Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos
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| Data de Publicação: | 2013 |
| Tipo de documento: | Dissertação |
| Idioma: | por |
| Título da fonte: | Biblioteca Digital de Teses e Dissertações da UFRRJ |
| Texto Completo: | https://tede.ufrrj.br/jspui/handle/jspui/3823 |
Resumo: | Formamide (FA) is the simplest model capable of mimicking the interactions that take place between peptides, proteins and DNA structures, so that the understanding of its acidbase chemistry is paramount. Its behavior as an acid has been investigated towards two biologically relevant bases: pyridine (Py) and pyridazine (PRD), by means of Raman spectra of ternary mixtures in several compositions. Molecular association extent values (1-a) reveal that the concentration of the 1:1 Py:FA adduct is always greater in the equilibrium as compared to the 1:2 PRD:FA complex, thus confirming that Py is the stronger base, following the trend exhibited by the Proton Affinity (P.A.) values reported for such azabenzenes. The thermodynamic parameters of the PRD/FA system have been determined through temperature dependent Raman experiments, and the comparison between the values determined in this study and those available for the Py/FA system confirmed the conclusions drawn from the concentration dependent investigation. Furthermore, the calculated DfG? values show that the whole process is not spontaneous, due to an extremely negative DfS? value, which is explained in terms of the two hydrogen bonds formed in the complex containing PRD. The basic behavior of FA has been evaluated through coordination reactions with main group metal cations Mg(II), Ca(II) and Al(III), aiming to predict the catalytic potential of the solvates towards neutral amide hydrolysis. This has been accomplished by monitoring the changes on the vibrational modes nCO e nCN of FA provoked by coordination. From the downshift of the former vibrational mode and upshift of the second vibration, it was possible to observe the formation of [Mg(FA)6](ClO4)2, whose ionic FA form (I) is present and has been regarded as the active intermediate in the most likely hydrolysis mechanism. The trend observed in the presence of Ca(II) is markedly different, since both vibrational modes are upshifted on the formation of [Ca(FA)4](ClO4)2, implying that the molecular FA structure (II) prevails. Coordination of FA to Al(III) leads to changes in many regions and allows the observation of metal-ligand (nAlO e nAlN) vibrations for the first time. Both nCO e nCN modes are upshifted, indicating that FA form II is stabilized upon formation of [Al(FA)5]Cl3, which is stable up to around 110?C. Stabilization of different FA structures seems to be related to the size of the studied ions as compared to the ion radius values of the transition metals. |
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Alves, Wagner de Assis012.536.367-29http://lattes.cnpq.br/5177340148368546Andrade, Gustavo F. S.Faria, Roberto B.002.022.197-55http://lattes.cnpq.br/1846610965418096Silva, Elaine Felix da2020-08-17T12:52:47Z2013-08-02SILVA, Elaine Felix da. Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos. 2013. 69 f. Disserta??o (Mestrado em Qu?mica) - Instituto de Ci?ncias Exatas, Universidade Federal Rural do Rio de Janeiro, Serop?dica, 2013.https://tede.ufrrj.br/jspui/handle/jspui/3823Formamide (FA) is the simplest model capable of mimicking the interactions that take place between peptides, proteins and DNA structures, so that the understanding of its acidbase chemistry is paramount. Its behavior as an acid has been investigated towards two biologically relevant bases: pyridine (Py) and pyridazine (PRD), by means of Raman spectra of ternary mixtures in several compositions. Molecular association extent values (1-a) reveal that the concentration of the 1:1 Py:FA adduct is always greater in the equilibrium as compared to the 1:2 PRD:FA complex, thus confirming that Py is the stronger base, following the trend exhibited by the Proton Affinity (P.A.) values reported for such azabenzenes. The thermodynamic parameters of the PRD/FA system have been determined through temperature dependent Raman experiments, and the comparison between the values determined in this study and those available for the Py/FA system confirmed the conclusions drawn from the concentration dependent investigation. Furthermore, the calculated DfG? values show that the whole process is not spontaneous, due to an extremely negative DfS? value, which is explained in terms of the two hydrogen bonds formed in the complex containing PRD. The basic behavior of FA has been evaluated through coordination reactions with main group metal cations Mg(II), Ca(II) and Al(III), aiming to predict the catalytic potential of the solvates towards neutral amide hydrolysis. This has been accomplished by monitoring the changes on the vibrational modes nCO e nCN of FA provoked by coordination. From the downshift of the former vibrational mode and upshift of the second vibration, it was possible to observe the formation of [Mg(FA)6](ClO4)2, whose ionic FA form (I) is present and has been regarded as the active intermediate in the most likely hydrolysis mechanism. The trend observed in the presence of Ca(II) is markedly different, since both vibrational modes are upshifted on the formation of [Ca(FA)4](ClO4)2, implying that the molecular FA structure (II) prevails. Coordination of FA to Al(III) leads to changes in many regions and allows the observation of metal-ligand (nAlO e nAlN) vibrations for the first time. Both nCO e nCN modes are upshifted, indicating that FA form II is stabilized upon formation of [Al(FA)5]Cl3, which is stable up to around 110?C. Stabilization of different FA structures seems to be related to the size of the studied ions as compared to the ion radius values of the transition metals.A mol?cula de formamida (FA) ? o modelo mais simples capaz de mimetizar as intera??es que ocorrem entre pept?deos, prote?nas e estruturas de DNA, portanto, o estudo de sua qu?mica ?cido-base torna-se essencial. Seu comportamento como ?cido foi estudado em presen?a de duas bases de import?ncia biol?gica: piridina (Py) e piridazina (PRD), atrav?s dos espectros Raman das solu??es tern?rias em diferentes concentra??es. Os valores de grau de associa??o (1-a) revelam que o aduto 1:1 Py:FA est? sempre em maior concentra??o no equil?brio quando comparado ao aduto 1:2 PRD:FA, indicando que Py ? a base mais forte, conforme sugerido pelos valores de Afinidade ao Pr?ton (A.P.). O estudo dos espectros Raman em diferentes temperaturas possibilitou a determina??o de par?metros termodin?micos para o sistema PRD/FA, cuja compara??o com os dados do sistema Py/FA corroborou a conclus?o do estudo dependente da concentra??o. Al?m disto, os valores de DfG? mostraram que o processo n?o ? espont?neo, devido ? contribui??o extremamente negativa de DfS?, que ? explicado pela presen?a das duas liga??es hidrog?nio no complexo com PRD. O comportamento b?sico de FA foi investigado atrav?s da forma??o de complexos com os ?ons Mg(II), Ca(II) e Al(III), como forma de prever a atividade catal?tica destes metais em rea??es de hidr?lise neutra de amidas, atrav?s do monitoramento das mudan?as provocadas aos modos nCO e nCN de FA, pela complexa??o. Foi poss?vel observar, a partir do ?downshift? do primeiro modo vibracional e ?upshift? do segundo, a forma??o do complexo [Mg(FA)6](ClO4)2, onde a estrutura i?nica (I) de FA est? presente, a qual ? considerada como a esp?cie ativa no mecanismo mais prov?vel de hidr?lise. O comportamento observado em presen?a de Ca(II) ? diferente, onde ambos os modos vibracionais de FA sofrem ?upshifts? pela forma??o do complexo [Ca(FA)4(ClO4)2], indicando que a estrutura molecular (II) da amida ? favorecida. A coordena??o de FA ao Al(III) provoca mudan?as em v?rias regi?es do espectro e permite a observa??o dos modos vibracionais metal-ligante, in?ditos nos sistemas anteriores. Ambos os modos nCO e nCN da amida sofrem ?upshifts?, indicando que a estrutura II ? estabilizada pela forma??o do complexo [Al(FA)5]Cl3, que ? est?vel at? cerca de 110?C. A estabiliza??o das diferentes estruturas de FA parece estar relacionada aos tamanhos relativos dos ?ons estudados, quando comparados aos valores de raio dos ?ons de metais de transi??o.Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2020-08-17T12:52:47Z No. of bitstreams: 1 2013 - Elaine Felix da Silva.pdf: 826124 bytes, checksum: c91b6a0f45d60d3bf8d73c39d7e44e0a (MD5)Made available in DSpace on 2020-08-17T12:52:47Z (GMT). No. of bitstreams: 1 2013 - Elaine Felix da Silva.pdf: 826124 bytes, checksum: c91b6a0f45d60d3bf8d73c39d7e44e0a (MD5) Previous issue date: 2013-08-02Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior, CAPES, Brasil.application/pdfhttps://tede.ufrrj.br/retrieve/61650/2013%20-%20Elaine%20Felix%20da%20Silva.pdf.jpgporUniversidade Federal Rural do Rio de JaneiroPrograma de P?s-Gradua??o em Qu?micaUFRRJBrasilInstituto de Ci?ncias Exatas[1] Huheey, J. E., Keiter, E. A., Keiter, R. L. Inorganic Chemistry: Principles of Structure and Reactivity. 4? edi??o. 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| dc.title.por.fl_str_mv |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| dc.title.alternative.eng.fl_str_mv |
Vibrational investigation on the amphoteric behavior of formamide: a model compound to biological systems |
| title |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| spellingShingle |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos Silva, Elaine Felix da formamida rea??es ?cido-base espectroscopia vibracional formamide acid-base reactions vibrational spectroscopy Qu?mica |
| title_short |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| title_full |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| title_fullStr |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| title_full_unstemmed |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| title_sort |
Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos |
| author |
Silva, Elaine Felix da |
| author_facet |
Silva, Elaine Felix da |
| author_role |
author |
| dc.contributor.advisor1.fl_str_mv |
Alves, Wagner de Assis |
| dc.contributor.advisor1ID.fl_str_mv |
012.536.367-29 |
| dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/5177340148368546 |
| dc.contributor.referee1.fl_str_mv |
Andrade, Gustavo F. S. |
| dc.contributor.referee2.fl_str_mv |
Faria, Roberto B. |
| dc.contributor.authorID.fl_str_mv |
002.022.197-55 |
| dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/1846610965418096 |
| dc.contributor.author.fl_str_mv |
Silva, Elaine Felix da |
| contributor_str_mv |
Alves, Wagner de Assis Andrade, Gustavo F. S. Faria, Roberto B. |
| dc.subject.por.fl_str_mv |
formamida rea??es ?cido-base espectroscopia vibracional |
| topic |
formamida rea??es ?cido-base espectroscopia vibracional formamide acid-base reactions vibrational spectroscopy Qu?mica |
| dc.subject.eng.fl_str_mv |
formamide acid-base reactions vibrational spectroscopy |
| dc.subject.cnpq.fl_str_mv |
Qu?mica |
| description |
Formamide (FA) is the simplest model capable of mimicking the interactions that take place between peptides, proteins and DNA structures, so that the understanding of its acidbase chemistry is paramount. Its behavior as an acid has been investigated towards two biologically relevant bases: pyridine (Py) and pyridazine (PRD), by means of Raman spectra of ternary mixtures in several compositions. Molecular association extent values (1-a) reveal that the concentration of the 1:1 Py:FA adduct is always greater in the equilibrium as compared to the 1:2 PRD:FA complex, thus confirming that Py is the stronger base, following the trend exhibited by the Proton Affinity (P.A.) values reported for such azabenzenes. The thermodynamic parameters of the PRD/FA system have been determined through temperature dependent Raman experiments, and the comparison between the values determined in this study and those available for the Py/FA system confirmed the conclusions drawn from the concentration dependent investigation. Furthermore, the calculated DfG? values show that the whole process is not spontaneous, due to an extremely negative DfS? value, which is explained in terms of the two hydrogen bonds formed in the complex containing PRD. The basic behavior of FA has been evaluated through coordination reactions with main group metal cations Mg(II), Ca(II) and Al(III), aiming to predict the catalytic potential of the solvates towards neutral amide hydrolysis. This has been accomplished by monitoring the changes on the vibrational modes nCO e nCN of FA provoked by coordination. From the downshift of the former vibrational mode and upshift of the second vibration, it was possible to observe the formation of [Mg(FA)6](ClO4)2, whose ionic FA form (I) is present and has been regarded as the active intermediate in the most likely hydrolysis mechanism. The trend observed in the presence of Ca(II) is markedly different, since both vibrational modes are upshifted on the formation of [Ca(FA)4](ClO4)2, implying that the molecular FA structure (II) prevails. Coordination of FA to Al(III) leads to changes in many regions and allows the observation of metal-ligand (nAlO e nAlN) vibrations for the first time. Both nCO e nCN modes are upshifted, indicating that FA form II is stabilized upon formation of [Al(FA)5]Cl3, which is stable up to around 110?C. Stabilization of different FA structures seems to be related to the size of the studied ions as compared to the ion radius values of the transition metals. |
| publishDate |
2013 |
| dc.date.issued.fl_str_mv |
2013-08-02 |
| dc.date.accessioned.fl_str_mv |
2020-08-17T12:52:47Z |
| 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.citation.fl_str_mv |
SILVA, Elaine Felix da. Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos. 2013. 69 f. Disserta??o (Mestrado em Qu?mica) - Instituto de Ci?ncias Exatas, Universidade Federal Rural do Rio de Janeiro, Serop?dica, 2013. |
| dc.identifier.uri.fl_str_mv |
https://tede.ufrrj.br/jspui/handle/jspui/3823 |
| identifier_str_mv |
SILVA, Elaine Felix da. Investiga??o vibracional do comportamento anf?tero de formamida: um composto modelo para sistemas biol?gicos. 2013. 69 f. Disserta??o (Mestrado em Qu?mica) - Instituto de Ci?ncias Exatas, Universidade Federal Rural do Rio de Janeiro, Serop?dica, 2013. |
| url |
https://tede.ufrrj.br/jspui/handle/jspui/3823 |
| dc.language.iso.fl_str_mv |
por |
| language |
por |
| dc.relation.references.por.fl_str_mv |
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