info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/21635porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2021-08-05T17:07:51Zoai:repositorio.ufsm.br:1/21635Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2021-08-05T17:07:51Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi Optimization and validation of single residue method for determination of diquat and paraquat for UPLC-MS/MS in cowpea |
title |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
spellingShingle |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi Vela, Giovana Milagros Espinoza Feijão-caupi Herbicidas UPLC-MS/MS Método individual Diquate Paraquate Cowpea Herbicides Single residue method Diquat Paraquat CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
title_full |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
title_fullStr |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
title_full_unstemmed |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
title_sort |
Otimização e validação de método individual para determinação de diquate e paraquate por UPLC-MS/MS em feijão-caupi |
author |
Vela, Giovana Milagros Espinoza |
author_facet |
Vela, Giovana Milagros Espinoza |
author_role |
author |
dc.contributor.none.fl_str_mv |
Pizzutti, Ionara Regina http://lattes.cnpq.br/3883506164936996 Carvalho, Leandro Machado de Corbellini, Valeriano Antonio |
dc.contributor.author.fl_str_mv |
Vela, Giovana Milagros Espinoza |
dc.subject.por.fl_str_mv |
Feijão-caupi Herbicidas UPLC-MS/MS Método individual Diquate Paraquate Cowpea Herbicides Single residue method Diquat Paraquat CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Feijão-caupi Herbicidas UPLC-MS/MS Método individual Diquate Paraquate Cowpea Herbicides Single residue method Diquat Paraquat CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
In this study, a method for determination of diquat and paraquat in Cowpea was optimized and validated. In order to obtain a good homogeneous sample, the Cowpea were milled and then prepared a slurry of matrix and water (ratio 1:1.5; m/m). The extraction procedure was based on the QuPPe-Method and modifications of the method were developed. As extraction solution, it was used methanol containing hydrochloric acid 5 mol L-1 (6:4 v/v) plus isotopically labeled (IL) analogues of the targets analytes, which were used as internal standards (ISTDs). In order to promote a better extraction, the mixture between slurry plus extraction solvent was manually shaked for 2 min, vigorously, and then taken to a water bath, at 80°C, for 15 min. After, the mixture was cooled down to room temperature and then centrifuged for 4 min at 4000 rpm. The supernatant was used for the analysis. All analytical solutions of diquat and paraquat have been prepared and stored in polypropylene vessels. The determination of diquat and paraquat was done into a liquid chromatographic system coupled to a tandem mass spectrometer (UPLC-MS/MS). The validation was performed by analyzing spiked samples at three different concentrations (10, 20 and 50 μg kg-1), with seven replicates (n = 7) for each concentration. Assessed, both as to diquat and paraquat, was determined the linearity (r) of analytical curves, accuracy (as recovery %), instrument and method limits of detection and quantification (LOD and LOQ), precision (as RSD %) and matrix effects (%). In the recovery study of Diquat, the average recovery obtained was between 77 and 85% with RSD% values ≤ 20%, for all 3 spike concentrations. On the other hand, paraquat presented averages between 68-103% and averages of RSD between 14.4-25.4 %. The LOQ of the method was 10 and 20 μg kg-1 for diquat and paraquat, respectively. The matrix effect was present for both pesticides even using isotopically labeled (IL) analogues of the target analytes, which were used as internal standard (ISTD), therefore requiring matrix-matched calibration standards for application in routine analysis. This study was applied for samples from EMBRAPA study. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-02-03 2021-07-29T13:55:37Z 2021-07-29T13:55:37Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/21635 |
url |
http://repositorio.ufsm.br/handle/1/21635 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1805922073158090752 |