Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas
Ano de defesa: | 2017 |
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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 São Carlos
Câmpus São Carlos |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química - PPGQ
|
Departamento: |
Não Informado pela instituição
|
País: |
Não Informado pela instituição
|
Palavras-chave em Português: | |
Área do conhecimento CNPq: | |
Link de acesso: | https://repositorio.ufscar.br/handle/ufscar/10331 |
Resumo: | Besides its properties as a “green solvent”, organic molecule Gamma-valerolactone is also a chiral compound, presenting potential applications in enantioselective processes. Once obtained the adequate parameters for liquid phase simulations, different computational models were employed in order to investigate how chirality influences its thermodynamic properties. Under thermodynamic equilibrium, neither energetic nor structural differences between GVL racemic mixture and its enantiomeric pure counterparts were observed. Analysis of the most stable dimers extracted from a Monte Carlo simulation of the racemic mixture revealed subtle interaction energy differences when homochiral (RR and SS) pairs were compared to heterochiral (RS and SR) pairs, which indicated a subtle energetic preference for the homochiral ones. On the other hand, significant chiral discrimination were obtained using nonequilibrium methods. Solvation process for both R and S enantiomers of 1-chloro-1-aminoethane (CAE) in liquid SGVL via Thermodynamic Perturbation Theory resulted in a chemical potential nearly 3;3 kJ mol-1 lower for R-CAE when compared to S-CAE, indicating that the utilization of GVL as a chiral liquid could increase the yield of processes involving chiral species in condensed phase. Binding process of GVL molecules giving rise to both homochiral (SS) and heterochiral (SR) dimers in vacuum, via Umbrella Sampling method, could show that although both pairs had similar binding free energy values, major differences could be observed on these free energy profiles when higher molecular contact was imposed by Umbrella Sampling spatial confinement. Such binding process of GVL molecules was also studied in both RGVL and SGVL liquids. Thus, although lower binding free energy values were obtained, a nearly 20 % difference could be observed due to solvent chirality. |
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Colombari, Felippe MarianoFreitas, Luiz Carlos Gomidehttp://lattes.cnpq.br/3461414255262928http://lattes.cnpq.br/91252847895257992018-08-07T12:50:53Z2018-08-07T12:50:53Z2017-07-21COLOMBARI, Felippe Mariano. Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10331.https://repositorio.ufscar.br/handle/ufscar/10331Besides its properties as a “green solvent”, organic molecule Gamma-valerolactone is also a chiral compound, presenting potential applications in enantioselective processes. Once obtained the adequate parameters for liquid phase simulations, different computational models were employed in order to investigate how chirality influences its thermodynamic properties. Under thermodynamic equilibrium, neither energetic nor structural differences between GVL racemic mixture and its enantiomeric pure counterparts were observed. Analysis of the most stable dimers extracted from a Monte Carlo simulation of the racemic mixture revealed subtle interaction energy differences when homochiral (RR and SS) pairs were compared to heterochiral (RS and SR) pairs, which indicated a subtle energetic preference for the homochiral ones. On the other hand, significant chiral discrimination were obtained using nonequilibrium methods. Solvation process for both R and S enantiomers of 1-chloro-1-aminoethane (CAE) in liquid SGVL via Thermodynamic Perturbation Theory resulted in a chemical potential nearly 3;3 kJ mol-1 lower for R-CAE when compared to S-CAE, indicating that the utilization of GVL as a chiral liquid could increase the yield of processes involving chiral species in condensed phase. Binding process of GVL molecules giving rise to both homochiral (SS) and heterochiral (SR) dimers in vacuum, via Umbrella Sampling method, could show that although both pairs had similar binding free energy values, major differences could be observed on these free energy profiles when higher molecular contact was imposed by Umbrella Sampling spatial confinement. Such binding process of GVL molecules was also studied in both RGVL and SGVL liquids. Thus, although lower binding free energy values were obtained, a nearly 20 % difference could be observed due to solvent chirality.A molécula orgânica Gama-valerolactona (GVL), além de possuir características que a classificam como “solvente verde”, é uma molécula quiral, apresentando potenciais aplicações em processos enantiosseletivos diversos. Uma vez refinados os parâmetros de simulação adequados para que dados termodinâmicos do líquido pudessem ser reproduzidos, diferentes modelos computacionais foram empregados na investigação do potencial deste líquido como meio quiral para químicos processos diversos. Em situações de equilíbrio termodinâmico não foram observadas diferenças energéticas ou estruturais quando líquidos enantiometicamente puros foram comparados com a mistura racêmica, tampouco foram observadas quaisquer diferenças nas interações entre enantiômeros R e S na mistura racêmica de GVL. A análise dos pares GVL-GVL mais estáveis extraídos ao longo de uma simulação de Monte Carlo da mistura racêmica foi capaz de revelar diferenças sutis nas energias de interação obtidas para pares homoquirais (R-R e S-S) e para pares heteroquirais (R-S e S-R), mostrando um sutil favorecimento energético para os pares homoquirais. Discriminação quiral mais significativa foi obtida com a utilização de métodos fora do equilíbrio termodinâmico. O processo de solvatação dos enantiômeros R e S da molécula quiral 1-cloro-1-aminoetano (CAE) no líquido quiral SGVL via Perturbação Termodinâmica resultou em um potencial químico cerca de −3,3 kJ mol −1 menor para enantiômero R-CAE, indicando que a utilização de GVL como líquido quiral tem a capacidade de aumentar o rendimento de processos que envolvam espécies quirais em fase condensada. Também foi estudado o processo de associação de pares GVL-GVL homoquirais (S-S) e heteroquirais (S-R) no vácuo com a utilização do método de Umbrella Sampling. Embora ambos os pares tenham apresentado valores praticamente iguais de energia livre para o processo de associação, puderam ser observadas diferenças significativas em situações de confinamento espacial, no qual a separação entre as moléculas é menor do que a distância de equilíbrio e há maior contato molecular. Com metodologia similar, o processo de associação de pares GVL-GVL homoquirais (R-R ou S-S) e heteroquirais (S-R) também foi estudado na presença de solvente RGVL ou SGVL. Assim, embora valores significativamente menores de energia livre tenham sido obtidos, diferenças de aproximadamente 20 % puderam ser observadas em função da quiralidade do solvente.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)porUniversidade Federal de São CarlosCâmpus São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarGama-valerolactonaSolventes verdes quiraisTeoria da perturbação termodinâmicaPotencial químicoPotencial de força médiaEnergia quirodiastálticaCIENCIAS EXATAS E DA TERRA::QUIMICAEstudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicasinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisOnlineinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINALmaster.pdfmaster.pdfTeseapplication/pdf3154370https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10331/1/master.pdfcbf4c2bb490536b280e798c12bbb00d9MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81957https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10331/3/license.txtae0398b6f8b235e40ad82cba6c50031dMD53TEXTmaster.pdf.txtmaster.pdf.txtExtracted texttext/plain178086https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10331/4/master.pdf.txt3c88de258f976d6aaf4057ff5e008ff0MD54THUMBNAILmaster.pdf.jpgmaster.pdf.jpgIM Thumbnailimage/jpeg9394https://{{ getenv "DSPACE_HOST" "repositorio.ufscar.br" }}/bitstream/ufscar/10331/5/master.pdf.jpg7a0ab9800e8d376a5a0369fcd743fe9fMD55ufscar/103312019-09-11 03:19:28.099oai:repositorio.ufscar.br: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Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-05-25T12:56:17.681718Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
title |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
spellingShingle |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas Colombari, Felippe Mariano Gama-valerolactona Solventes verdes quirais Teoria da perturbação termodinâmica Potencial químico Potencial de força média Energia quirodiastáltica CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
title_full |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
title_fullStr |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
title_full_unstemmed |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
title_sort |
Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas |
author |
Colombari, Felippe Mariano |
author_facet |
Colombari, Felippe Mariano |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/9125284789525799 |
dc.contributor.author.fl_str_mv |
Colombari, Felippe Mariano |
dc.contributor.advisor1.fl_str_mv |
Freitas, Luiz Carlos Gomide |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/3461414255262928 |
contributor_str_mv |
Freitas, Luiz Carlos Gomide |
dc.subject.por.fl_str_mv |
Gama-valerolactona Solventes verdes quirais Teoria da perturbação termodinâmica Potencial químico Potencial de força média Energia quirodiastáltica |
topic |
Gama-valerolactona Solventes verdes quirais Teoria da perturbação termodinâmica Potencial químico Potencial de força média Energia quirodiastáltica CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Besides its properties as a “green solvent”, organic molecule Gamma-valerolactone is also a chiral compound, presenting potential applications in enantioselective processes. Once obtained the adequate parameters for liquid phase simulations, different computational models were employed in order to investigate how chirality influences its thermodynamic properties. Under thermodynamic equilibrium, neither energetic nor structural differences between GVL racemic mixture and its enantiomeric pure counterparts were observed. Analysis of the most stable dimers extracted from a Monte Carlo simulation of the racemic mixture revealed subtle interaction energy differences when homochiral (RR and SS) pairs were compared to heterochiral (RS and SR) pairs, which indicated a subtle energetic preference for the homochiral ones. On the other hand, significant chiral discrimination were obtained using nonequilibrium methods. Solvation process for both R and S enantiomers of 1-chloro-1-aminoethane (CAE) in liquid SGVL via Thermodynamic Perturbation Theory resulted in a chemical potential nearly 3;3 kJ mol-1 lower for R-CAE when compared to S-CAE, indicating that the utilization of GVL as a chiral liquid could increase the yield of processes involving chiral species in condensed phase. Binding process of GVL molecules giving rise to both homochiral (SS) and heterochiral (SR) dimers in vacuum, via Umbrella Sampling method, could show that although both pairs had similar binding free energy values, major differences could be observed on these free energy profiles when higher molecular contact was imposed by Umbrella Sampling spatial confinement. Such binding process of GVL molecules was also studied in both RGVL and SGVL liquids. Thus, although lower binding free energy values were obtained, a nearly 20 % difference could be observed due to solvent chirality. |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017-07-21 |
dc.date.accessioned.fl_str_mv |
2018-08-07T12:50:53Z |
dc.date.available.fl_str_mv |
2018-08-07T12:50:53Z |
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 |
COLOMBARI, Felippe Mariano. Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10331. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/10331 |
identifier_str_mv |
COLOMBARI, Felippe Mariano. Estudo computacional do líquido GVL (Gama-valerolactona): Influência da quiralidade nas propriedades termodinâmicas. 2017. Tese (Doutorado em Química) – Universidade Federal de São Carlos, São Carlos, 2017. Disponível em: https://repositorio.ufscar.br/handle/ufscar/10331. |
url |
https://repositorio.ufscar.br/handle/ufscar/10331 |
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por |
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por |
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info:eu-repo/semantics/openAccess |
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openAccess |
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Universidade Federal de São Carlos Câmpus São Carlos |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química - PPGQ |
dc.publisher.initials.fl_str_mv |
UFSCar |
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Universidade Federal de São Carlos Câmpus São Carlos |
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