Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’
Autor(a) principal: | |
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Data de Publicação: | 2024 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFMS |
Texto Completo: | https://repositorio.ufms.br/handle/123456789/8666 |
Resumo: | In this work, the unpolarized (MEENP) and polarized (MEEP) excitation-emission matrices of undiluted (BDBND) and diluted (BDBD) diesel-biodiesel blends were analyzed using the parallel factor analysis method (PARAFAC). Through this analysis, analytical models to predict the biodiesel content in BDBND and BDBD were constructed. Regarding the PARAFAC analysis of the MEENP of the BDBND (MEENP-BDBND), the loadings values related to the concentration were used to construct the pseudo-univariate model. This model presented limits of detection (LOD) and limit of quantification (LOQ) of 2.5% and 11% w/w, respectively. According to the values of the root mean square error of predictions (RMSEP) and relative standard deviation of prediction (RSDP), the pseudo-univariate model showed robustness in predicting biodiesel in the samples from the external validation set, with values between 0.53-0.70% w/w and 3.65-5.10%, respectively. For the analysis of the MEEP of BDBND (MEEP(ND)) and BDBD (MEEP(D)), PARAFAC was applied to evaluate the best excitation-emission variables for the construction of polarized analytical models. Additionally, polarized 2D fluorescence measurements of external validation samples were used to validate the polarized models. For MEEP(ND), the best analytical curves were obtained in HV and HH polarizations, with LOD values equal to 1.05% w/w and 0.12% w/w while the LOQ values were 3.31% w/w and 0.38% w/w, respectively. In relation to the predicted biodiesel content, the model obtained in HV polarization presented the best RMSEP and RSDP values, which were 0.32% w/w and 2.14%, respectively. Regarding MEEP(D), all analytical curves showed low LOD and LOQ values. However, only the model obtained in VV polarization presented the best RMSEP and RSDP values, which were 0.49% w/w and 3.24%, respectively. Therefore, according to the RMSEP and RSDP values, the best analytical optical model was obtained through the analysis of MEEP(ND) with PARAFAC, in HV and HH polarizations. In addition to analytical optical models, the molecular properties of BDBD were evaluated using anisotropy resolved multidimensional emission spectroscopy (ARMES). As a result, anisotropy maps were constructed and showed low fluorescence anisotropy values of the fluorophores that belong to BDBD. These low fluorescence anisotropy values were attributed to rotational depolarization of the fluorophores. Keywords: Biodiesel; Diesel; Quantification; EEM; EEMp; PARAFAC; ARMES |
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2024-04-15T11:41:45Z2024-04-15T11:41:45Z2024https://repositorio.ufms.br/handle/123456789/8666In this work, the unpolarized (MEENP) and polarized (MEEP) excitation-emission matrices of undiluted (BDBND) and diluted (BDBD) diesel-biodiesel blends were analyzed using the parallel factor analysis method (PARAFAC). Through this analysis, analytical models to predict the biodiesel content in BDBND and BDBD were constructed. Regarding the PARAFAC analysis of the MEENP of the BDBND (MEENP-BDBND), the loadings values related to the concentration were used to construct the pseudo-univariate model. This model presented limits of detection (LOD) and limit of quantification (LOQ) of 2.5% and 11% w/w, respectively. According to the values of the root mean square error of predictions (RMSEP) and relative standard deviation of prediction (RSDP), the pseudo-univariate model showed robustness in predicting biodiesel in the samples from the external validation set, with values between 0.53-0.70% w/w and 3.65-5.10%, respectively. For the analysis of the MEEP of BDBND (MEEP(ND)) and BDBD (MEEP(D)), PARAFAC was applied to evaluate the best excitation-emission variables for the construction of polarized analytical models. Additionally, polarized 2D fluorescence measurements of external validation samples were used to validate the polarized models. For MEEP(ND), the best analytical curves were obtained in HV and HH polarizations, with LOD values equal to 1.05% w/w and 0.12% w/w while the LOQ values were 3.31% w/w and 0.38% w/w, respectively. In relation to the predicted biodiesel content, the model obtained in HV polarization presented the best RMSEP and RSDP values, which were 0.32% w/w and 2.14%, respectively. Regarding MEEP(D), all analytical curves showed low LOD and LOQ values. However, only the model obtained in VV polarization presented the best RMSEP and RSDP values, which were 0.49% w/w and 3.24%, respectively. Therefore, according to the RMSEP and RSDP values, the best analytical optical model was obtained through the analysis of MEEP(ND) with PARAFAC, in HV and HH polarizations. In addition to analytical optical models, the molecular properties of BDBD were evaluated using anisotropy resolved multidimensional emission spectroscopy (ARMES). As a result, anisotropy maps were constructed and showed low fluorescence anisotropy values of the fluorophores that belong to BDBD. These low fluorescence anisotropy values were attributed to rotational depolarization of the fluorophores. Keywords: Biodiesel; Diesel; Quantification; EEM; EEMp; PARAFAC; ARMESNeste trabalho as matrizes de excitação-emissão, não polarizada (MEENP) e polarizada (MEEP), de blendas de diesel-biodiesel não diluídas (BDBND) e diluídas (BDBD), foram analisadas através do método análise dos fatores paralelos (PARAFAC). Através dessa análise, modelos analíticos para predizer o teor de biodiesel em BDBND e BDBD foram construídos. Em relação a análise PARAFAC das MEENP das BDBND (MEENP-BDBND), os valores dos “loadings” relacionados à concentração foram utilizados para a construção do modelo pseudo-univariado. Esse modelo apresentou limites de detecção (LOD) e limite de quantificação (LOQ) de 2,5% e 11% (m/m), respectivamente. De acordo com os valores da raiz do erro quadrático médio de predição (RMSEP) e desvio padrão relativo de predição (RSDP), o modelo pseudo-univariado apresentou robustez na predição de biodiesel nas amostras do conjunto de validação externa, com valores entre 0,53-0,70% (m/m) e 3,65-5,10%, respectivamente. Para a análise das MEEP das BDBND (MEEP(ND)) e das BDBD (MEEP(D)), o PARAFAC foi aplicado para avaliar as melhores variáveis de excitação-emissão para a construção de modelos analíticos a partir dos resultados de fluorescência polarizada. Adicionalmente, medidas de fluorescência 2D polarizada das amostras de validação externa foram utilizadas para validação dos modelos. Para as MEEP(ND), as melhores curvas analíticas foram obtidas nas polarizações HV e HH, com valores de LOD iguais a 1,05% (m/m) e 0,12% (m/m) enquanto os valores de LOQ foram de 3,31% (m/m) e 0,38% (m/m), respectivamente. Em relação ao teor de biodiesel predito, o modelo obtido na polarização HV apresentou os melhores valores de RMSEP e RSDP, os quais foram 0,32% (m/m) e 2,14%, respectivamente. Para as MEEP(D), todas as curvas analíticas apresentaram baixos valores de LOD e LOQ. No entanto, apenas o modelo obtido na polarização VV, apresentou os melhores valores de RMSEP e RSDP, os quais foram 0,49% (m/m) e 3,24%, respectivamente. Portanto, de acordo com os valores de RMSEP e RSDP, o melhor modelo óptico analítico foi obtido através da análise das MEEP(ND) com PARAFAC com as polarizações HV e HH. Além dos modelos ópticos analíticos, as propriedades moleculares das BDBD foram avaliadas através da espectroscopia de emissão multidimensional resolvida por anisotropia (ARMES). Como resultado, os mapas de anisotropia (MDA) foram construídos e evidenciaram baixos valores de anisotropia de fluorescência dos fluoróforos que compõem as BDBD. Esses baixos valores de anisotropia de fluorescência foram atribuídos a despolarização por rotação dos fluoróforos. Palavras-Chave: Biodiesel; Diesel; Quantificação; MEE; MEEP; PARAFAC; ARMESFundação Universidade Federal de Mato Grosso do SulUFMSBrasilBiodieselDieselQuantificaçãoMEEMEEpPARAFACARMESDesenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisAnderson Rodrigues Lima CairesFernando Rodrigues da Conceiçãoinfo:eu-repo/semantics/openAccessporreponame:Repositório Institucional da UFMSinstname:Universidade Federal de Mato Grosso do Sul (UFMS)instacron:UFMSORIGINALTese_Fernando_Rodrigues_da_Conceição.pdfTese_Fernando_Rodrigues_da_Conceição.pdfapplication/pdf5645113https://repositorio.ufms.br/bitstream/123456789/8666/-1/Tese_Fernando_Rodrigues_da_Concei%c3%a7%c3%a3o.pdfa45e1981b6e8777244602d216595aba3MD5-1123456789/86662024-04-15 07:41:46.538oai:repositorio.ufms.br:123456789/8666Repositório InstitucionalPUBhttps://repositorio.ufms.br/oai/requestri.prograd@ufms.bropendoar:21242024-04-15T11:41:46Repositório Institucional da UFMS - Universidade Federal de Mato Grosso do Sul (UFMS)false |
dc.title.pt_BR.fl_str_mv |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
title |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
spellingShingle |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ Fernando Rodrigues da Conceição Biodiesel Diesel Quantificação MEE MEEp PARAFAC ARMES |
title_short |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
title_full |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
title_fullStr |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
title_full_unstemmed |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
title_sort |
Desenvolvimento de métodos ópticos analíticos baseado na fluorescência multidimensional para quantificar biodiesel em blendas de diesel-biodiesel’ |
author |
Fernando Rodrigues da Conceição |
author_facet |
Fernando Rodrigues da Conceição |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Anderson Rodrigues Lima Caires |
dc.contributor.author.fl_str_mv |
Fernando Rodrigues da Conceição |
contributor_str_mv |
Anderson Rodrigues Lima Caires |
dc.subject.por.fl_str_mv |
Biodiesel Diesel Quantificação MEE MEEp PARAFAC ARMES |
topic |
Biodiesel Diesel Quantificação MEE MEEp PARAFAC ARMES |
description |
In this work, the unpolarized (MEENP) and polarized (MEEP) excitation-emission matrices of undiluted (BDBND) and diluted (BDBD) diesel-biodiesel blends were analyzed using the parallel factor analysis method (PARAFAC). Through this analysis, analytical models to predict the biodiesel content in BDBND and BDBD were constructed. Regarding the PARAFAC analysis of the MEENP of the BDBND (MEENP-BDBND), the loadings values related to the concentration were used to construct the pseudo-univariate model. This model presented limits of detection (LOD) and limit of quantification (LOQ) of 2.5% and 11% w/w, respectively. According to the values of the root mean square error of predictions (RMSEP) and relative standard deviation of prediction (RSDP), the pseudo-univariate model showed robustness in predicting biodiesel in the samples from the external validation set, with values between 0.53-0.70% w/w and 3.65-5.10%, respectively. For the analysis of the MEEP of BDBND (MEEP(ND)) and BDBD (MEEP(D)), PARAFAC was applied to evaluate the best excitation-emission variables for the construction of polarized analytical models. Additionally, polarized 2D fluorescence measurements of external validation samples were used to validate the polarized models. For MEEP(ND), the best analytical curves were obtained in HV and HH polarizations, with LOD values equal to 1.05% w/w and 0.12% w/w while the LOQ values were 3.31% w/w and 0.38% w/w, respectively. In relation to the predicted biodiesel content, the model obtained in HV polarization presented the best RMSEP and RSDP values, which were 0.32% w/w and 2.14%, respectively. Regarding MEEP(D), all analytical curves showed low LOD and LOQ values. However, only the model obtained in VV polarization presented the best RMSEP and RSDP values, which were 0.49% w/w and 3.24%, respectively. Therefore, according to the RMSEP and RSDP values, the best analytical optical model was obtained through the analysis of MEEP(ND) with PARAFAC, in HV and HH polarizations. In addition to analytical optical models, the molecular properties of BDBD were evaluated using anisotropy resolved multidimensional emission spectroscopy (ARMES). As a result, anisotropy maps were constructed and showed low fluorescence anisotropy values of the fluorophores that belong to BDBD. These low fluorescence anisotropy values were attributed to rotational depolarization of the fluorophores. Keywords: Biodiesel; Diesel; Quantification; EEM; EEMp; PARAFAC; ARMES |
publishDate |
2024 |
dc.date.accessioned.fl_str_mv |
2024-04-15T11:41:45Z |
dc.date.available.fl_str_mv |
2024-04-15T11:41:45Z |
dc.date.issued.fl_str_mv |
2024 |
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.ufms.br/handle/123456789/8666 |
url |
https://repositorio.ufms.br/handle/123456789/8666 |
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.publisher.none.fl_str_mv |
Fundação Universidade Federal de Mato Grosso do Sul |
dc.publisher.initials.fl_str_mv |
UFMS |
dc.publisher.country.fl_str_mv |
Brasil |
publisher.none.fl_str_mv |
Fundação Universidade Federal de Mato Grosso do Sul |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFMS instname:Universidade Federal de Mato Grosso do Sul (UFMS) instacron:UFMS |
instname_str |
Universidade Federal de Mato Grosso do Sul (UFMS) |
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UFMS |
institution |
UFMS |
reponame_str |
Repositório Institucional da UFMS |
collection |
Repositório Institucional da UFMS |
bitstream.url.fl_str_mv |
https://repositorio.ufms.br/bitstream/123456789/8666/-1/Tese_Fernando_Rodrigues_da_Concei%c3%a7%c3%a3o.pdf |
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a45e1981b6e8777244602d216595aba3 |
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MD5 |
repository.name.fl_str_mv |
Repositório Institucional da UFMS - Universidade Federal de Mato Grosso do Sul (UFMS) |
repository.mail.fl_str_mv |
ri.prograd@ufms.br |
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1807552806814482432 |