Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose.
Ano de defesa: | 2012 |
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Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal Rural do Rio de Janeiro
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Programa de Pós-Graduação: |
Programa de P?s-Gradua??o em Qu?mica
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Departamento: |
Instituto de Ci?ncias Exatas
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País: |
Brasil
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Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | https://tede.ufrrj.br/jspui/handle/jspui/3764 |
Resumo: | Experimental results obtained for monosaccharides are always an average of the several conformations of the system. A theoretical study is necessary to obtain the most stable individual conformations. The goal of this work is to select the most stable conformers of D-mannose in aqueous solution at room temperature, and validate them by comparing the experimental value of specific rotation with those obtained from the selected conformations. We started from two initial conformations (? anomer and ? anomer), geometrically optimized in vacuum using B3LYP/6-31+G*. Starting from the respective anomeric initial geometries, 1458 possible conformations (729 ? + 729 ?) were obtained assuming that staggered conformations of the hydrogen atoms of hydroxyl groups with regard to the C-OH bond are energetically favored (3 (C1) x 3 (C2) x 3 (C3) x 3 (C4) x 3 (C5) x 3 (C6) = 729). Single-point calculations in vacuum were performed for all 1458 conformational possibilities using B3LYP/6-31+G *. 97 conformational possibilities were selected (those which had relative energy values lower than 10 kcal/mol, from the energy value of the initial geometry, taken as reference), and their geometry optimized in vacuum from B3LYP/6-31+G* calculations, which reduced the original set from 97 to 64 conformers. Geometry optimization and vibrational frequency calculations were performed and used to calculate the specific rotation for the system. The anomeric ratio value (?:?) obtained was 50:50. The result of rotameric abundance approached to the experimental data only for the gt rotamer. Two conformations presented a peculiar behavior when solvated: the relative abundance of ?_336661 conformation showed a drastic increase, while the conformation ?_111166 has decreased very much. Analyzing the solvation process, it was found that when we use the value of Gibbs free energy in solution without computing the entropy, there are changes in the values of the Boltzmann population, which can reproduce the experimental value of anomeric ratio (?:?), suggesting that the entropy for the system perhaps is not properly computed from the harmonic approximation. The specific rotation value also is closer to the experimental data when the new population values are used. |
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Silva, Clarissa Oliveira da014.109.957-71http://lattes.cnpq.br/3211933004567550Bruns, Roy EdwardBauerfeldt, Glauco Favilla057.775.217-03http://lattes.cnpq.br/9571154466212777Andrade, Renato Ramos de2020-07-28T18:55:12Z2012-03-06ANDRADE, Renato Ramos de. Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose.. 2012. 96 f. Disserta??o (Programa de P?s-Gradua??o em Qu?mica) - Universidade Federal Rural do Rio de Janeiro, Serop?dica.https://tede.ufrrj.br/jspui/handle/jspui/3764Experimental results obtained for monosaccharides are always an average of the several conformations of the system. A theoretical study is necessary to obtain the most stable individual conformations. The goal of this work is to select the most stable conformers of D-mannose in aqueous solution at room temperature, and validate them by comparing the experimental value of specific rotation with those obtained from the selected conformations. We started from two initial conformations (? anomer and ? anomer), geometrically optimized in vacuum using B3LYP/6-31+G*. Starting from the respective anomeric initial geometries, 1458 possible conformations (729 ? + 729 ?) were obtained assuming that staggered conformations of the hydrogen atoms of hydroxyl groups with regard to the C-OH bond are energetically favored (3 (C1) x 3 (C2) x 3 (C3) x 3 (C4) x 3 (C5) x 3 (C6) = 729). Single-point calculations in vacuum were performed for all 1458 conformational possibilities using B3LYP/6-31+G *. 97 conformational possibilities were selected (those which had relative energy values lower than 10 kcal/mol, from the energy value of the initial geometry, taken as reference), and their geometry optimized in vacuum from B3LYP/6-31+G* calculations, which reduced the original set from 97 to 64 conformers. Geometry optimization and vibrational frequency calculations were performed and used to calculate the specific rotation for the system. The anomeric ratio value (?:?) obtained was 50:50. The result of rotameric abundance approached to the experimental data only for the gt rotamer. Two conformations presented a peculiar behavior when solvated: the relative abundance of ?_336661 conformation showed a drastic increase, while the conformation ?_111166 has decreased very much. Analyzing the solvation process, it was found that when we use the value of Gibbs free energy in solution without computing the entropy, there are changes in the values of the Boltzmann population, which can reproduce the experimental value of anomeric ratio (?:?), suggesting that the entropy for the system perhaps is not properly computed from the harmonic approximation. The specific rotation value also is closer to the experimental data when the new population values are used.Os resultados obtidos experimentalmente para os monossacar?deos s?o sempre uma m?dia das v?rias conforma??es presentes no sistema. Faz-se necess?rio o estudo te?rico para obten??o individual das conforma??es mais est?veis. Diante disso o objetivo deste trabalho ? selecionar os conf?rmeros mais est?veis da D-manose em solu??o aquosa, na temperatura ambiente, e valid?-los atrav?s da compara??o com o valor de rota??o espec?fica experimental. Partiu-se de duas conforma??es iniciais (um an?mero ? e um an?mero ?), constru?das no v?cuo e geometricamente otimizadas utilizando B3LYP/6-31+G*. Partindo-se das respectivas geometrias anom?ricas iniciais, um total final de 1458 possibilidades conformacionais (729 ?+ 729 ?) foram obtidas supondo que somente posi??es estreladas para os ?tomos de hidrog?nio dos grupos hidroxila ao longo da liga??o C-OH s?o energeticamente favorecidas (3 (C1) x 3 (C2) x 3 (C3) x 3 (C4) x 3 (C5) x 3 (C6) = 729). C?lculos "single-point" no v?cuo foram realizados para as 1458 possibilidades conformacionais utilizando B3LYP/6-31+G*. 97 possibilidades conformacionais foram selecionadas (aquelas que apresentaram valor de energia relativa menor que 10 kcal/mol, tomando como referencia a respectiva geometria inicial) e tiveram a geometria otimizada no v?cuo utilizando B3LYP/6-31+G*, o que reduziu o conjunto de 97 possibilidades conformacionais para 64 conf?rmeros. C?lculos de otimiza??o de geometria e frequ?ncia vibracional foram realizados e calculou-se a rota??o espec?fica para o sistema.O valor de raz?o anom?rica (?:?) obtido foi 50:50. O resultado de abundancia rotam?rica se aproximou do dado experimental apenas para o rot?mero gt. Duas conforma??es apresentaram um comportamento um tanto peculiar na mudan?a do v?cuo para solu??o. A conforma??o ?_336661 apresentou um aumento dr?stico no seu valor de abundancia enquanto a conforma??o ?_111166 uma diminui??o. Analisando o processo de solvata??o, constatou-se que quando utiliza-se o valor de energia livre de Gibbs em solu??o sem computar a entropia, h? altera??o nos valores de popula??o de Boltzmann, que passam a reproduzir o valor experimental de raz?o anom?rica (?:?), indicando que a entropia para o sistema solvatado talvez n?o esteja sendo bem descrita. O resultado de rota??o especifica tamb?m aproxima-se do dado experimental, quando os novos valores de popula??o s?o utilizados.Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2020-07-28T18:55:11Z No. of bitstreams: 1 2012 - Renato Ramos de Andrade.pdf: 1828147 bytes, checksum: 247209edc6272eeb9f5d9dbd8317526d (MD5)Made available in DSpace on 2020-07-28T18:55:12Z (GMT). No. of bitstreams: 1 2012 - Renato Ramos de Andrade.pdf: 1828147 bytes, checksum: 247209edc6272eeb9f5d9dbd8317526d (MD5) Previous issue date: 2012-03-06Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico, CNPq, Brasil.application/pdfhttps://tede.ufrrj.br/retrieve/61372/2012%20-%20Renato%20Ramos%20de%20Andrade.pdf.jpgporUniversidade Federal Rural do Rio de JaneiroPrograma de P?s-Gradua??o em Qu?micaUFRRJBrasilInstituto de Ci?ncias Exatas1K. P. C. Vollhardt, N. E. Schore. Qu?mica Org?nica: Estrutura e Fun??o, 4? ed. Bookman, 2004. 2Devulapalle, K. S.; Segura, A. G.; Ferrer, M.; Alcalde, G. M.; Plou, F. J. Carbohyd. Res. 2004, 339, 1029. 3Veres-Bencomo, V.; Fernandez-Santana, V.; Hardy, E.; Toledo, M. E.; Rodriguez, M. C.; Heynngnezz, L., Rodrigues, A.; Baly, A., Herrera, L.; Izquierdo, W.; Villar, A.; Valdes, Y.; Cosme, V.; Deler, M. 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Chem., 29, 1249-1265. 87U. Schnupf, J. L. Willett, F. Momany. DFTMD studies of glucose and epimers: anomeric ratios, rotamer populations, and hydration energies. Carbohyd. Res., 2010, 345, 503?511. 88Andrade, Renato R.; da Silva, Clarissa O. Specific rotation as a property to validate monosaccharide conformations.Carbohyd.Res., v. 350, p. 62-67, 2012. 89Bates, F. J. Polarimetry, Saccharimetry and the Sugars, NBS Circular C440,U.S. Government Printing Office, Washington D.C., 1942, p. 762.Monossacar?deoraz?o anom?ricarota??o espec?ficaMonosaccharideanomeric ratiospecific rotationQu?micaEstudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose.Theoretical study for obtaining the most stable D-mannose conformers in aqueous solution.info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFRRJinstname:Universidade Federal Rural do Rio de Janeiro (UFRRJ)instacron:UFRRJTHUMBNAIL2012 - Renato Ramos de Andrade.pdf.jpg2012 - Renato Ramos de Andrade.pdf.jpgimage/jpeg1943http://localhost:8080/tede/bitstream/jspui/3764/4/2012+-+Renato+Ramos+de+Andrade.pdf.jpgcc73c4c239a4c332d642ba1e7c7a9fb2MD54TEXT2012 - Renato Ramos de Andrade.pdf.txt2012 - Renato Ramos de Andrade.pdf.txttext/plain168382http://localhost:8080/tede/bitstream/jspui/3764/3/2012+-+Renato+Ramos+de+Andrade.pdf.txt0005b0b23fd6aa84a5176b4f15869c4eMD53ORIGINAL2012 - Renato Ramos de Andrade.pdf2012 - Renato Ramos de Andrade.pdfapplication/pdf1828147http://localhost:8080/tede/bitstream/jspui/3764/2/2012+-+Renato+Ramos+de+Andrade.pdf247209edc6272eeb9f5d9dbd8317526dMD52LICENSElicense.txtlicense.txttext/plain; charset=utf-82089http://localhost:8080/tede/bitstream/jspui/3764/1/license.txt7b5ba3d2445355f386edab96125d42b7MD51jspui/37642022-08-02 13:58:05.536oai:localhost: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Biblioteca Digital de Teses e Dissertaçõeshttps://tede.ufrrj.br/PUBhttps://tede.ufrrj.br/oai/requestbibliot@ufrrj.br||bibliot@ufrrj.bropendoar:2022-08-02T16:58:05Biblioteca Digital de Teses e Dissertações da UFRRJ - Universidade Federal Rural do Rio de Janeiro (UFRRJ)false |
dc.title.por.fl_str_mv |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
dc.title.alternative.eng.fl_str_mv |
Theoretical study for obtaining the most stable D-mannose conformers in aqueous solution. |
title |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
spellingShingle |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. Andrade, Renato Ramos de Monossacar?deo raz?o anom?rica rota??o espec?fica Monosaccharide anomeric ratio specific rotation Qu?mica |
title_short |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
title_full |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
title_fullStr |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
title_full_unstemmed |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
title_sort |
Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose. |
author |
Andrade, Renato Ramos de |
author_facet |
Andrade, Renato Ramos de |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Silva, Clarissa Oliveira da |
dc.contributor.advisor1ID.fl_str_mv |
014.109.957-71 |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3211933004567550 |
dc.contributor.referee1.fl_str_mv |
Bruns, Roy Edward |
dc.contributor.referee2.fl_str_mv |
Bauerfeldt, Glauco Favilla |
dc.contributor.authorID.fl_str_mv |
057.775.217-03 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/9571154466212777 |
dc.contributor.author.fl_str_mv |
Andrade, Renato Ramos de |
contributor_str_mv |
Silva, Clarissa Oliveira da Bruns, Roy Edward Bauerfeldt, Glauco Favilla |
dc.subject.por.fl_str_mv |
Monossacar?deo raz?o anom?rica rota??o espec?fica |
topic |
Monossacar?deo raz?o anom?rica rota??o espec?fica Monosaccharide anomeric ratio specific rotation Qu?mica |
dc.subject.eng.fl_str_mv |
Monosaccharide anomeric ratio specific rotation |
dc.subject.cnpq.fl_str_mv |
Qu?mica |
description |
Experimental results obtained for monosaccharides are always an average of the several conformations of the system. A theoretical study is necessary to obtain the most stable individual conformations. The goal of this work is to select the most stable conformers of D-mannose in aqueous solution at room temperature, and validate them by comparing the experimental value of specific rotation with those obtained from the selected conformations. We started from two initial conformations (? anomer and ? anomer), geometrically optimized in vacuum using B3LYP/6-31+G*. Starting from the respective anomeric initial geometries, 1458 possible conformations (729 ? + 729 ?) were obtained assuming that staggered conformations of the hydrogen atoms of hydroxyl groups with regard to the C-OH bond are energetically favored (3 (C1) x 3 (C2) x 3 (C3) x 3 (C4) x 3 (C5) x 3 (C6) = 729). Single-point calculations in vacuum were performed for all 1458 conformational possibilities using B3LYP/6-31+G *. 97 conformational possibilities were selected (those which had relative energy values lower than 10 kcal/mol, from the energy value of the initial geometry, taken as reference), and their geometry optimized in vacuum from B3LYP/6-31+G* calculations, which reduced the original set from 97 to 64 conformers. Geometry optimization and vibrational frequency calculations were performed and used to calculate the specific rotation for the system. The anomeric ratio value (?:?) obtained was 50:50. The result of rotameric abundance approached to the experimental data only for the gt rotamer. Two conformations presented a peculiar behavior when solvated: the relative abundance of ?_336661 conformation showed a drastic increase, while the conformation ?_111166 has decreased very much. Analyzing the solvation process, it was found that when we use the value of Gibbs free energy in solution without computing the entropy, there are changes in the values of the Boltzmann population, which can reproduce the experimental value of anomeric ratio (?:?), suggesting that the entropy for the system perhaps is not properly computed from the harmonic approximation. The specific rotation value also is closer to the experimental data when the new population values are used. |
publishDate |
2012 |
dc.date.issued.fl_str_mv |
2012-03-06 |
dc.date.accessioned.fl_str_mv |
2020-07-28T18:55:12Z |
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 |
ANDRADE, Renato Ramos de. Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose.. 2012. 96 f. Disserta??o (Programa de P?s-Gradua??o em Qu?mica) - Universidade Federal Rural do Rio de Janeiro, Serop?dica. |
dc.identifier.uri.fl_str_mv |
https://tede.ufrrj.br/jspui/handle/jspui/3764 |
identifier_str_mv |
ANDRADE, Renato Ramos de. Estudo te?rico para obten??o dos conf?rmeros mais est?veis em solu??o aquosa para D-manose.. 2012. 96 f. Disserta??o (Programa de P?s-Gradua??o em Qu?mica) - Universidade Federal Rural do Rio de Janeiro, Serop?dica. |
url |
https://tede.ufrrj.br/jspui/handle/jspui/3764 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.references.por.fl_str_mv |
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