Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS

Bibliographic Details
Main Author: Crisóstomo, Sabrina Gabriceli
Publication Date: 2023
Format: Master thesis
Language: por
Source: Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
Download full: http://repositorio.ufes.br/handle/10/12694
Summary: With the increase in agricultural activities, vegetables are increasingly subject to exposure to pesticides, such as insecticides and fungicides. Excessive use of these products during cultivation is an aggravating factor, causing harmful effects on health. In order to control the use involved in these materials and ensure food safety, the scientific community has carried out research and developed methods capable of elucidating the composition and distribution of these agents in vegetable samples. Conventional techniques, such as gas chromatography and liquid chromatography, have traditionally been used in studies in these segments. However, recent studies point to the great potential of using mass spectrometry techniques with laser desorption ionization (LDI-MS) and matrix-assisted laser desorption/ionization (MALDI-MS) sources for the analysis of plant tissues. In the latest studies published by the regulatory body in Brazil, the National Health Surveillance Agency (ANVISA), the involved use of pesticides in food was presented due to the high rate of Identificação of these substances, often above the established limit. Kale, a very common vegetable in the Brazilian population's diet, stood out in this survey, due to the unsatisfactory results related to the use of pesticides. In this sense, the present work developed a method for monitoring pesticides presented in cabbage leaves by direct analysis, using the LDI and MALDI techniques. To develop the method, the ten most detected pesticides in the last ANVISA survey for cabbage crops were monitored, namely: Carbendazine, Cyromazine, Chlorpyrifos, Clothianidin, Deltamethrin, Imidacloriprid, Lambda-Cialothrin, Methomyl, Tebuconazole Trifloxystrobin. The MALDI-MS source was optimized by varying the type of matrix (2,5-dihydroxybenzoic acid, (DHB), α-cyano-4-hydroxycinnamic acid (CHCA) and 2-mercaptobenzothiazole (MBT)), its concentration (from 0.025 at 1.00 mg mL-1) and application method, mixture or sandwich. The results suggest a better ionization efficiency of the MALDI(+)MS technique, when the DHB matrix is used in low concentrations, that is, 0.050 mg mL-1 , and when applied in the form of a mixture, making it possible to detect seven pesticides out of the ten trained with ICTs, in most cases, higher than 106 . This performance was demonstrated to be superior to the LDI(±)MS technique.
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spelling Estudo químico de agrotóxicos em tecido vegetal por MALDI-MSMALDI MSLDICouveAgrotóxicoANVISAQuímicaWith the increase in agricultural activities, vegetables are increasingly subject to exposure to pesticides, such as insecticides and fungicides. Excessive use of these products during cultivation is an aggravating factor, causing harmful effects on health. In order to control the use involved in these materials and ensure food safety, the scientific community has carried out research and developed methods capable of elucidating the composition and distribution of these agents in vegetable samples. Conventional techniques, such as gas chromatography and liquid chromatography, have traditionally been used in studies in these segments. However, recent studies point to the great potential of using mass spectrometry techniques with laser desorption ionization (LDI-MS) and matrix-assisted laser desorption/ionization (MALDI-MS) sources for the analysis of plant tissues. In the latest studies published by the regulatory body in Brazil, the National Health Surveillance Agency (ANVISA), the involved use of pesticides in food was presented due to the high rate of Identificação of these substances, often above the established limit. Kale, a very common vegetable in the Brazilian population's diet, stood out in this survey, due to the unsatisfactory results related to the use of pesticides. In this sense, the present work developed a method for monitoring pesticides presented in cabbage leaves by direct analysis, using the LDI and MALDI techniques. To develop the method, the ten most detected pesticides in the last ANVISA survey for cabbage crops were monitored, namely: Carbendazine, Cyromazine, Chlorpyrifos, Clothianidin, Deltamethrin, Imidacloriprid, Lambda-Cialothrin, Methomyl, Tebuconazole Trifloxystrobin. The MALDI-MS source was optimized by varying the type of matrix (2,5-dihydroxybenzoic acid, (DHB), α-cyano-4-hydroxycinnamic acid (CHCA) and 2-mercaptobenzothiazole (MBT)), its concentration (from 0.025 at 1.00 mg mL-1) and application method, mixture or sandwich. The results suggest a better ionization efficiency of the MALDI(+)MS technique, when the DHB matrix is used in low concentrations, that is, 0.050 mg mL-1 , and when applied in the form of a mixture, making it possible to detect seven pesticides out of the ten trained with ICTs, in most cases, higher than 106 . This performance was demonstrated to be superior to the LDI(±)MS technique.Com o aumento das atividades agrícolas, as hortaliças estão cada vez mais sujeitas à exposição de agrotóxicos, como inseticidas e fungicidas. O uso excessivo desses produtos durante o cultivo é um fator agravante, acarretando efeitos nocivos à saúde. Com o intuito de controlar o uso indiscriminado dessas substâncias e garantir a segurança alimentar, a comunidade científica tem realizado pesquisas e desenvolvido metodologias capazes de elucidar a composição e a distribuição desses agentes em amostras de vegetais. Técnicas convencionais, como cromatografia gasosa e cromatografia líquida, têm sido tradicionalmente utilizadas em estudos neste segmento. No entanto, pesquisas recentes apontam para o grande potencial do uso das técnicas de espectrometria de massa com fonte ionização por dessorção a laser (LDI-MS) e dessorção/ionização a laser assistida por matriz (MALDI-MS) para a análise de tecidos vegetais. Nos últimos estudos publicados pelo órgão regulamentador no Brasil, Agência Nacional de Vigilância Sanitária (ANVISA), foi observado o uso indiscriminado de agrotóxicos em alimentos devido ao alto índice de identificação dessas substâncias, muitas vezes acima do limite estabelecido. A couve, um vegetal muito comum na alimentação da população brasileira, se destacou neste levantamento, devido aos resultados insatisfatórios relacionados ao uso de agrotóxicos. Nesse sentido, o presente trabalho desenvolveu um método para monitoramento de agrotóxicos presentes em folhas de couve por análise direta, utilizando as fontes LDI e MALDI. Para desenvolvimento do método, foram monitorados os dez agrotóxicos mais detectados no último levantamento da ANVISA para a cultura da couve, sendo: Carbendazina, Ciromazina, Clorpirifós, Clotianidina, Deltametrina, Imidacloriprido, Lambda-Cialotrina, Metomil, Tebuconazol Trifloxistrobina. A fonte MALDI-MS foi otimizada, variando-se o tipo de matriz (2,5- dihydroxybenzoic acid, (DHB), α-cyano-4- hydroxycinnamic acid (CHCA) e 2- mercaptobenzotiazole (MBT)), sua concentração (de 0,025 à 1,00 mg mL-1 ) e forma de aplicação, mistura ou sanduíche. Os resultados sugerem uma melhor eficiência de ionização da tecnica MALDI(+)MS, quando a matriz DHB é utilizada em baixas concentrações, isto é, 0,050 mg mL-1 , e sob aplicação na forma de mistura, sendo possível detectar sete agrotóxicos dos dez estudados com TICs, na maior parte dos casos, superiores a 106 . Este desempenho se mostrou superior a técnica de LDI(±)MS. Universidade Federal do Espírito SantoBRMestrado em QuímicaCentro de Ciências ExatasUFESPrograma de Pós-Graduação em QuímicaRomao, Wandersonhttps://orcid.org/0000000222546683http://lattes.cnpq.br/9121022613112821https://orcid.org/0009-0004-7503-1669http://lattes.cnpq.br/2699098884412745Kitagawa, Rodrigo Rezendehttps://orcid.org/0000000222086699http://lattes.cnpq.br/4424075292014459Scherer, RodrigoFronza, MarcioCrisóstomo, Sabrina Gabriceli2024-05-29T20:55:41Z2024-05-29T20:55:41Z2023-11-07info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisTextapplication/pdfhttp://repositorio.ufes.br/handle/10/12694porinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)instname:Universidade Federal do Espírito Santo (UFES)instacron:UFES2024-10-21T09:53:50Zoai:repositorio.ufes.br:10/12694Repositório InstitucionalPUBhttp://repositorio.ufes.br/oai/requestriufes@ufes.bropendoar:21082024-10-21T09:53:50Repositório Institucional da Universidade Federal do Espírito Santo (riUfes) - Universidade Federal do Espírito Santo (UFES)false
dc.title.none.fl_str_mv Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
title Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
spellingShingle Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
Crisóstomo, Sabrina Gabriceli
MALDI MS
LDI
Couve
Agrotóxico
ANVISA
Química
title_short Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
title_full Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
title_fullStr Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
title_full_unstemmed Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
title_sort Estudo químico de agrotóxicos em tecido vegetal por MALDI-MS
author Crisóstomo, Sabrina Gabriceli
author_facet Crisóstomo, Sabrina Gabriceli
author_role author
dc.contributor.none.fl_str_mv Romao, Wanderson
https://orcid.org/0000000222546683
http://lattes.cnpq.br/9121022613112821
https://orcid.org/0009-0004-7503-1669
http://lattes.cnpq.br/2699098884412745
Kitagawa, Rodrigo Rezende
https://orcid.org/0000000222086699
http://lattes.cnpq.br/4424075292014459
Scherer, Rodrigo
Fronza, Marcio
dc.contributor.author.fl_str_mv Crisóstomo, Sabrina Gabriceli
dc.subject.por.fl_str_mv MALDI MS
LDI
Couve
Agrotóxico
ANVISA
Química
topic MALDI MS
LDI
Couve
Agrotóxico
ANVISA
Química
description With the increase in agricultural activities, vegetables are increasingly subject to exposure to pesticides, such as insecticides and fungicides. Excessive use of these products during cultivation is an aggravating factor, causing harmful effects on health. In order to control the use involved in these materials and ensure food safety, the scientific community has carried out research and developed methods capable of elucidating the composition and distribution of these agents in vegetable samples. Conventional techniques, such as gas chromatography and liquid chromatography, have traditionally been used in studies in these segments. However, recent studies point to the great potential of using mass spectrometry techniques with laser desorption ionization (LDI-MS) and matrix-assisted laser desorption/ionization (MALDI-MS) sources for the analysis of plant tissues. In the latest studies published by the regulatory body in Brazil, the National Health Surveillance Agency (ANVISA), the involved use of pesticides in food was presented due to the high rate of Identificação of these substances, often above the established limit. Kale, a very common vegetable in the Brazilian population's diet, stood out in this survey, due to the unsatisfactory results related to the use of pesticides. In this sense, the present work developed a method for monitoring pesticides presented in cabbage leaves by direct analysis, using the LDI and MALDI techniques. To develop the method, the ten most detected pesticides in the last ANVISA survey for cabbage crops were monitored, namely: Carbendazine, Cyromazine, Chlorpyrifos, Clothianidin, Deltamethrin, Imidacloriprid, Lambda-Cialothrin, Methomyl, Tebuconazole Trifloxystrobin. The MALDI-MS source was optimized by varying the type of matrix (2,5-dihydroxybenzoic acid, (DHB), α-cyano-4-hydroxycinnamic acid (CHCA) and 2-mercaptobenzothiazole (MBT)), its concentration (from 0.025 at 1.00 mg mL-1) and application method, mixture or sandwich. The results suggest a better ionization efficiency of the MALDI(+)MS technique, when the DHB matrix is used in low concentrations, that is, 0.050 mg mL-1 , and when applied in the form of a mixture, making it possible to detect seven pesticides out of the ten trained with ICTs, in most cases, higher than 106 . This performance was demonstrated to be superior to the LDI(±)MS technique.
publishDate 2023
dc.date.none.fl_str_mv 2023-11-07
2024-05-29T20:55:41Z
2024-05-29T20:55:41Z
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.ufes.br/handle/10/12694
url http://repositorio.ufes.br/handle/10/12694
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv Text
application/pdf
dc.publisher.none.fl_str_mv Universidade Federal do Espírito Santo
BR
Mestrado em Química
Centro de Ciências Exatas
UFES
Programa de Pós-Graduação em Química
publisher.none.fl_str_mv Universidade Federal do Espírito Santo
BR
Mestrado em Química
Centro de Ciências Exatas
UFES
Programa de Pós-Graduação em Química
dc.source.none.fl_str_mv reponame:Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
instname:Universidade Federal do Espírito Santo (UFES)
instacron:UFES
instname_str Universidade Federal do Espírito Santo (UFES)
instacron_str UFES
institution UFES
reponame_str Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
collection Repositório Institucional da Universidade Federal do Espírito Santo (riUfes)
repository.name.fl_str_mv Repositório Institucional da Universidade Federal do Espírito Santo (riUfes) - Universidade Federal do Espírito Santo (UFES)
repository.mail.fl_str_mv riufes@ufes.br
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