Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização
Autor(a) principal: | |
---|---|
Data de Publicação: | 2017 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/14029 |
Resumo: | This work presents the use of N-phenylamides as models for the study of self-association and intermolecular interactions. Obtaining the crystal of N-phenyltrifluoroacetamide allowed its diffraction and inclusion in the series to be studied. The N-phenylamides with H, CH3, (CH3)3, Ph, CF3, CCl3 and CBr3 substituents were used together with the supramolecular cluster approach to obtain topological and energetic data and to verify differences in crystalline packing. Analyzes were carried out through several tools including theoretical calculations at the ωB97X-D/cc-pVDZ level, molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and NMR. After the use of the tools, it was observed that the more energetic dimers were governed mainly by the hydrogen bond NH···O. Through the energy data, it was possible to propose crystallization mechanisms. Growth through chains in the early stages has been observed for almost all compounds, mainly due to the NH···O interaction, which helps to anchor molecules. Significant differences were observed between proposed mechanisms. For the solution study, 1H NMR spectroscopy was used in order to obtain the variation of the chemical displacements as a function of the concentration. By monitoring the amide hydrogen, it was possible to obtain the association constants of the molecules (Ka). The correlation of Ka data with the hydrogen bond strength (GNH···O) showed a good trend, showing a direct relationship between experimental and theoretical data. |
id |
UFSM-20_ca867dc403d2483b080259101dfb8524 |
---|---|
oai_identifier_str |
oai:repositorio.ufsm.br:1/14029 |
network_acronym_str |
UFSM-20 |
network_name_str |
Repositório Institucional Manancial UFSM |
repository_id_str |
3913 |
spelling |
2018-08-07T18:11:07Z2018-08-07T18:11:07Z2017-07-21http://repositorio.ufsm.br/handle/1/14029This work presents the use of N-phenylamides as models for the study of self-association and intermolecular interactions. Obtaining the crystal of N-phenyltrifluoroacetamide allowed its diffraction and inclusion in the series to be studied. The N-phenylamides with H, CH3, (CH3)3, Ph, CF3, CCl3 and CBr3 substituents were used together with the supramolecular cluster approach to obtain topological and energetic data and to verify differences in crystalline packing. Analyzes were carried out through several tools including theoretical calculations at the ωB97X-D/cc-pVDZ level, molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and NMR. After the use of the tools, it was observed that the more energetic dimers were governed mainly by the hydrogen bond NH···O. Through the energy data, it was possible to propose crystallization mechanisms. Growth through chains in the early stages has been observed for almost all compounds, mainly due to the NH···O interaction, which helps to anchor molecules. Significant differences were observed between proposed mechanisms. For the solution study, 1H NMR spectroscopy was used in order to obtain the variation of the chemical displacements as a function of the concentration. By monitoring the amide hydrogen, it was possible to obtain the association constants of the molecules (Ka). The correlation of Ka data with the hydrogen bond strength (GNH···O) showed a good trend, showing a direct relationship between experimental and theoretical data.Este trabalho apresenta a utilização de N-fenilamidas como modelos para o estudo da autoassociação e de interações intermoleculares. A obtenção do cristal do composto N-feniltrifluoracetamida permitiu a difração do mesmo e inclusão na série a ser estudada. As N-fenilamidas com substituintes H, CH3, (CH3)3, Ph, CF3, CCl3 e CBr3 foram utilizadas juntamente com a abordagem do cluster supramolecular, a fim de se obterem dados topológicos e energéticos e de se verificarem as diferenças no empacotamento cristalino. Foram realizadas análises através de diversas ferramentas, incluindo cálculos teóricos no nível ωB97X-D/cc-pVDZ, potencial eletrostático molecular (MEP), teoria quântica dos átomos em moléculas (QTAIM) e RMN. Após o emprego das ferramentas, observou-se que os dímeros mais energéticos formados nos arranjos foram regidos, principalmente, pela ligação de hidrogênio NH···O. Através dos dados energéticos, foi possível propor mecanismos de cristalização. O crescimento através de fitas, nos primeiros estágios, foi observado para quase todos os compostos, principalmente, devido à interação NH···O, que ajuda a ancorar as moléculas. Diferenças significativas foram observadas entre os mecanismos propostos. Para o estudo em solução, utilizou-se a espectroscopia de RMN de 1H com o intuito de se obterem as variações dos deslocamentos químicos em função da concentração. Monitorando-se a ressonância do hidrogênio da amida, foi possível obter as constantes de associação das moléculas (Ka). A correlação dos dados de Ka com a força da ligação de hidrogênio (GNH···O) apresentou uma boa tendência, mostrando uma relação direta entre dados experimentais e teóricos.porUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessN-fenilamidasLigação de hidrogênioQuímica supramolecularMecanismos de cristalizaçãoN-phenylamidesHydrogen bondSupramolecular chemistryCrystallization mechanismsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAutoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalizaçãoSelf-assembly of aromatic amides: supramolecular approach and crystallization mechanismsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisHörner, Manfredohttp://lattes.cnpq.br/8922528250830998Resende, Jarbas Magalhãeshttp://lattes.cnpq.br/4995867883627482Tirloni, Bárbarahttp://lattes.cnpq.br/2866324870100182http://lattes.cnpq.br/1160858609160308Pagliari, Anderson Berti1006000000006007e7796b1-053d-4bbe-8e62-e769f0da5cea8c03bba8-b5a6-481f-a86e-57c37bd7264269b1a367-c945-49b7-9f5f-e5d128197da7c1e37583-819e-4d38-bfe8-27059d8abef6reponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMCC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8804http://repositorio.ufsm.br/bitstream/1/14029/2/license_rdfc1efe8e24d7281448e873be30ea326ffMD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/14029/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD53ORIGINALDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdfDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdfDissertação de Mestradoapplication/pdf9496780http://repositorio.ufsm.br/bitstream/1/14029/1/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdfb83143fcf95fd8aa24ec5b96d2c9514cMD51TEXTDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.txtDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.txtExtracted texttext/plain214788http://repositorio.ufsm.br/bitstream/1/14029/4/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.txt16d122177767fac764b1200ba6728de1MD54THUMBNAILDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.jpgDIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.jpgIM Thumbnailimage/jpeg5620http://repositorio.ufsm.br/bitstream/1/14029/5/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.jpg303d60f00695d1422e3801ae6f448323MD551/140292018-08-07 15:11:07.198oai:repositorio.ufsm.br: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ório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132018-08-07T18:11:07Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
dc.title.alternative.eng.fl_str_mv |
Self-assembly of aromatic amides: supramolecular approach and crystallization mechanisms |
title |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
spellingShingle |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização Pagliari, Anderson Berti N-fenilamidas Ligação de hidrogênio Química supramolecular Mecanismos de cristalização N-phenylamides Hydrogen bond Supramolecular chemistry Crystallization mechanisms CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
title_full |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
title_fullStr |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
title_full_unstemmed |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
title_sort |
Autoassociação de amidas aromáticas: abordagem supramolecular e mecanismos de cristalização |
author |
Pagliari, Anderson Berti |
author_facet |
Pagliari, Anderson Berti |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Hörner, Manfredo |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/8922528250830998 |
dc.contributor.referee1.fl_str_mv |
Resende, Jarbas Magalhães |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/4995867883627482 |
dc.contributor.referee2.fl_str_mv |
Tirloni, Bárbara |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/2866324870100182 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/1160858609160308 |
dc.contributor.author.fl_str_mv |
Pagliari, Anderson Berti |
contributor_str_mv |
Hörner, Manfredo Resende, Jarbas Magalhães Tirloni, Bárbara |
dc.subject.por.fl_str_mv |
N-fenilamidas Ligação de hidrogênio Química supramolecular Mecanismos de cristalização |
topic |
N-fenilamidas Ligação de hidrogênio Química supramolecular Mecanismos de cristalização N-phenylamides Hydrogen bond Supramolecular chemistry Crystallization mechanisms CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
N-phenylamides Hydrogen bond Supramolecular chemistry Crystallization mechanisms |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the use of N-phenylamides as models for the study of self-association and intermolecular interactions. Obtaining the crystal of N-phenyltrifluoroacetamide allowed its diffraction and inclusion in the series to be studied. The N-phenylamides with H, CH3, (CH3)3, Ph, CF3, CCl3 and CBr3 substituents were used together with the supramolecular cluster approach to obtain topological and energetic data and to verify differences in crystalline packing. Analyzes were carried out through several tools including theoretical calculations at the ωB97X-D/cc-pVDZ level, molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and NMR. After the use of the tools, it was observed that the more energetic dimers were governed mainly by the hydrogen bond NH···O. Through the energy data, it was possible to propose crystallization mechanisms. Growth through chains in the early stages has been observed for almost all compounds, mainly due to the NH···O interaction, which helps to anchor molecules. Significant differences were observed between proposed mechanisms. For the solution study, 1H NMR spectroscopy was used in order to obtain the variation of the chemical displacements as a function of the concentration. By monitoring the amide hydrogen, it was possible to obtain the association constants of the molecules (Ka). The correlation of Ka data with the hydrogen bond strength (GNH···O) showed a good trend, showing a direct relationship between experimental and theoretical data. |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017-07-21 |
dc.date.accessioned.fl_str_mv |
2018-08-07T18:11:07Z |
dc.date.available.fl_str_mv |
2018-08-07T18:11:07Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/14029 |
url |
http://repositorio.ufsm.br/handle/1/14029 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
dc.relation.authority.fl_str_mv |
7e7796b1-053d-4bbe-8e62-e769f0da5cea 8c03bba8-b5a6-481f-a86e-57c37bd72642 69b1a367-c945-49b7-9f5f-e5d128197da7 c1e37583-819e-4d38-bfe8-27059d8abef6 |
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.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional Manancial 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 |
Repositório Institucional Manancial UFSM |
collection |
Repositório Institucional Manancial UFSM |
bitstream.url.fl_str_mv |
http://repositorio.ufsm.br/bitstream/1/14029/2/license_rdf http://repositorio.ufsm.br/bitstream/1/14029/3/license.txt http://repositorio.ufsm.br/bitstream/1/14029/1/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf http://repositorio.ufsm.br/bitstream/1/14029/4/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.txt http://repositorio.ufsm.br/bitstream/1/14029/5/DIS_PPGQUIMICA_2017_PAGLIARI_ANDERSON.pdf.jpg |
bitstream.checksum.fl_str_mv |
c1efe8e24d7281448e873be30ea326ff 2f0571ecee68693bd5cd3f17c1e075df b83143fcf95fd8aa24ec5b96d2c9514c 16d122177767fac764b1200ba6728de1 303d60f00695d1422e3801ae6f448323 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
ouvidoria@ufsm.br |
_version_ |
1808854709611528192 |