Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis)
Ano de defesa: | 2022 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/24647 |
Resumo: | Dithiocarbamates (DTC) are one of the main classes of fungicides applied to the control of fungal diseases on a large variety of crops. In this work, a fast and cheap sample preparation procedure for DTC analysis in yerba mate using gas chromatography-mass spectrometry (GC-MS) was developed. A multivariate approach by Placket-Burmann Design (PBD) was carried out for screening of DTC extraction variables (concentration and volume of hydrolysis acid solution, isooctane volume, and water bath shaking time and temperature). The significant variables were studied by a Central Composite Rotational Design (CCRD) to optimize the DTC recovery. A complete validation study was performed according to the European Union guideline -SANTE document. The screening experiment obtained by PBD indicates that three experimental parameters were significant: concentration and volume of hydrolysis solution, and time of hydrolysis. The final optimized and validated method proved to be reproducible and robust in routine analysis. For recovery studies, blank yerba mate samples were spiked with a thiram solution at the 3 spike concentrations of 0.1; 0.5 and 2.0 mg kg-¹, as CS2, and analyzed by 3 analysts (n = 7, per analyst). Excellent recoveries, in the range of 81.4 to 116.2%, with good precision (all RSDs ≤ 16.1%), were obtained. The intermediate precision (RSDR) was evaluated by different analysts (1 and 2) and a RSDR≤ 8.2% was obtained, indicating the very good repeatability of the method. The interlaboratory reproducibility also showed recovery and precision values within the acceptable limits (70-120%, and <20%, respectively). The robustness of the method was proven to be good, based on the acceptable deviations with changes of most conditions of the critical parameters. The analytical curves were linear in the concentration range of 0.05-10 mg L-¹ CS2, r²> 0.999, and the matrix effect was not significant (-14.9%). The LOD and LOQ were 0.05 and 0.1 mg kg-¹ CS2, respectively. The method presented important advantages: a five-fold reduction of the isooctane extraction volume; an increase of sample throughput from 1 to 30 sample extractions, due to sample mass reduction without HCl addition; a two-fold reduction of extraction time; a smaller sample amount to process, and less waste volume aiming at green chemistry principles. The application of the multivariate approach proved to be of influence in improving the extraction efficiency. |
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2022-06-07T17:05:00Z2022-06-07T17:05:00Z2022-03-30http://repositorio.ufsm.br/handle/1/24647Dithiocarbamates (DTC) are one of the main classes of fungicides applied to the control of fungal diseases on a large variety of crops. In this work, a fast and cheap sample preparation procedure for DTC analysis in yerba mate using gas chromatography-mass spectrometry (GC-MS) was developed. A multivariate approach by Placket-Burmann Design (PBD) was carried out for screening of DTC extraction variables (concentration and volume of hydrolysis acid solution, isooctane volume, and water bath shaking time and temperature). The significant variables were studied by a Central Composite Rotational Design (CCRD) to optimize the DTC recovery. A complete validation study was performed according to the European Union guideline -SANTE document. The screening experiment obtained by PBD indicates that three experimental parameters were significant: concentration and volume of hydrolysis solution, and time of hydrolysis. The final optimized and validated method proved to be reproducible and robust in routine analysis. For recovery studies, blank yerba mate samples were spiked with a thiram solution at the 3 spike concentrations of 0.1; 0.5 and 2.0 mg kg-¹, as CS2, and analyzed by 3 analysts (n = 7, per analyst). Excellent recoveries, in the range of 81.4 to 116.2%, with good precision (all RSDs ≤ 16.1%), were obtained. The intermediate precision (RSDR) was evaluated by different analysts (1 and 2) and a RSDR≤ 8.2% was obtained, indicating the very good repeatability of the method. The interlaboratory reproducibility also showed recovery and precision values within the acceptable limits (70-120%, and <20%, respectively). The robustness of the method was proven to be good, based on the acceptable deviations with changes of most conditions of the critical parameters. The analytical curves were linear in the concentration range of 0.05-10 mg L-¹ CS2, r²> 0.999, and the matrix effect was not significant (-14.9%). The LOD and LOQ were 0.05 and 0.1 mg kg-¹ CS2, respectively. The method presented important advantages: a five-fold reduction of the isooctane extraction volume; an increase of sample throughput from 1 to 30 sample extractions, due to sample mass reduction without HCl addition; a two-fold reduction of extraction time; a smaller sample amount to process, and less waste volume aiming at green chemistry principles. The application of the multivariate approach proved to be of influence in improving the extraction efficiency.A erva mate, originária da América Latina, vem sendo consumida de diversas formas, devido aos seus efeitos benéficos para a saúde humana. Ao longo dos anos os fungicidas ditiocarbamatos (DTC) tem sido utilizado no controle de doenças fúngicas em uma grande variedade de culturas. Atualmente não existe na legislação brasileira recomendações fitossanitárias nem Limite Máximo de Resíduos (LMR) para a erva mate, por isso a necessidade de desenvolver e otimizar um método confiável para a identificação e quantificação de resíduos de DTC. Neste trabalho, foi realizado um delineamento experimental por Placket-Burmam (PB), para determinar as variáveis experimentais independentes. Em seguida, foi utilizado o Delineamento Composto Central Rotacional (DCCR) para obter os melhores resultados para a otimização do método. Após os resultados obtidos, foi realizado um estudo univariado bem como a miniaturização do método. Por último o estudo da validação do método foi realizado, sendo avaliados os seguintes parâmetros: linearidade, limite de detecção (LOD), limite de quantificação (LOQ), seletividade precisão e exatidão. As curvas analíticas foram lineares na faixa de 0,05 a 10 mg L-¹ de CS2, com um coeficiente de determinação (r²) maior que 0,99, o LOD do método foi de 0,05 mg kg-¹ de CS2. Já o LOQ do método foi de 0,1 mg Kg-¹. A precisão mostrou-se adequada, com valores de RSD médios entre 8,2 e 16,1% e recuperações médias de 81,4 e 116,2%. O efeito matriz (-14,9) não foi significativo. Assim os resultados obtidos pela otimização e validação do método foram satisfatórios e apresentam um grande avanço no método analítico para a determinação de DTC em erva mate, por se ter um procedimento de rápido e barato de preparação de amostras para análise de (DTC) em erva-mate, usando Cromatografia gasosa acoplado a Espectrometria de Massas (GC-MS), além de ser um método amigável com o meio ambiente, pois gera menos resíduos químicos. Amostras de erva mate de diferentes supermercados de Santa Maria/ RS foram analisadas e em nenhuma delas detectada a presença de DTC.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessPlacket-BurmamDCCRDTCCS2Erva mateCCRDDithiocarbamateYerba mateCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis)Anwendung eines statistischen experimentellen designs zur optimierung eines verfahrens zur bestimmung von dithiocarbamat in yerva mate (Ilex paraguariensis)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisPizzutti, Ionara Reginahttp://lattes.cnpq.br/3883506164936996Cardoso, Carmem DickowSilva, Rosselei Caiél daRossi, Rochele Cassantahttp://lattes.cnpq.br/9895482437517604Neu, Júlia Paula100600000000600600600600600600961b4a4a-1465-4d87-b4e8-6428b5a3ad385ba97bb3-daa8-4711-91a3-e9264551af691e9fefd8-5900-456e-8798-d27c3ab238e5a44174cb-8124-43d7-858f-82a87996217329544f6f-d71e-4a71-8806-4f825073950freponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUÍMICA_2022_NEU_JULIA.pdfDIS_PPGQUÍMICA_2022_NEU_JULIA.pdfDissertação de Mestradoapplication/pdf1047878http://repositorio.ufsm.br/bitstream/1/24647/1/DIS_PPGQU%c3%8dMICA_2022_NEU_JULIA.pdf10c3ee341e7d26eca96a086172a496d9MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/24647/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD53CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/24647/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD521/246472022-06-07 14:05:00.469oai:repositorio.ufsm.br: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 Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-06-07T17:05Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
dc.title.alternative.eng.fl_str_mv |
Anwendung eines statistischen experimentellen designs zur optimierung eines verfahrens zur bestimmung von dithiocarbamat in yerva mate (Ilex paraguariensis) |
title |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
spellingShingle |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) Neu, Júlia Paula Placket-Burmam DCCR DTC CS2 Erva mate CCRD Dithiocarbamate Yerba mate CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
title_full |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
title_fullStr |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
title_full_unstemmed |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
title_sort |
Aplicação de desenho experimental estatístico para otimização de método para determinação de ditiocarbamato em erva-mate (Ilex paraguariensis) |
author |
Neu, Júlia Paula |
author_facet |
Neu, Júlia Paula |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Pizzutti, Ionara Regina |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3883506164936996 |
dc.contributor.advisor-co1.fl_str_mv |
Cardoso, Carmem Dickow |
dc.contributor.referee1.fl_str_mv |
Silva, Rosselei Caiél da |
dc.contributor.referee2.fl_str_mv |
Rossi, Rochele Cassanta |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/9895482437517604 |
dc.contributor.author.fl_str_mv |
Neu, Júlia Paula |
contributor_str_mv |
Pizzutti, Ionara Regina Cardoso, Carmem Dickow Silva, Rosselei Caiél da Rossi, Rochele Cassanta |
dc.subject.por.fl_str_mv |
Placket-Burmam DCCR DTC CS2 Erva mate |
topic |
Placket-Burmam DCCR DTC CS2 Erva mate CCRD Dithiocarbamate Yerba mate CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
CCRD Dithiocarbamate Yerba mate |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Dithiocarbamates (DTC) are one of the main classes of fungicides applied to the control of fungal diseases on a large variety of crops. In this work, a fast and cheap sample preparation procedure for DTC analysis in yerba mate using gas chromatography-mass spectrometry (GC-MS) was developed. A multivariate approach by Placket-Burmann Design (PBD) was carried out for screening of DTC extraction variables (concentration and volume of hydrolysis acid solution, isooctane volume, and water bath shaking time and temperature). The significant variables were studied by a Central Composite Rotational Design (CCRD) to optimize the DTC recovery. A complete validation study was performed according to the European Union guideline -SANTE document. The screening experiment obtained by PBD indicates that three experimental parameters were significant: concentration and volume of hydrolysis solution, and time of hydrolysis. The final optimized and validated method proved to be reproducible and robust in routine analysis. For recovery studies, blank yerba mate samples were spiked with a thiram solution at the 3 spike concentrations of 0.1; 0.5 and 2.0 mg kg-¹, as CS2, and analyzed by 3 analysts (n = 7, per analyst). Excellent recoveries, in the range of 81.4 to 116.2%, with good precision (all RSDs ≤ 16.1%), were obtained. The intermediate precision (RSDR) was evaluated by different analysts (1 and 2) and a RSDR≤ 8.2% was obtained, indicating the very good repeatability of the method. The interlaboratory reproducibility also showed recovery and precision values within the acceptable limits (70-120%, and <20%, respectively). The robustness of the method was proven to be good, based on the acceptable deviations with changes of most conditions of the critical parameters. The analytical curves were linear in the concentration range of 0.05-10 mg L-¹ CS2, r²> 0.999, and the matrix effect was not significant (-14.9%). The LOD and LOQ were 0.05 and 0.1 mg kg-¹ CS2, respectively. The method presented important advantages: a five-fold reduction of the isooctane extraction volume; an increase of sample throughput from 1 to 30 sample extractions, due to sample mass reduction without HCl addition; a two-fold reduction of extraction time; a smaller sample amount to process, and less waste volume aiming at green chemistry principles. The application of the multivariate approach proved to be of influence in improving the extraction efficiency. |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-06-07T17:05:00Z |
dc.date.available.fl_str_mv |
2022-06-07T17:05:00Z |
dc.date.issued.fl_str_mv |
2022-03-30 |
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/1/24647 |
url |
http://repositorio.ufsm.br/handle/1/24647 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 600 |
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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.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações do UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
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