Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/15074 |
Resumo: | The use of food supplements grows around the world every day. In order to improve physical performance, prevent disease, maintain and improve health, obtain and / or maintain desired body weight and still fill nutritional gaps in the diet, many individuals consume these products even without proven efficacy or safety. As a result of the growth of this market, cases of adulteration by synthetic substances increase. This implies the need to develop rapid, sensitive, selective methodologies that reach a considerable number of drugs of analytical interest. In this work two methods of analysis of multi-drug classes are described. The method of chromatographic separation with pulse-amperometric detection comprises 15 drugs: anorexigenics (amfepramone and femproporex), stimulants (caffeine, yohimbine, sildenafil and tadalafil), diuretics (furosemide), antidepressants (fluoxetine and sertraline), anxiolytics (lorazepam, clonazepam, midazolam and diazepam) and laxatives (bisacodyl). The characteristics related to the separation column (biphenyl) favored the study of a large number of compounds. The optimized conditions were: ammonium acetate 10 mmol L-1, methanol 64%, pH 4.0, 1.0 mL min -1, 40ºC, detection potential +0.8 V. The second method, using voltammetric pulse technique on the mercury electrode in organic medium, comprises a total of 10 pharmaceutical compounds being anxiolytics (alprazolam, bromazepam, clonazepam, chlordiazepoxide, midazolam and diazepam), diuretics (amiloride), antidepressants (bupropion) and anorectics (amfepramone and femproporex). The optimized conditions were: 0.01 mol L-1 NaClO4 in ACN, HMDE operating in differential pulse mode, scanning speed 30 mV/s. Of the two methods, a total of 20 drugs can be studied in real samples. Both methods were validated according to AOAC recommended parameters. Selectivity, linearity, limits of detection and quantification, precision and accuracy were evaluated. The chromatographic method (HPLC-PAD) was applied in 81 samples of food supplements marketed in Brazil. 1.23% of the samples had a positive signal for femproporex, 1.23% for amfepramone, 6.17% for yohimbine, 53.10% for caffeine, 1.23% for furosemide, 1.23% for tadalafil and 9.87 % for diazepam. From this total of samples containing drugs declared or not, two or more drugs were found in approximately 15% of the supplements analyzed. The concentration of the drugs varied from 0.20 to 866.88 mg/daily dose recommended by the manufacturer. The voltammetric method was applied only to samples with dilutions of at least one hundred times, since there is interference of the matrix in the redox reactions in the mercury electrode. The great differential of this work is the screening of 20 drugs as possible adulterants in food supplement samples, due to the characteristics of the stationary phase in chromatography and to the non-aqueous medium in voltammetry. |
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Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétricaStudy of the presence of drugs as adulterants in food supplements employing amperometric and voltametric detectionSuplementos alimentaresCromatografiaDetecção pulso–amperométricaVoltametria em meio orgânicoDietary supplementsChromatographyPulsed amperometric detectionNon–aqueous voltammetryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe use of food supplements grows around the world every day. In order to improve physical performance, prevent disease, maintain and improve health, obtain and / or maintain desired body weight and still fill nutritional gaps in the diet, many individuals consume these products even without proven efficacy or safety. As a result of the growth of this market, cases of adulteration by synthetic substances increase. This implies the need to develop rapid, sensitive, selective methodologies that reach a considerable number of drugs of analytical interest. In this work two methods of analysis of multi-drug classes are described. The method of chromatographic separation with pulse-amperometric detection comprises 15 drugs: anorexigenics (amfepramone and femproporex), stimulants (caffeine, yohimbine, sildenafil and tadalafil), diuretics (furosemide), antidepressants (fluoxetine and sertraline), anxiolytics (lorazepam, clonazepam, midazolam and diazepam) and laxatives (bisacodyl). The characteristics related to the separation column (biphenyl) favored the study of a large number of compounds. The optimized conditions were: ammonium acetate 10 mmol L-1, methanol 64%, pH 4.0, 1.0 mL min -1, 40ºC, detection potential +0.8 V. The second method, using voltammetric pulse technique on the mercury electrode in organic medium, comprises a total of 10 pharmaceutical compounds being anxiolytics (alprazolam, bromazepam, clonazepam, chlordiazepoxide, midazolam and diazepam), diuretics (amiloride), antidepressants (bupropion) and anorectics (amfepramone and femproporex). The optimized conditions were: 0.01 mol L-1 NaClO4 in ACN, HMDE operating in differential pulse mode, scanning speed 30 mV/s. Of the two methods, a total of 20 drugs can be studied in real samples. Both methods were validated according to AOAC recommended parameters. Selectivity, linearity, limits of detection and quantification, precision and accuracy were evaluated. The chromatographic method (HPLC-PAD) was applied in 81 samples of food supplements marketed in Brazil. 1.23% of the samples had a positive signal for femproporex, 1.23% for amfepramone, 6.17% for yohimbine, 53.10% for caffeine, 1.23% for furosemide, 1.23% for tadalafil and 9.87 % for diazepam. From this total of samples containing drugs declared or not, two or more drugs were found in approximately 15% of the supplements analyzed. The concentration of the drugs varied from 0.20 to 866.88 mg/daily dose recommended by the manufacturer. The voltammetric method was applied only to samples with dilutions of at least one hundred times, since there is interference of the matrix in the redox reactions in the mercury electrode. The great differential of this work is the screening of 20 drugs as possible adulterants in food supplement samples, due to the characteristics of the stationary phase in chromatography and to the non-aqueous medium in voltammetry.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESO uso de suplementos alimentares cresce ao redor do mundo a cada dia. No intuito de melhorar o desempenho físico, prevenir doenças, manter e melhorar a saúde, obter e/ou manter o peso corporal desejado e ainda preencher lacunas nutricionais na dieta, muitos indivíduos consomem estes produtos, mesmo sem a comprovada eficácia ou segurança. Em consequência ao crescimento deste mercado, aumentam os casos de adulteração por substâncias sintéticas. Isto implica na necessidade de desenvolverem–se metodologias rápidas, sensíveis, seletivas e que alcancem um número considerável de fármacos de interesse analítico. Neste trabalho estão descritos dois métodos de análise de multi classes de fármacos. O método de separação cromatográfico com detecção pulso–amperométrica abrange 15 fármacos: anorexígenos (anfepramona e femproporex), estimulantes (cafeína, ioimbina, sildenafil e tadalafil), diuréticos (furosemida), antidepressivos (fluoxetina e sertralina), ansiolíticos (lorazepam, clonazepam, midazolam e diazepam) e laxantes (bisacodil). As características relacionadas à coluna de separação (bifenil) favoreceram o estudo de um grande número de compostos. As condições otimizadas foram: acetato de amônio 10 mmol L–1, metanol 64 %, pH 4,0, 1,0 mL min –1, 40ºC, potencial de detecção +0,8 V. O segundo método, utilizando técnica voltamétrica de pulso no eletrodo de mercúrio em meio orgânico, abrange um total de 10 compostos farmacêuticos sendo ansiolíticos (alprazolam, bromazepam, clonazepam, clordiazepóxido, midazolam e diazepam), diuréticos (amilorida), antidepressivos (bupropiona) e anorexígenos (anfepramona e femproporex). As condições otimizadas foram: 0,01 mol L–1 NaClO4 em ACN, HMDE operando no modo pulso diferencial, velocidade varredura 30 mV/s. Dentre os dois métodos, um total de 20 fármacos podem ser estudados em amostras reais. Ambos os métodos foram validados de acordo com os parâmetros recomendados pela AOAC. Seletividade, linearidade, limites de detecção e quantificação, precisão e exatidão foram avaliados. O método cromatográfico (HPLC–PAD) foi aplicado em 81 amostras de suplementos alimentares comercializados no Brasil. 1,23 % das amostras apresentou sinal positivo para femproporex, 1,23 % para anfepramona, 6,17 % para ioimbina, 53,10 % para cafeína, 1,23 % para furosemida, 1,23 % para tadalafil e 9,87 % para diazepam. Deste total de amostras contendo fármacos declarados ou não, foram encontrados dois ou mais fármacos em aproximadamente 15 % dos suplementos analisados. A concentração encontrada dos fármacos variou de 0,20 a 866,88 mg/dose diária recomendada pelo fabricante. O método voltamétrico foi aplicável somente a amostras com diluições de no mínimo cem vezes, uma vez que há interferência da matriz nas reações redox no eletrodo de mercúrio. O grande diferencial deste trabalho consiste no rastreio de 20 fármacos como possíveis adulterantes em amostras de suplementos alimentares, devido as características da fase estacionária em cromatografia e ao meio não aquoso em voltametria.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasCarvalho, Leandro Machado dehttp://lattes.cnpq.br/6652387343920028Pilau, Eduardo Jorgehttp://lattes.cnpq.br/0859421816184957Stülp, Simonehttp://lattes.cnpq.br/1793007242678493Nascimento, Paulo Cícero dohttp://lattes.cnpq.br/7151513617218161Silva, Carine Vianahttp://lattes.cnpq.br/2004872342535591Muratt, Diana Tomazi2018-12-11T19:07:12Z2018-12-11T19:07:12Z2018-02-28info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/15074porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2018-12-12T05:02:26Zoai:repositorio.ufsm.br:1/15074Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2018-12-12T05:02:26Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica Study of the presence of drugs as adulterants in food supplements employing amperometric and voltametric detection |
title |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
spellingShingle |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica Muratt, Diana Tomazi Suplementos alimentares Cromatografia Detecção pulso–amperométrica Voltametria em meio orgânico Dietary supplements Chromatography Pulsed amperometric detection Non–aqueous voltammetry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
title_full |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
title_fullStr |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
title_full_unstemmed |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
title_sort |
Estudo da presença de fármacos como adulterantes em suplementos alimentares empregando detecção amperométrica e voltamétrica |
author |
Muratt, Diana Tomazi |
author_facet |
Muratt, Diana Tomazi |
author_role |
author |
dc.contributor.none.fl_str_mv |
Carvalho, Leandro Machado de http://lattes.cnpq.br/6652387343920028 Pilau, Eduardo Jorge http://lattes.cnpq.br/0859421816184957 Stülp, Simone http://lattes.cnpq.br/1793007242678493 Nascimento, Paulo Cícero do http://lattes.cnpq.br/7151513617218161 Silva, Carine Viana http://lattes.cnpq.br/2004872342535591 |
dc.contributor.author.fl_str_mv |
Muratt, Diana Tomazi |
dc.subject.por.fl_str_mv |
Suplementos alimentares Cromatografia Detecção pulso–amperométrica Voltametria em meio orgânico Dietary supplements Chromatography Pulsed amperometric detection Non–aqueous voltammetry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Suplementos alimentares Cromatografia Detecção pulso–amperométrica Voltametria em meio orgânico Dietary supplements Chromatography Pulsed amperometric detection Non–aqueous voltammetry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The use of food supplements grows around the world every day. In order to improve physical performance, prevent disease, maintain and improve health, obtain and / or maintain desired body weight and still fill nutritional gaps in the diet, many individuals consume these products even without proven efficacy or safety. As a result of the growth of this market, cases of adulteration by synthetic substances increase. This implies the need to develop rapid, sensitive, selective methodologies that reach a considerable number of drugs of analytical interest. In this work two methods of analysis of multi-drug classes are described. The method of chromatographic separation with pulse-amperometric detection comprises 15 drugs: anorexigenics (amfepramone and femproporex), stimulants (caffeine, yohimbine, sildenafil and tadalafil), diuretics (furosemide), antidepressants (fluoxetine and sertraline), anxiolytics (lorazepam, clonazepam, midazolam and diazepam) and laxatives (bisacodyl). The characteristics related to the separation column (biphenyl) favored the study of a large number of compounds. The optimized conditions were: ammonium acetate 10 mmol L-1, methanol 64%, pH 4.0, 1.0 mL min -1, 40ºC, detection potential +0.8 V. The second method, using voltammetric pulse technique on the mercury electrode in organic medium, comprises a total of 10 pharmaceutical compounds being anxiolytics (alprazolam, bromazepam, clonazepam, chlordiazepoxide, midazolam and diazepam), diuretics (amiloride), antidepressants (bupropion) and anorectics (amfepramone and femproporex). The optimized conditions were: 0.01 mol L-1 NaClO4 in ACN, HMDE operating in differential pulse mode, scanning speed 30 mV/s. Of the two methods, a total of 20 drugs can be studied in real samples. Both methods were validated according to AOAC recommended parameters. Selectivity, linearity, limits of detection and quantification, precision and accuracy were evaluated. The chromatographic method (HPLC-PAD) was applied in 81 samples of food supplements marketed in Brazil. 1.23% of the samples had a positive signal for femproporex, 1.23% for amfepramone, 6.17% for yohimbine, 53.10% for caffeine, 1.23% for furosemide, 1.23% for tadalafil and 9.87 % for diazepam. From this total of samples containing drugs declared or not, two or more drugs were found in approximately 15% of the supplements analyzed. The concentration of the drugs varied from 0.20 to 866.88 mg/daily dose recommended by the manufacturer. The voltammetric method was applied only to samples with dilutions of at least one hundred times, since there is interference of the matrix in the redox reactions in the mercury electrode. The great differential of this work is the screening of 20 drugs as possible adulterants in food supplement samples, due to the characteristics of the stationary phase in chromatography and to the non-aqueous medium in voltammetry. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-12-11T19:07:12Z 2018-12-11T19:07:12Z 2018-02-28 |
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 |
http://repositorio.ufsm.br/handle/1/15074 |
url |
http://repositorio.ufsm.br/handle/1/15074 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
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1805922077655433216 |