Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar

Detalhes bibliográficos
Ano de defesa: 2013
Autor(a) principal: Minetto, Luciane lattes
Orientador(a): Martins, Ayrton Figueiredo lattes
Banca de defesa: Arsand, Daniel Ricardo lattes, Primel, Ednei Gilberto lattes, Vasconcelos, Tibiriçá Gonçalves lattes, Martins, Manoel Leonardo lattes
Tipo de documento: Tese
Tipo de acesso: Acesso aberto
Idioma: por
Instituição de defesa: Universidade Federal de Santa Maria
Programa de Pós-Graduação: Programa de Pós-Graduação em Química
Departamento: Química
País: BR
Palavras-chave em Português:
Palavras-chave em Inglês:
Área do conhecimento CNPq:
Link de acesso: http://repositorio.ufsm.br/handle/1/4262
Resumo: Macrolide antibiotics are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. In the present study, it was developed and optimized a chromatographic method to assess the occurrence of macrolide antibiotics Azithromycin, Clarithromycin, Erythromycin and Roxithromycin in the effluent of the University Hospital of Santa Maria, in two sampling points, by applying high performance liquid chromatography coupled to mass detection with quadrupole ion trap (HPLC-MS/MS_QTrap) and clean-up/pre-concentration by solid phase extraction with the aid of Surface Methodology Response. The concentrations measured during a week in the hospital effluent were 1.32±0.13 and 0.22±0.06 μg L-1 for Azithromycin and Clarithromycin; in the receptor water sream was 1.12±0.20, 0.20±0.05 and 0.01±0.004 μg L-1 for Azithromycin, Clarithromycin and Erythromycin. Roxithromycin was not detected in all effluent samples. After this, it was done the evaluation of the risk quotient of the macrolide antibiotics. The value of the risk quotient for the hospital effluent for Azithromycin and Clarithromycin was 11 (high risk), and for the receptor water stream the risk quotient was 9.3 and 10.0 for Azithromycin and Clarithromycin; for Erythromycin, a quocient risk value of 0.5 (medium risk). For degradation of the antibiotics in aqueous solution, it was used UV-photolysis, by which the influence of pH (3-11) was evaluated. Azithromycin showed low degradation by acid pH; for other pH, as well, for all the other antibiotics, the degradation was above 70% after 60 min of treatment. It was conducted a kinetic study of the degradation process of macrolide antibiotics in different pHs, by which Azithromycin revealed a recalcitrant profile, and Roxithromycin, as the more easily degradable one. For identification of the products formed during the photolysis experiments it was used independent information acquisition and as precursor ions of fragments m/z 116 and 158, characteristic of the macrolide compounds, at three collision energies (30, 45, and 60 V). It was proposed fragmentation routes of the degradation products: 8 products for Azithromycin, 7 for Clarithromycin, 6 of Erythromycin and 8 Roxithromycin. Through the same experiments with independent information acquisition, it was investigated the presence of eventual metabolites in hospital effluent, and three metabolites were found. By applying photolysis to the hospital effluent fortified, at pH 7, it was observed that the degradation occurs above 80% for all compounds after 60 min of irradiation. It was observed the formation of degradation products previously determined by experiments in aqueous solution. It was also found three degradation products for Azithromycin, 2 for Clarithromycin, 1 for Erythromycin and 3 for Roxithromycin.
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spelling 2017-05-182017-05-182013-08-09MINETTO, Luciane. Macrolides antibiotics: determination and identification of metabolites and degradation subproducts in hospital effluent. 2013. 146 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/4262Macrolide antibiotics are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. In the present study, it was developed and optimized a chromatographic method to assess the occurrence of macrolide antibiotics Azithromycin, Clarithromycin, Erythromycin and Roxithromycin in the effluent of the University Hospital of Santa Maria, in two sampling points, by applying high performance liquid chromatography coupled to mass detection with quadrupole ion trap (HPLC-MS/MS_QTrap) and clean-up/pre-concentration by solid phase extraction with the aid of Surface Methodology Response. The concentrations measured during a week in the hospital effluent were 1.32±0.13 and 0.22±0.06 μg L-1 for Azithromycin and Clarithromycin; in the receptor water sream was 1.12±0.20, 0.20±0.05 and 0.01±0.004 μg L-1 for Azithromycin, Clarithromycin and Erythromycin. Roxithromycin was not detected in all effluent samples. After this, it was done the evaluation of the risk quotient of the macrolide antibiotics. The value of the risk quotient for the hospital effluent for Azithromycin and Clarithromycin was 11 (high risk), and for the receptor water stream the risk quotient was 9.3 and 10.0 for Azithromycin and Clarithromycin; for Erythromycin, a quocient risk value of 0.5 (medium risk). For degradation of the antibiotics in aqueous solution, it was used UV-photolysis, by which the influence of pH (3-11) was evaluated. Azithromycin showed low degradation by acid pH; for other pH, as well, for all the other antibiotics, the degradation was above 70% after 60 min of treatment. It was conducted a kinetic study of the degradation process of macrolide antibiotics in different pHs, by which Azithromycin revealed a recalcitrant profile, and Roxithromycin, as the more easily degradable one. For identification of the products formed during the photolysis experiments it was used independent information acquisition and as precursor ions of fragments m/z 116 and 158, characteristic of the macrolide compounds, at three collision energies (30, 45, and 60 V). It was proposed fragmentation routes of the degradation products: 8 products for Azithromycin, 7 for Clarithromycin, 6 of Erythromycin and 8 Roxithromycin. Through the same experiments with independent information acquisition, it was investigated the presence of eventual metabolites in hospital effluent, and three metabolites were found. By applying photolysis to the hospital effluent fortified, at pH 7, it was observed that the degradation occurs above 80% for all compounds after 60 min of irradiation. It was observed the formation of degradation products previously determined by experiments in aqueous solution. It was also found three degradation products for Azithromycin, 2 for Clarithromycin, 1 for Erythromycin and 3 for Roxithromycin.Os antibióticos macrolídeos são uma importante classe de fármacos preescritos no tratamento das mais variadas infecções, e como consequência se seu grande e continuo uso são comumente encontradas no ambiente. No presente estudo foi desenvolvido e otimizado método de cromatografia líquida de alta eficiência acoplada à detector de massas quadrupolo íon trap (HPLC-MS/MS_QTrap) e de clean-up/pré-concentração por extração em fase sólida com auxílio de Metodologia de Superfície de Resposta para avaliar a ocorrência dos antibióticos macrolídeos Azitromicina, Claritromicina, Eritromicina e Roxitromicina no efluente hospitalar do Hospital Universitário de Santa Maria em dois ponto de amostragem. As concentrações médias durante o ciclo de uma semana de amostragem no efluente do pronto atendimento foram de 1,32±0,13 e 0,22±0,06 g L-1 para Azitromicina e Claritromicina; no corpo recpetor foram de 1,12±0,20; 0,20±0,05 e 0,01±0,004 g L-1 para Azitromicina, Claritromicina e Eritromicina, respectivamente. Roxitromicina não foi detectada. Após foi feita a avaliação do quociente de risco dos antibióticos macrolídeos. O quociente de risco no efluente do pronto atendimento para Azitromicina e Claritromicina foi de 11, risco alto, o qual também foi evidenciado no corpo receptor com quociente de risco de 9,3 e 10 para Azitromicina e Claritromicna, e risco médio para Eritromicina de 0,5. Para degradação dos antibióticos foi utilizado fotólise artificial em solução aquosa, sendo avaliado a influência do pH de 3-11 na degradação destes compostos. Azitromicina apresentou baixa degradação em pH ácido, para os outros pH e demais compostos a degradação foi acima de 70% após 60 min de tratamento. Foi feito um estudo cinético do processo de degradação dos antibióticos macrolídeos em diferentes pH, observando-se que a Azitromicina apresentou um perfil recalcitrante para o processo, e Roxitromicina foi degradada com maior facilidade. Para a identificação dos produtos formados durante os experimentos de fotodegradação foram montados experimentos de informação independente de aquisição utilizando como íons precursores os íons de m/z 116 e 158 característicos dos compostos macrolídeos em três energias de colisão (30, 45 e 60 V). Foram identificadas e propostas rotas de fragmentação para 8 produtos de degradação de Azitromicina, 7 para Claritromicina, 6 para Eritromicina e 8 produtos de degradação de Roxiromicina. Através dos mesmos experimentos de informação independente de aquisição, foi investigada a presença de possíveis metabólitos no efluente hospitalar sendo encontrados 3 metabólitos. Com a aplicação de fotólise ao efluente hospitalar fortificado, em pH 7, observou-se que ocorre degradação acima de 80% para todos os compostos após 60 min de tratamneto. Foi observada a formação de produtos de degradação, que tinham sido previamente determinados em solução aquosa. Foram encontrados 3 produtos de degradação de Azitromicina, 2 para Claritromicina, 1 para Eritromicina e 3 produtos para Roxitromicina.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaAntibióticos macrolídeosEfluente hospitalarFotodegradaçãoProdutos de degradaçãoMetabólitosMacrolide antibioticsEffluent hospitalPhotodegradationDegradation productsMetabolitesCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAntibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalarMacrolides antibiotics: determination and identification of metabolites and degradation subproducts in hospital effluentinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, Ayrton Figueiredohttp://lattes.cnpq.br/2113532494494821Arsand, Daniel Ricardohttp://lattes.cnpq.br/2243464346389170Primel, Ednei Gilbertohttp://lattes.cnpq.br/3259602390948297Vasconcelos, Tibiriçá Gonçalveshttp://lattes.cnpq.br/6407925163803842Martins, Manoel Leonardohttp://lattes.cnpq.br/4404290090180984http://lattes.cnpq.br/4274099156631023Minetto, Luciane100600000000400300300300300300300ade6000d-a348-4d49-a531-6500a65a153af775fb47-cff7-44de-aa52-36571057f2c8f9f1fa17-342a-440a-be40-ce70604409130c786b4b-66ef-43b1-b48a-ab7b6b9c71d4cb7a3b79-c5a7-4353-ab4f-8f070c639dcdda593b38-50b4-45a4-b98d-2f9d0fa5d7f9info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALMINETTO, LUCIANE.pdfapplication/pdf2813769http://repositorio.ufsm.br/bitstream/1/4262/1/MINETTO%2c%20LUCIANE.pdf5dd6f07aa942b388af751e0d2ab23333MD51TEXTMINETTO, LUCIANE.pdf.txtMINETTO, LUCIANE.pdf.txtExtracted texttext/plain212264http://repositorio.ufsm.br/bitstream/1/4262/2/MINETTO%2c%20LUCIANE.pdf.txt248b15eec46cfe62decbb4e945b09c79MD52THUMBNAILMINETTO, LUCIANE.pdf.jpgMINETTO, LUCIANE.pdf.jpgIM Thumbnailimage/jpeg6125http://repositorio.ufsm.br/bitstream/1/4262/3/MINETTO%2c%20LUCIANE.pdf.jpg79742e2794546354d8f33a14558d2966MD531/42622022-06-03 09:54:28.396oai:repositorio.ufsm.br:1/4262Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132022-06-03T12:54:28Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
dc.title.alternative.eng.fl_str_mv Macrolides antibiotics: determination and identification of metabolites and degradation subproducts in hospital effluent
title Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
spellingShingle Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
Minetto, Luciane
Antibióticos macrolídeos
Efluente hospitalar
Fotodegradação
Produtos de degradação
Metabólitos
Macrolide antibiotics
Effluent hospital
Photodegradation
Degradation products
Metabolites
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
title_full Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
title_fullStr Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
title_full_unstemmed Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
title_sort Antibióticos macrolídeos: determinação e identificação de metabólitos e subprodutos de degradação em efluente hospitalar
author Minetto, Luciane
author_facet Minetto, Luciane
author_role author
dc.contributor.advisor1.fl_str_mv Martins, Ayrton Figueiredo
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/2113532494494821
dc.contributor.referee1.fl_str_mv Arsand, Daniel Ricardo
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/2243464346389170
dc.contributor.referee2.fl_str_mv Primel, Ednei Gilberto
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/3259602390948297
dc.contributor.referee3.fl_str_mv Vasconcelos, Tibiriçá Gonçalves
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/6407925163803842
dc.contributor.referee4.fl_str_mv Martins, Manoel Leonardo
dc.contributor.referee4Lattes.fl_str_mv http://lattes.cnpq.br/4404290090180984
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/4274099156631023
dc.contributor.author.fl_str_mv Minetto, Luciane
contributor_str_mv Martins, Ayrton Figueiredo
Arsand, Daniel Ricardo
Primel, Ednei Gilberto
Vasconcelos, Tibiriçá Gonçalves
Martins, Manoel Leonardo
dc.subject.por.fl_str_mv Antibióticos macrolídeos
Efluente hospitalar
Fotodegradação
Produtos de degradação
Metabólitos
topic Antibióticos macrolídeos
Efluente hospitalar
Fotodegradação
Produtos de degradação
Metabólitos
Macrolide antibiotics
Effluent hospital
Photodegradation
Degradation products
Metabolites
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Macrolide antibiotics
Effluent hospital
Photodegradation
Degradation products
Metabolites
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description Macrolide antibiotics are an important group of prescription drugs; as a consequence of the large and continuous use, they are commonly found in the environment. In the present study, it was developed and optimized a chromatographic method to assess the occurrence of macrolide antibiotics Azithromycin, Clarithromycin, Erythromycin and Roxithromycin in the effluent of the University Hospital of Santa Maria, in two sampling points, by applying high performance liquid chromatography coupled to mass detection with quadrupole ion trap (HPLC-MS/MS_QTrap) and clean-up/pre-concentration by solid phase extraction with the aid of Surface Methodology Response. The concentrations measured during a week in the hospital effluent were 1.32±0.13 and 0.22±0.06 μg L-1 for Azithromycin and Clarithromycin; in the receptor water sream was 1.12±0.20, 0.20±0.05 and 0.01±0.004 μg L-1 for Azithromycin, Clarithromycin and Erythromycin. Roxithromycin was not detected in all effluent samples. After this, it was done the evaluation of the risk quotient of the macrolide antibiotics. The value of the risk quotient for the hospital effluent for Azithromycin and Clarithromycin was 11 (high risk), and for the receptor water stream the risk quotient was 9.3 and 10.0 for Azithromycin and Clarithromycin; for Erythromycin, a quocient risk value of 0.5 (medium risk). For degradation of the antibiotics in aqueous solution, it was used UV-photolysis, by which the influence of pH (3-11) was evaluated. Azithromycin showed low degradation by acid pH; for other pH, as well, for all the other antibiotics, the degradation was above 70% after 60 min of treatment. It was conducted a kinetic study of the degradation process of macrolide antibiotics in different pHs, by which Azithromycin revealed a recalcitrant profile, and Roxithromycin, as the more easily degradable one. For identification of the products formed during the photolysis experiments it was used independent information acquisition and as precursor ions of fragments m/z 116 and 158, characteristic of the macrolide compounds, at three collision energies (30, 45, and 60 V). It was proposed fragmentation routes of the degradation products: 8 products for Azithromycin, 7 for Clarithromycin, 6 of Erythromycin and 8 Roxithromycin. Through the same experiments with independent information acquisition, it was investigated the presence of eventual metabolites in hospital effluent, and three metabolites were found. By applying photolysis to the hospital effluent fortified, at pH 7, it was observed that the degradation occurs above 80% for all compounds after 60 min of irradiation. It was observed the formation of degradation products previously determined by experiments in aqueous solution. It was also found three degradation products for Azithromycin, 2 for Clarithromycin, 1 for Erythromycin and 3 for Roxithromycin.
publishDate 2013
dc.date.issued.fl_str_mv 2013-08-09
dc.date.accessioned.fl_str_mv 2017-05-18
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dc.identifier.citation.fl_str_mv MINETTO, Luciane. Macrolides antibiotics: determination and identification of metabolites and degradation subproducts in hospital effluent. 2013. 146 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.
dc.identifier.uri.fl_str_mv http://repositorio.ufsm.br/handle/1/4262
identifier_str_mv MINETTO, Luciane. Macrolides antibiotics: determination and identification of metabolites and degradation subproducts in hospital effluent. 2013. 146 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.
url http://repositorio.ufsm.br/handle/1/4262
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