Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos
Ano de defesa: | 2015 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
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: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4270 |
Resumo: | This thesis describes the studies carried out using the reagent 6- hydrazinonicotinic hydrazide for the synthesis of new trihalomethylated pyrazolylpyridine systems using the 4-alkoxy-4-alkyl(aryl/heteroaryl-1,1,1-trihaloalk-3-en-2- ones [CX3C(O)CH=CROCH3, in which R = CH3, C6H5, 4-CH3C6H4, 4-OCH3C6H4, 2- Furyl and X = F, Cl]. In four reactional steps, compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1Hpyrazol- 1-yl]nicotinohydrazides were isolated after the treatment of their respective methyl nicotinate hydrochlorides with hydrazine hydrate. Because of the synthetic potential of these molecules, afterwards, type [3 + 2] and type [4 + 1] cyclocondensation reactions were carried out to develop various polyheterocyclic systems. Initially, systems containing trihalomethylated bis-pyrazolyl-pyridine were sythesized in yields of 67 91% and in a following step, are subjected to intramolecular dehydration reactions in the midst pyridine/benzene and thionyl chloride. Furthermore, this study shows the synthetic routes of systems 5-alkyl(aryl)-1,3,4-oxadiazolylpyrazolyl- pyridinic, 2-thione-3H-1,3,4-oxadiazolyl-pyrazolyl-pyridinic. Subsequently, to illustrate the possibility of obtaining different heterocycles, we describe an example of the convertion of 1,3,4-oxadiazole-2(3H)-thione into 2H-1,2,4- triazole-3(4H)-thione. Still, we describe the synthesis of 6-(2-thione-3H-1,3,4- oxadiazole-5-yl)-3(4H)-thioxo-2H-1,2,4-triazolo[4,3-a]pyridine, when reagent 6- hydrazinonicotinic hydrazide reacts with carbon disulfide under basic conditions. In continuation of the study, we demonstrate the synthesis of N-(2,5-dimethyl- 1H-pirrole-1-yl)-6-[3-alkyl(aryl/heteroaryl)-5-trifluoromethyl-1H-pyrazole-1- yl]nicotineamides, obtained when pyrazolyl-nicotinohydrazides reacts with hexane-2,5- dione. Finally, cyclocondensation reactions using aryl-aldehydes or 1-feniletanone in compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1H-pyrazol-1-yl]nicotinohydrazides are described. In the second part of this study, the synthesized compounds were evaluated in vitro for antimicrobial activites by determining the minimal inhibitory concentration (MIC) and minimal lethal concentration (MLC) through broth microdilution against Gram-positive and Gram-negative bacteria and fungi of clinical interest; for their inhibitory activity of the acetylcholinesterase enzyme (AChE); for the antioxidant potential by the method of free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) and the total antioxidant capacity (TAC) of compounds was evaluated by the phosphomolybdenum assay. The compounds were characterized by 1H , 13C {1H}, 19F, COSY 90, DEPT 135, HSQC RMN Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GCMS), Liquid Chromatography coupled to Mass Spectrometry (LC-ESI-MS/MS), Infrared Spectroscopy (IR), X-Ray Diffraction and their purities determined by CHN Elemental Analysis. |
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2017-05-252017-05-252015-03-02MEIRA, Susiane Cavinatto. Synthesis and bioactivity of trihalomethylated pyrazolyl-pyridine substituted systems. 2015. 308 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015.http://repositorio.ufsm.br/handle/1/4270This thesis describes the studies carried out using the reagent 6- hydrazinonicotinic hydrazide for the synthesis of new trihalomethylated pyrazolylpyridine systems using the 4-alkoxy-4-alkyl(aryl/heteroaryl-1,1,1-trihaloalk-3-en-2- ones [CX3C(O)CH=CROCH3, in which R = CH3, C6H5, 4-CH3C6H4, 4-OCH3C6H4, 2- Furyl and X = F, Cl]. In four reactional steps, compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1Hpyrazol- 1-yl]nicotinohydrazides were isolated after the treatment of their respective methyl nicotinate hydrochlorides with hydrazine hydrate. Because of the synthetic potential of these molecules, afterwards, type [3 + 2] and type [4 + 1] cyclocondensation reactions were carried out to develop various polyheterocyclic systems. Initially, systems containing trihalomethylated bis-pyrazolyl-pyridine were sythesized in yields of 67 91% and in a following step, are subjected to intramolecular dehydration reactions in the midst pyridine/benzene and thionyl chloride. Furthermore, this study shows the synthetic routes of systems 5-alkyl(aryl)-1,3,4-oxadiazolylpyrazolyl- pyridinic, 2-thione-3H-1,3,4-oxadiazolyl-pyrazolyl-pyridinic. Subsequently, to illustrate the possibility of obtaining different heterocycles, we describe an example of the convertion of 1,3,4-oxadiazole-2(3H)-thione into 2H-1,2,4- triazole-3(4H)-thione. Still, we describe the synthesis of 6-(2-thione-3H-1,3,4- oxadiazole-5-yl)-3(4H)-thioxo-2H-1,2,4-triazolo[4,3-a]pyridine, when reagent 6- hydrazinonicotinic hydrazide reacts with carbon disulfide under basic conditions. In continuation of the study, we demonstrate the synthesis of N-(2,5-dimethyl- 1H-pirrole-1-yl)-6-[3-alkyl(aryl/heteroaryl)-5-trifluoromethyl-1H-pyrazole-1- yl]nicotineamides, obtained when pyrazolyl-nicotinohydrazides reacts with hexane-2,5- dione. Finally, cyclocondensation reactions using aryl-aldehydes or 1-feniletanone in compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1H-pyrazol-1-yl]nicotinohydrazides are described. In the second part of this study, the synthesized compounds were evaluated in vitro for antimicrobial activites by determining the minimal inhibitory concentration (MIC) and minimal lethal concentration (MLC) through broth microdilution against Gram-positive and Gram-negative bacteria and fungi of clinical interest; for their inhibitory activity of the acetylcholinesterase enzyme (AChE); for the antioxidant potential by the method of free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) and the total antioxidant capacity (TAC) of compounds was evaluated by the phosphomolybdenum assay. The compounds were characterized by 1H , 13C {1H}, 19F, COSY 90, DEPT 135, HSQC RMN Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GCMS), Liquid Chromatography coupled to Mass Spectrometry (LC-ESI-MS/MS), Infrared Spectroscopy (IR), X-Ray Diffraction and their purities determined by CHN Elemental Analysis.A presente tese descreve os estudos desenvolvidos empregando o reagente hidrazida 6-hidrazinonicotínica para a síntese de novos sistemas pirazolil-piridínicos trialometilados utilizando as 4-alcóxi-4-alquil(aril/heteroaril)-1,1,1-trialo-3-alquen-2- onas [CX3C(O)CHCROCH3, onde X= Cl, F; R= CH3, C6H5, 4-CH3C6H4, 4-OCH3C6H4, Fur-2-ila]. Em quatro etapas reacionais os compostos 6-[3-alquil(aril/heteroaril)-5- trifluormetil-1H-pirazol-1-il] nicotinoidrazidas foram isolados após o tratamento de seus respectivos metil-estéres com hidrazina hidratada. Em vista do potencial sintético destas moléculas, posteriormente, promoveram-se reações de ciclocondensação do tipo [3 + 2] e do tipo [4 + 1] para o desenvolvimento de diferentes sistemas poliheterocíclicos. Inicialmente, os sistemas contendo bis-pirazóis trialometilados foram sintetizados em rendimentos de 67 91% e em uma etapa posterior foram submetidos a reações de desidratação intramolecular em meio piridina/benzeno e cloreto de tionila. Ainda, neste trabalho é mostrada a rota sintética dos sistemas 5-alquil(aril)-1,3,4- oxadiazol-pirazolil-piridínico, 2-tiona-3H-1,3,4-oxadiazol-pirazolil-piridínico. Na sequencia, para exemplificar a possibilidade de obtenção de diferentes heterociclos, é descrito o exemplo da conversão de 1,3,4-oxadiazol-2(3H)-tiona a 2H-1,2,4-triazol- 3(4H)-tiona. Ainda, descreve a síntese de 6-(2-tiona-3H-1,3,4-oxadiazol-5-il)-3(4H)- tiona-2H-1,2,4-triazolo[4,3-a]piridina, quando o reagente hidrazida 6- hidrazinonicotínica reage com dissulfeto de carbono em meio básico. Em continuação do estudo, é demonstrada a síntese do N-(2,5-dimetil-1H-pirrol- 1-il)-6-[3-alquil(aril/heteroaril)-5-trifluormetil-1H-pirazol-1-il]nicotinamidas obtidas quando pirazolil-nicotinoidrazidas reagem com hexano-2,5-diona. Finalmente, são descritas reações de condensação no composto 6-[3-fenil-5-trifluormetil-1H-pirazol-1- il] nicotinoidrazidas utilizando aldeídos arilícos subtituídos ou acetofenona. Na segunda parte desse trabalho, os compostos sintetizados foram avaliados in vitro quanto à atividade antimicrobiana determinando a concentração mínima inibitória (CIM) e a concentração letal mínima (CLM) através do método por microdiluição em caldo frente a bactérias Gram-positivas e Gram-negativas e a fungos de interesse clínico; quanto à sua atividade inibitória da enzima acetilcolinesterase (AChE); e quando a seu potencial antioxidante pelo método do radical livre 2,2-difenil-1- picrilhidrazila (DPPH) e sua capacidade antioxidante total pelo método de fosfomolibdênio. A caracterização estrutural dos compostos foi realizada por Espectroscopia de RMN de 1H, 13C {1H}, 19F, COSY 90, DEPT 135, HSQC, Cromatografia Gasosa acoplada à Espectrometria de Massas (CG-EM), Cromatografia Líquida acoplada à Espectrometria de Massas (LC-ESI-MS/MS), Espectrometria de Massas de Alta Resolução (HMRS), Espectroscopia de Infravermelho (IV), Difração de Raios-X e suas purezas foram determinadas via Análise Elementar CHN.application/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídosSynthesis and bioactivity of trihalomethylated pyrazolyl-pyridine substituted systemsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Appelt, Helmoz Roseniaimhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723562D2Dalcol, Ionara Irionhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9Costa, Michelle Budkehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4739018Y3Rodrigues, Oscar Endrigo Dorneleshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6http://lattes.cnpq.br/2568211387303193Meira, Susiane Cavinatto10060000000040030030030030030050006c852ad-d805-43c3-99d6-93a6a86f507c5ecfaa7f-d65b-4970-a3cf-f2e533b6aec3860ad4f7-eed3-4629-9f37-0e78f2263bada40bb239-8ee1-458e-9d6a-c027ca35d1ff0bb46b37-f7f8-4803-b4a4-0c21f6c5b20b9dfccbe0-bd16-4e23-a1fb-8e55f871ce46info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALMEIRA, SUSIANE CAVINATTO.pdfapplication/pdf6409313http://repositorio.ufsm.br/bitstream/1/4270/1/MEIRA%2c%20SUSIANE%20CAVINATTO.pdf857238c47fcd092ee72654f1d52673d0MD51TEXTMEIRA, SUSIANE CAVINATTO.pdf.txtMEIRA, SUSIANE CAVINATTO.pdf.txtExtracted texttext/plain427954http://repositorio.ufsm.br/bitstream/1/4270/2/MEIRA%2c%20SUSIANE%20CAVINATTO.pdf.txtdcab7c92f5fb3e2a00c04a925a2e6054MD52THUMBNAILMEIRA, SUSIANE CAVINATTO.pdf.jpgMEIRA, SUSIANE CAVINATTO.pdf.jpgIM Thumbnailimage/jpeg5088http://repositorio.ufsm.br/bitstream/1/4270/3/MEIRA%2c%20SUSIANE%20CAVINATTO.pdf.jpg84f7ad3e982bbe5939c88e7cb3269bebMD531/42702017-07-25 11:05:15.15oai:repositorio.ufsm.br:1/4270Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:15Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
dc.title.alternative.eng.fl_str_mv |
Synthesis and bioactivity of trihalomethylated pyrazolyl-pyridine substituted systems |
title |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
spellingShingle |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos Meira, Susiane Cavinatto Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
title_full |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
title_fullStr |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
title_full_unstemmed |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
title_sort |
Síntese e bioatividade de sistemas pirazolil-piridínicos poli-heterocíclicos trialometil substituídos |
author |
Meira, Susiane Cavinatto |
author_facet |
Meira, Susiane Cavinatto |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.referee1.fl_str_mv |
Appelt, Helmoz Roseniaim |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723562D2 |
dc.contributor.referee2.fl_str_mv |
Dalcol, Ionara Irion |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4797864E9 |
dc.contributor.referee3.fl_str_mv |
Costa, Michelle Budke |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4739018Y3 |
dc.contributor.referee4.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2568211387303193 |
dc.contributor.author.fl_str_mv |
Meira, Susiane Cavinatto |
contributor_str_mv |
Bonacorso, Helio Gauze Appelt, Helmoz Roseniaim Dalcol, Ionara Irion Costa, Michelle Budke Rodrigues, Oscar Endrigo Dorneles |
dc.subject.por.fl_str_mv |
Química |
topic |
Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This thesis describes the studies carried out using the reagent 6- hydrazinonicotinic hydrazide for the synthesis of new trihalomethylated pyrazolylpyridine systems using the 4-alkoxy-4-alkyl(aryl/heteroaryl-1,1,1-trihaloalk-3-en-2- ones [CX3C(O)CH=CROCH3, in which R = CH3, C6H5, 4-CH3C6H4, 4-OCH3C6H4, 2- Furyl and X = F, Cl]. In four reactional steps, compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1Hpyrazol- 1-yl]nicotinohydrazides were isolated after the treatment of their respective methyl nicotinate hydrochlorides with hydrazine hydrate. Because of the synthetic potential of these molecules, afterwards, type [3 + 2] and type [4 + 1] cyclocondensation reactions were carried out to develop various polyheterocyclic systems. Initially, systems containing trihalomethylated bis-pyrazolyl-pyridine were sythesized in yields of 67 91% and in a following step, are subjected to intramolecular dehydration reactions in the midst pyridine/benzene and thionyl chloride. Furthermore, this study shows the synthetic routes of systems 5-alkyl(aryl)-1,3,4-oxadiazolylpyrazolyl- pyridinic, 2-thione-3H-1,3,4-oxadiazolyl-pyrazolyl-pyridinic. Subsequently, to illustrate the possibility of obtaining different heterocycles, we describe an example of the convertion of 1,3,4-oxadiazole-2(3H)-thione into 2H-1,2,4- triazole-3(4H)-thione. Still, we describe the synthesis of 6-(2-thione-3H-1,3,4- oxadiazole-5-yl)-3(4H)-thioxo-2H-1,2,4-triazolo[4,3-a]pyridine, when reagent 6- hydrazinonicotinic hydrazide reacts with carbon disulfide under basic conditions. In continuation of the study, we demonstrate the synthesis of N-(2,5-dimethyl- 1H-pirrole-1-yl)-6-[3-alkyl(aryl/heteroaryl)-5-trifluoromethyl-1H-pyrazole-1- yl]nicotineamides, obtained when pyrazolyl-nicotinohydrazides reacts with hexane-2,5- dione. Finally, cyclocondensation reactions using aryl-aldehydes or 1-feniletanone in compounds 6-[3-alkyl(aryl)-5-trifluoromethyl-1H-pyrazol-1-yl]nicotinohydrazides are described. In the second part of this study, the synthesized compounds were evaluated in vitro for antimicrobial activites by determining the minimal inhibitory concentration (MIC) and minimal lethal concentration (MLC) through broth microdilution against Gram-positive and Gram-negative bacteria and fungi of clinical interest; for their inhibitory activity of the acetylcholinesterase enzyme (AChE); for the antioxidant potential by the method of free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) and the total antioxidant capacity (TAC) of compounds was evaluated by the phosphomolybdenum assay. The compounds were characterized by 1H , 13C {1H}, 19F, COSY 90, DEPT 135, HSQC RMN Spectroscopy, Gas Chromatography coupled to Mass Spectrometry (GCMS), Liquid Chromatography coupled to Mass Spectrometry (LC-ESI-MS/MS), Infrared Spectroscopy (IR), X-Ray Diffraction and their purities determined by CHN Elemental Analysis. |
publishDate |
2015 |
dc.date.issued.fl_str_mv |
2015-03-02 |
dc.date.accessioned.fl_str_mv |
2017-05-25 |
dc.date.available.fl_str_mv |
2017-05-25 |
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.citation.fl_str_mv |
MEIRA, Susiane Cavinatto. Synthesis and bioactivity of trihalomethylated pyrazolyl-pyridine substituted systems. 2015. 308 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4270 |
identifier_str_mv |
MEIRA, Susiane Cavinatto. Synthesis and bioactivity of trihalomethylated pyrazolyl-pyridine substituted systems. 2015. 308 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2015. |
url |
http://repositorio.ufsm.br/handle/1/4270 |
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