Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos

Detalhes bibliográficos
Autor(a) principal: Lourenço, Anabel Santos
Data de Publicação: 2020
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/123456789/18534
Resumo: The need to study and quantify constituents present in numerous matrices justifies the development of analytical methods and the use of chemically modified electrodes with redox mediators. The use of these sensors allows studies with species of great impact, industrial, environmental and for human health. In this context, the use of metallic phthalocyanines (MPCs), as electron mediators, has been used in electroanalysis because they have properties that facilitate the transfer of electrons. The present work proposed the development of voltammetric methods using carbon paste electrodes (CPE) modified with metallic phthalocyanines. The first study consisted of investigating the voltammetric behavior of different PCs for determining TA in wines. With this objective it was verified that only cobalt (II) phthalocyanine (CoPC) is able to electrocatalyze the oxidation of TA, a fact that is related to the presence of cobalt in this complex. In this way, CoPC - CPE was developed associated with multipath calibration for the determination of tartaric acid (TA) in wines. TA is present in wine in high concentrations, and its quantification is extremely important, considering its influence on the organoleptic properties, stability and microbiological characteristics of this drink. The presence of other organic acids in wine made it impossible to univariate the determination of TA, since these acids show a response signal in potentials very close to that of TA, thus using U-PLS/RBL modeling, a chemometric tool capable of quantifying a or more analyte in the presence of interferents. The response potential and sensitivity vary with the pH change of the medium, presenting greater sensitivity in acetate buffer (pH = 4.5) with a linear response range of 10 to 100 μmol L-1 (r = 0.9999) and LOD and LOQ of 7.29 mol L-1 and 22.1 mol L-1, respectively. Still with the study of wines, the second study proposed the simultaneous determination of biogenic amines (ABs), constituents that are also present in wines and can decrease the quality of this drink. In addition, these ABs, especially tryptamine (Trip) and histamine (Hist), have high toxicological potential for human health, even causing several symptoms of intoxication, even when present in low concentrations. Although there are no regulations that determine the quantity of these substances in wines, knowledge of the presence of these species is extremely important to assess the quality of the wine and to avoid intoxication caused by the ingestion of this drink. Thus, the CPE - NiPC was developed for simultaneous determination of Hist and Trip in wines. Studies have shown that, in addition to NiPC, other MPCs electrocatalyze the oxidation reaction of these amines, however only NiPC contributed to the high sensitivity of the proposed method. The response potential and sensitivity of the two analytes depend on the pH, obtaining optimal responses in phosphate buffer, pH = 8.5 with a linear response range of 0.49 - 3.93 ng mL-1 for Trip and 0.37 - 2.9 μg mL-1 for Hist and LOD of 0.168 ng mL-1 and 0.038 μg mL-1 and LOQ of 0.59 ng mL-1 and 0.115 μg mL-1, for Trip and Hist, respectively. The results obtained revealed the importance of using MPCs as electron mediators for the electrocatalysis of the different chemical species present in wines.
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spelling Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhosFtalocianinas metálicasEletrodo de pasta de carbonoÁcido tartáricoAminas biogênicasVinhosMetal phthalocyaninesTartaric acidBiogenic aminesCarbon paste electrodeWinesSquare wave voltammetricCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe need to study and quantify constituents present in numerous matrices justifies the development of analytical methods and the use of chemically modified electrodes with redox mediators. The use of these sensors allows studies with species of great impact, industrial, environmental and for human health. In this context, the use of metallic phthalocyanines (MPCs), as electron mediators, has been used in electroanalysis because they have properties that facilitate the transfer of electrons. The present work proposed the development of voltammetric methods using carbon paste electrodes (CPE) modified with metallic phthalocyanines. The first study consisted of investigating the voltammetric behavior of different PCs for determining TA in wines. With this objective it was verified that only cobalt (II) phthalocyanine (CoPC) is able to electrocatalyze the oxidation of TA, a fact that is related to the presence of cobalt in this complex. In this way, CoPC - CPE was developed associated with multipath calibration for the determination of tartaric acid (TA) in wines. TA is present in wine in high concentrations, and its quantification is extremely important, considering its influence on the organoleptic properties, stability and microbiological characteristics of this drink. The presence of other organic acids in wine made it impossible to univariate the determination of TA, since these acids show a response signal in potentials very close to that of TA, thus using U-PLS/RBL modeling, a chemometric tool capable of quantifying a or more analyte in the presence of interferents. The response potential and sensitivity vary with the pH change of the medium, presenting greater sensitivity in acetate buffer (pH = 4.5) with a linear response range of 10 to 100 μmol L-1 (r = 0.9999) and LOD and LOQ of 7.29 mol L-1 and 22.1 mol L-1, respectively. Still with the study of wines, the second study proposed the simultaneous determination of biogenic amines (ABs), constituents that are also present in wines and can decrease the quality of this drink. In addition, these ABs, especially tryptamine (Trip) and histamine (Hist), have high toxicological potential for human health, even causing several symptoms of intoxication, even when present in low concentrations. Although there are no regulations that determine the quantity of these substances in wines, knowledge of the presence of these species is extremely important to assess the quality of the wine and to avoid intoxication caused by the ingestion of this drink. Thus, the CPE - NiPC was developed for simultaneous determination of Hist and Trip in wines. Studies have shown that, in addition to NiPC, other MPCs electrocatalyze the oxidation reaction of these amines, however only NiPC contributed to the high sensitivity of the proposed method. The response potential and sensitivity of the two analytes depend on the pH, obtaining optimal responses in phosphate buffer, pH = 8.5 with a linear response range of 0.49 - 3.93 ng mL-1 for Trip and 0.37 - 2.9 μg mL-1 for Hist and LOD of 0.168 ng mL-1 and 0.038 μg mL-1 and LOQ of 0.59 ng mL-1 and 0.115 μg mL-1, for Trip and Hist, respectively. The results obtained revealed the importance of using MPCs as electron mediators for the electrocatalysis of the different chemical species present in wines.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESA necessidade de estudar e quantificar constituintes presentes em inúmeras matrizes justifica o desenvolvimento de métodos analíticos e o uso de eletrodos quimicamente modificados com mediadores redox. A utilização desses sensores viabiliza estudos com espécies de grande impacto, industrial, ambiental e para a saúde humana. Nesse contexto, o uso de ftalocianinas metálicas (MPCs), como mediadores de elétrons, tem sido empregado em eletroanálise por possuirem propriedades que facilitam a transferência de elétrons. O presente trabalho propôs o desenvolvimento de métodos voltamétricos utilizando eletrodos de pasta de carbono (CPE) modificados com ftalocianinas metálicas. O primeiro estudo consistiu em investigar o comportamento voltamétrico das diferentes PCs para determinação do TA em vinhos. Com essse objetivo verificou-se que apenas a ftalocianina de cobalto (II) (CoPC) é capaz de eletrocatalizar a oxidação do TA, fato que está relacionado a presença do cobalto neste complexo. Dessa forma foi desenvolvido o CoPC – CPE associado a calibração multivias para determinação de ácido tartárico (TA) em vinhos. O TA encontra-se presente no vinho em altas concentrações, e sua quantificação é de extrema importância, tendo em vista sua influência nas propriedades organolépticas, estabilidade e características microbiológicas dessa bebida. A presença de outros ácidos orgânicos no vinho impossibilitou a determinação univariada do TA, uma vez que esses ácidos apresentam sinal de responta em potenciais muito próximo ao do TA, dessa forma foi utilizada a modelagem U-PLS/RBL, ferramenta quimiométrica capaz de quantificar um ou mais analito na presença de interferentes. O potencial de resposta e a sensibilidade variam com a mudança de pH do meio, apresentando maior sensibilidade em tampão acetato (pH = 4,5) com faixa linear de resposta de 10 a 100 μmol L-1 (r = 0,9991) e LOD e LOQ de 7,29 mol L-1 e 22,1 mol L-1, respectivamente. Ainda com o estudo de vinhos, o segundo estudo proprôs a determinação simultânea de aminas biogênicas (ABs), constituintes que também se encontram presentes nos vinhos e podem diminuir a qualidade dessa bebida. Além disso, essas ABs, em especial a triptamina (Trip) e histamina (Hist), apresentam elevado potencial toxicológico para a saúde humana, chegando a causar diversos sintomas de intoxicação, mesmo quando presentes em baixas concentrações. Apesar de não existir regulamentos que determinem a quantidade dessas substâncias em vinhos, o conhecimento da presença dessas espécies é de extrema importância para avaliar a qualidade do vinho e evitar a intoxicação causada pela ingestão dessa bebida. Dessa forma foi desenvolvido o CPE - NiPC para determinação simultânea de Hist e Trip em vinhos. Os estudos mostraram que, além da NiPC outras MPCs eletrocatalisa a reação de oxidação dessas aminas, entretanto apenas a NiPC contribuiu para a elevada sensibilidade do método proposto. O potencial de resposta e a sensibilidade dos dois analitos dependem do pH, obtendo respostas ótimas em tampão fosfato, pH = 8,5 com faixa linear de resposta de 0,49 – 3,93 ng mL-1 para Trip e 0,37 - 2,9 μg mL-1 para Hist e LOD de 0,168 ng mL-1 e 0,038 μg mL-1 e LOQ de 0,509 ng mL-1 e 0,115 μg mL-1, para Trip e Hist, respectivamente. Os resultados obtidos revelaram a importância do uso das MPCs como mediares de elétrons para a eletrocatálise das diferentes espécies químicas presentes nos vinhos.Universidade Federal da ParaíbaBrasilQuímicaPrograma de Pós-Graduação em QuímicaUFPBAraújo, Mário César Ugulino dehttp://lattes.cnpq.br/7281739070942782Ribeiro, Williame Fariashttp://lattes.cnpq.br/6179867510942876Lourenço, Anabel Santos2020-11-25T11:33:34Z2020-07-302020-11-25T11:33:34Z2020-07-20info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesishttps://repositorio.ufpb.br/jspui/handle/123456789/18534porhttp://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:UFPB2021-09-08T23:45:08Zoai:repositorio.ufpb.br:123456789/18534Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufpb.br/PUBhttp://tede.biblioteca.ufpb.br:8080/oai/requestdiretoria@ufpb.br|| diretoria@ufpb.bropendoar:2021-09-08T23:45:08Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)false
dc.title.none.fl_str_mv Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
title Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
spellingShingle Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
Lourenço, Anabel Santos
Ftalocianinas metálicas
Eletrodo de pasta de carbono
Ácido tartárico
Aminas biogênicas
Vinhos
Metal phthalocyanines
Tartaric acid
Biogenic amines
Carbon paste electrode
Wines
Square wave voltammetric
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
title_full Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
title_fullStr Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
title_full_unstemmed Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
title_sort Ftalocianinas metálicas como mediadores de elétrons para determinação voltamétrica de ácido tartárico e aminas biogênicas em vinhos
author Lourenço, Anabel Santos
author_facet Lourenço, Anabel Santos
author_role author
dc.contributor.none.fl_str_mv Araújo, Mário César Ugulino de
http://lattes.cnpq.br/7281739070942782
Ribeiro, Williame Farias
http://lattes.cnpq.br/6179867510942876
dc.contributor.author.fl_str_mv Lourenço, Anabel Santos
dc.subject.por.fl_str_mv Ftalocianinas metálicas
Eletrodo de pasta de carbono
Ácido tartárico
Aminas biogênicas
Vinhos
Metal phthalocyanines
Tartaric acid
Biogenic amines
Carbon paste electrode
Wines
Square wave voltammetric
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic Ftalocianinas metálicas
Eletrodo de pasta de carbono
Ácido tartárico
Aminas biogênicas
Vinhos
Metal phthalocyanines
Tartaric acid
Biogenic amines
Carbon paste electrode
Wines
Square wave voltammetric
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description The need to study and quantify constituents present in numerous matrices justifies the development of analytical methods and the use of chemically modified electrodes with redox mediators. The use of these sensors allows studies with species of great impact, industrial, environmental and for human health. In this context, the use of metallic phthalocyanines (MPCs), as electron mediators, has been used in electroanalysis because they have properties that facilitate the transfer of electrons. The present work proposed the development of voltammetric methods using carbon paste electrodes (CPE) modified with metallic phthalocyanines. The first study consisted of investigating the voltammetric behavior of different PCs for determining TA in wines. With this objective it was verified that only cobalt (II) phthalocyanine (CoPC) is able to electrocatalyze the oxidation of TA, a fact that is related to the presence of cobalt in this complex. In this way, CoPC - CPE was developed associated with multipath calibration for the determination of tartaric acid (TA) in wines. TA is present in wine in high concentrations, and its quantification is extremely important, considering its influence on the organoleptic properties, stability and microbiological characteristics of this drink. The presence of other organic acids in wine made it impossible to univariate the determination of TA, since these acids show a response signal in potentials very close to that of TA, thus using U-PLS/RBL modeling, a chemometric tool capable of quantifying a or more analyte in the presence of interferents. The response potential and sensitivity vary with the pH change of the medium, presenting greater sensitivity in acetate buffer (pH = 4.5) with a linear response range of 10 to 100 μmol L-1 (r = 0.9999) and LOD and LOQ of 7.29 mol L-1 and 22.1 mol L-1, respectively. Still with the study of wines, the second study proposed the simultaneous determination of biogenic amines (ABs), constituents that are also present in wines and can decrease the quality of this drink. In addition, these ABs, especially tryptamine (Trip) and histamine (Hist), have high toxicological potential for human health, even causing several symptoms of intoxication, even when present in low concentrations. Although there are no regulations that determine the quantity of these substances in wines, knowledge of the presence of these species is extremely important to assess the quality of the wine and to avoid intoxication caused by the ingestion of this drink. Thus, the CPE - NiPC was developed for simultaneous determination of Hist and Trip in wines. Studies have shown that, in addition to NiPC, other MPCs electrocatalyze the oxidation reaction of these amines, however only NiPC contributed to the high sensitivity of the proposed method. The response potential and sensitivity of the two analytes depend on the pH, obtaining optimal responses in phosphate buffer, pH = 8.5 with a linear response range of 0.49 - 3.93 ng mL-1 for Trip and 0.37 - 2.9 μg mL-1 for Hist and LOD of 0.168 ng mL-1 and 0.038 μg mL-1 and LOQ of 0.59 ng mL-1 and 0.115 μg mL-1, for Trip and Hist, respectively. The results obtained revealed the importance of using MPCs as electron mediators for the electrocatalysis of the different chemical species present in wines.
publishDate 2020
dc.date.none.fl_str_mv 2020-11-25T11:33:34Z
2020-07-30
2020-11-25T11:33:34Z
2020-07-20
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format doctoralThesis
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dc.publisher.none.fl_str_mv Universidade Federal da Paraíba
Brasil
Química
Programa de Pós-Graduação em Química
UFPB
publisher.none.fl_str_mv Universidade Federal da Paraíba
Brasil
Química
Programa de Pós-Graduação em Química
UFPB
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instname_str Universidade Federal da Paraíba (UFPB)
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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
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