Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFPB |
Texto Completo: | https://repositorio.ufpb.br/jspui/handle/123456789/13993 |
Resumo: | The Aedes aegypti mosquitoes are vectors of diseases such as dengue, chikungunya, zika and yellow fever. With the increase in the incidence of these diseases, the population has resorted to the use of repellents to try to protect themselves from the attack of these mosquitoes. The Brazilian market offers a wide variety of products which have different active ingredients (with varying levels of concentration), protection time and different prices. The most important repellents are the base on DEET (N, N-diethyl-3-methylbenzamide), IR3535 (ethyl butyl acetylaminopropionate) and icaridin (hydroxyethyl isobutyl piperidine carboxylate) for use in adults and children. The action time of these repellents depends, among other factors, on the concentration of these active ingredients. This work proposes methodologies for classification and determination of active ingredients in insect repellents, considering that there is no reference method to perform the quality control of these products. In the first stage the development and validation of a method based on high performance liquid chromatography (HPLC-DAD) was carried out. The validated method according to EURACHEM showed good linearity (0.25 to 22 mg L-1 for DEET, r2 = 0.9986 and 0.5 to 40 mg L-1, r2 = 0.9976 for IR 3535 ), with intra- and inter-day precision calculated using a Horwitz ratio of less than 2 and recoveries of 89.2 - 111.6% and 94.7 - 109.2% for DEET and IR3535, respectively. Infrared spectroscopy and chemometric techniques for classification, calibration and calibration transfer of commercial repellents were used. In the multivariate classification part, the near infrared spectroscopy (NIR) was obtained the best result with the discriminant analysis by the partial least squares (PLS/DA) and MLR with selection of stepwise variables (MLR/SW), reaching a rate Correct Classification (TCC) of 100% for the three active ingredients studied (DEET, IR 3535 and icaridin). Regarding the multivariate calibration, NIR and medium infrared (MIR) spectroscopies were used to determine DEET and IR 3535 in repellents. For DEET, using the NIR data, satisfactory results were obtained using the interval partial least squares regression (iPLS) and multiple linear regression with variable selection by the successive projection algorithm (MLR/SPA), reaching a RMSEP of 0.70% and 0.74% (m m-1), respectively. The IR 3535 samples measured in the NIR showed better results with PLS and MLR/SW reaching RMSEP of 0.64% and 1.03% (m m-1), respectively. The best results using MIR were obtained with the PLS model, with RMSEP of 1.38% and 1.69% (m m-1), for DEET and IR 3535, respectively. Finally, a calibration transfer study was carried out using two NIR spectroscopy equipment. For this purpose, Direct Standardization (DS), Reverse Standardization (RS) and Piecewise Direct Standardization (PDS) techniques were used. For DEET, the best result was obtained with PLS applied to the RS technique, in which RMSEP decreased from 7.95% to 1.21%. For IR 3535, the lowest value was reached with MLR/SPA, in which RMSEP decreased from 25.18% to 1.58% (DS). The proposed alternative methodologies based on NIR and MIR spectroscopy presented advantages because they are fast, non destructive, low cost and do not use reagents. And they are promising in the classification and calibration for quality control of active ingredients in insect repellent samples. |
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Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetosDEETIcaridinaIR 3535Cromatografia em fase líquidaEspectrometria no infravermelhoAnálise multivariadaIcaridinLiquid phase chromatographyInfrared spectrometryMultivariate analysisRepelente - princípios ativosInsetosControle qualidade - repelentesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe Aedes aegypti mosquitoes are vectors of diseases such as dengue, chikungunya, zika and yellow fever. With the increase in the incidence of these diseases, the population has resorted to the use of repellents to try to protect themselves from the attack of these mosquitoes. The Brazilian market offers a wide variety of products which have different active ingredients (with varying levels of concentration), protection time and different prices. The most important repellents are the base on DEET (N, N-diethyl-3-methylbenzamide), IR3535 (ethyl butyl acetylaminopropionate) and icaridin (hydroxyethyl isobutyl piperidine carboxylate) for use in adults and children. The action time of these repellents depends, among other factors, on the concentration of these active ingredients. This work proposes methodologies for classification and determination of active ingredients in insect repellents, considering that there is no reference method to perform the quality control of these products. In the first stage the development and validation of a method based on high performance liquid chromatography (HPLC-DAD) was carried out. The validated method according to EURACHEM showed good linearity (0.25 to 22 mg L-1 for DEET, r2 = 0.9986 and 0.5 to 40 mg L-1, r2 = 0.9976 for IR 3535 ), with intra- and inter-day precision calculated using a Horwitz ratio of less than 2 and recoveries of 89.2 - 111.6% and 94.7 - 109.2% for DEET and IR3535, respectively. Infrared spectroscopy and chemometric techniques for classification, calibration and calibration transfer of commercial repellents were used. In the multivariate classification part, the near infrared spectroscopy (NIR) was obtained the best result with the discriminant analysis by the partial least squares (PLS/DA) and MLR with selection of stepwise variables (MLR/SW), reaching a rate Correct Classification (TCC) of 100% for the three active ingredients studied (DEET, IR 3535 and icaridin). Regarding the multivariate calibration, NIR and medium infrared (MIR) spectroscopies were used to determine DEET and IR 3535 in repellents. For DEET, using the NIR data, satisfactory results were obtained using the interval partial least squares regression (iPLS) and multiple linear regression with variable selection by the successive projection algorithm (MLR/SPA), reaching a RMSEP of 0.70% and 0.74% (m m-1), respectively. The IR 3535 samples measured in the NIR showed better results with PLS and MLR/SW reaching RMSEP of 0.64% and 1.03% (m m-1), respectively. The best results using MIR were obtained with the PLS model, with RMSEP of 1.38% and 1.69% (m m-1), for DEET and IR 3535, respectively. Finally, a calibration transfer study was carried out using two NIR spectroscopy equipment. For this purpose, Direct Standardization (DS), Reverse Standardization (RS) and Piecewise Direct Standardization (PDS) techniques were used. For DEET, the best result was obtained with PLS applied to the RS technique, in which RMSEP decreased from 7.95% to 1.21%. For IR 3535, the lowest value was reached with MLR/SPA, in which RMSEP decreased from 25.18% to 1.58% (DS). The proposed alternative methodologies based on NIR and MIR spectroscopy presented advantages because they are fast, non destructive, low cost and do not use reagents. And they are promising in the classification and calibration for quality control of active ingredients in insect repellent samples.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqOs mosquitos Aedes aegypti são vetores de doenças como a dengue, chikungunya, zika e febre amarela. Com o aumento da incidência dessas enfermidades a população tem recorrido ao uso de repelentes para tentar se proteger do ataque desses mosquitos. O mercado brasileiro disponibiliza uma variedade grande de produtos que possuem princípios ativos diferentes (com vários níveis de concentração), tempo de ação e preços distintos. Destacam-se os repelentes a base de DEET (N,N-dietil-3-metilbenzamida), do IR3535 (etil-butil-acetilaminopropionato) e icaridina (hidroxietil isobutil-piperidina carboxilato) para uso em adultos e em crianças. O tempo de ação desses repelentes depende, entre outros fatores, da concentração desses ingredientes ativos. Este trabalho propõe metodologias para classificação e determinação de princípios ativos em repelentes de insetos, tendo em vista que não existe um método de referência para realizar o controle de qualidade desses produtos. Na primeira etapa foi realizado o desenvolvimento e validação de um método baseado na cromatografia líquida de alta eficiência (HPLC-DAD). O método validado de acordo com a EURACHEM apresentou boa linearidade (0,25 a 22 mg L−1 para o DEET, r2 = 0,9986 e 0,5 a 40 mg L−1, r2 = 0,9976 para o IR 3535), com a precisão intra e interdia calculada usando uma razão de Horwitz menor que 2 e recuperações de 89,2 a 111,6% e 94,7 a 109,2% para DEET e IR3535, respectivamente. Foram utilizadas as espectroscopias no infravermelho e técnicas quimiométricas para classificação, calibração e transferência de calibração dos repelentes comerciais. Na parte de classificação multivariada foi utilizada a espectroscopia no infravermelho próximo (NIR) obteve-se o melhor resultado com a análise discriminante pelos mínimos quadrados parciais (PLS-DA) e MLR com seleção de variáveis stepwise (MLR/SW), alcançando uma Taxa de Classificação Correta (TCC) de 100% para os três princípios ativa estudada (DEET, IR 3535 e icaridina). Em relação à calibração multivariada, foram utilizadas as espectroscopias NIR e no infravermelho médio (MIR) para determinar DEET e IR 3535 em repelentes. Para o DEET empregando os dados NIR, foram encontrados resultados satisfatórios utilizando a regressão pelos mínimos quadrados parciais por intervalos (iPLS) e regressão linear múltipla com seleção de variáveis pelo algoritmo das projeções sucessivas (MLR/SPA) atingindo um RMSEP de 0,70% e 0,74% (m m1), respectivamente. As amostras de IR 3535 medidas no NIR apresentaram melhores resultados com PLS e MLR/SW alcançando RMSEP de 0,64% e 1,03% (m m-1), respectivamente. Os melhores resultados utilizando MIR foram alcançados com o modelo PLS, com RMSEP de 1,38% e 1,69% (m m-1), para DEET e IR 3535, respectivamente. Por fim, foi realizado um estudo de transferência de calibração empregando dois equipamentos de espectroscopia NIR. Para este propósito, técnicas de padronização direta (DS), reversa (RS) e direta por partes (PDS) foram utilizadas. Para DEET, o melhor resultado foi obtido com PLS aplicados à técnica RS onde o RMSEP diminuiu de 7,95% para 1,21%. Para o IR 3535, o menor valor foi alcançado com MLR/SPA, em que o RMSEP diminuiu de 25,18% para 1,58% (DS). As metodologias alternativas propostas baseadas na espectroscopia NIR e MIR apresentaram vantagens por serem rápidas, não destrutivas, baixo custo e não utilizam reagentes. E são promissoras na classificação e calibração para o controle de qualidade de princípios ativos em amostras de repelentes de insetos.Universidade Federal da ParaíbaBrasilQuímicaPrograma de Pós-Graduação em Engenharia QuímicaUFPBPontes, Marcio Jose Coelho dehttp://lattes.cnpq.br/1685611433864910Vilar, Welma Thaíse Silva2019-04-10T14:08:34Z2018-10-172019-04-10T14:08:34Z2018-09-28info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttps://repositorio.ufpb.br/jspui/handle/123456789/13993porAttribution-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nd/3.0/br/info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFPBinstname:Universidade Federal da Paraíba (UFPB)instacron:UFPB2019-04-10T14:08:34Zoai:repositorio.ufpb.br:123456789/13993Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufpb.br/PUBhttp://tede.biblioteca.ufpb.br:8080/oai/requestdiretoria@ufpb.br|| diretoria@ufpb.bropendoar:2019-04-10T14:08:34Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)false |
dc.title.none.fl_str_mv |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
title |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
spellingShingle |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos Vilar, Welma Thaíse Silva DEET Icaridina IR 3535 Cromatografia em fase líquida Espectrometria no infravermelho Análise multivariada Icaridin Liquid phase chromatography Infrared spectrometry Multivariate analysis Repelente - princípios ativos Insetos Controle qualidade - repelentes CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
title_full |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
title_fullStr |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
title_full_unstemmed |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
title_sort |
Desenvolvimento de metodologias analíticas baseadas em HPLC-DAD, espectroscopia no infravermelho e quimiometria para o controle de qualidade de repelentes de insetos |
author |
Vilar, Welma Thaíse Silva |
author_facet |
Vilar, Welma Thaíse Silva |
author_role |
author |
dc.contributor.none.fl_str_mv |
Pontes, Marcio Jose Coelho de http://lattes.cnpq.br/1685611433864910 |
dc.contributor.author.fl_str_mv |
Vilar, Welma Thaíse Silva |
dc.subject.por.fl_str_mv |
DEET Icaridina IR 3535 Cromatografia em fase líquida Espectrometria no infravermelho Análise multivariada Icaridin Liquid phase chromatography Infrared spectrometry Multivariate analysis Repelente - princípios ativos Insetos Controle qualidade - repelentes CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
DEET Icaridina IR 3535 Cromatografia em fase líquida Espectrometria no infravermelho Análise multivariada Icaridin Liquid phase chromatography Infrared spectrometry Multivariate analysis Repelente - princípios ativos Insetos Controle qualidade - repelentes CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The Aedes aegypti mosquitoes are vectors of diseases such as dengue, chikungunya, zika and yellow fever. With the increase in the incidence of these diseases, the population has resorted to the use of repellents to try to protect themselves from the attack of these mosquitoes. The Brazilian market offers a wide variety of products which have different active ingredients (with varying levels of concentration), protection time and different prices. The most important repellents are the base on DEET (N, N-diethyl-3-methylbenzamide), IR3535 (ethyl butyl acetylaminopropionate) and icaridin (hydroxyethyl isobutyl piperidine carboxylate) for use in adults and children. The action time of these repellents depends, among other factors, on the concentration of these active ingredients. This work proposes methodologies for classification and determination of active ingredients in insect repellents, considering that there is no reference method to perform the quality control of these products. In the first stage the development and validation of a method based on high performance liquid chromatography (HPLC-DAD) was carried out. The validated method according to EURACHEM showed good linearity (0.25 to 22 mg L-1 for DEET, r2 = 0.9986 and 0.5 to 40 mg L-1, r2 = 0.9976 for IR 3535 ), with intra- and inter-day precision calculated using a Horwitz ratio of less than 2 and recoveries of 89.2 - 111.6% and 94.7 - 109.2% for DEET and IR3535, respectively. Infrared spectroscopy and chemometric techniques for classification, calibration and calibration transfer of commercial repellents were used. In the multivariate classification part, the near infrared spectroscopy (NIR) was obtained the best result with the discriminant analysis by the partial least squares (PLS/DA) and MLR with selection of stepwise variables (MLR/SW), reaching a rate Correct Classification (TCC) of 100% for the three active ingredients studied (DEET, IR 3535 and icaridin). Regarding the multivariate calibration, NIR and medium infrared (MIR) spectroscopies were used to determine DEET and IR 3535 in repellents. For DEET, using the NIR data, satisfactory results were obtained using the interval partial least squares regression (iPLS) and multiple linear regression with variable selection by the successive projection algorithm (MLR/SPA), reaching a RMSEP of 0.70% and 0.74% (m m-1), respectively. The IR 3535 samples measured in the NIR showed better results with PLS and MLR/SW reaching RMSEP of 0.64% and 1.03% (m m-1), respectively. The best results using MIR were obtained with the PLS model, with RMSEP of 1.38% and 1.69% (m m-1), for DEET and IR 3535, respectively. Finally, a calibration transfer study was carried out using two NIR spectroscopy equipment. For this purpose, Direct Standardization (DS), Reverse Standardization (RS) and Piecewise Direct Standardization (PDS) techniques were used. For DEET, the best result was obtained with PLS applied to the RS technique, in which RMSEP decreased from 7.95% to 1.21%. For IR 3535, the lowest value was reached with MLR/SPA, in which RMSEP decreased from 25.18% to 1.58% (DS). The proposed alternative methodologies based on NIR and MIR spectroscopy presented advantages because they are fast, non destructive, low cost and do not use reagents. And they are promising in the classification and calibration for quality control of active ingredients in insect repellent samples. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-10-17 2018-09-28 2019-04-10T14:08:34Z 2019-04-10T14:08:34Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufpb.br/jspui/handle/123456789/13993 |
url |
https://repositorio.ufpb.br/jspui/handle/123456789/13993 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
Attribution-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nd/3.0/br/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nd/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Engenharia Química UFPB |
publisher.none.fl_str_mv |
Universidade Federal da Paraíba Brasil Química Programa de Pós-Graduação em Engenharia Química UFPB |
dc.source.none.fl_str_mv |
reponame:Biblioteca Digital de Teses e Dissertações da UFPB instname:Universidade Federal da Paraíba (UFPB) instacron:UFPB |
instname_str |
Universidade Federal da Paraíba (UFPB) |
instacron_str |
UFPB |
institution |
UFPB |
reponame_str |
Biblioteca Digital de Teses e Dissertações da UFPB |
collection |
Biblioteca Digital de Teses e Dissertações da UFPB |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB) |
repository.mail.fl_str_mv |
diretoria@ufpb.br|| diretoria@ufpb.br |
_version_ |
1801842945499856896 |