Estudo de N-metilformamida em meio não aquoso. O caso NMF-acetona
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Data
2011-05-02
Autores
Almeida, Glauco Garrido [UNESP]
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Editor
Universidade Estadual Paulista (Unesp)
Resumo
Apresenta-se neste trabalho o estudo das propriedades estruturais e termodinâmicas dos líquidos acetona (ACT), N-metilformamida (NMF) e de suas misturas, utilizando-se simulação computacional com método Monte Carlo. O estudo foi realizado com o intuito de se entender melhor os mecanismos moleculares envolvidos na estabilização enzimática em meios não aquosos, uma vez que há um aumento significativo no uso de biocatálise nas indústrias química e farmacêutica nos últimos anos. Os resultados estruturais obtidos para os líquidos puros foram comparados com os obtidos por difratometria de nêutrons com substituição isotópica e posterior refinamento por meio do método EPSR (refinamento estrutural por potencial empírico). As simulações foram feitas no ensemble isotérmico- isobárico com temperatura de 298 K e pressão de 1 atm. A energia de interação intermolecular foi calculada utilizando-se o potencial de pares clássico 6-12 Lennard-Jones somado ao potencial de Coulomb. Os valores teóricos obtidos para o calor de vaporização e densidade estão em bom acordo com os experimentais para os líquidos puros. Verificou-se uma boa concordância entre a estrutura teórica e experimental dos líquidos (especialmente para a NMF). Na análise dos líquidos puros foi constatada diferença estrutural e termodinâmica entre eles, sobretudo em decorrência da presença de ligações de hidrogênio na NMF e ausência destas na ACT. Para a mistura, observou-se uma maior energia de interação entre moléculas de NMF do que de ACT, devido à presença de ligações de hidrogênio na primeira. Verificou-se também a formação de ligações de hidrogênio entre moléculas dos dois líquidos, com um aumento da força de interação por ligações de hidrogênio encontradas entre moléculas de NMF à medida que se adiciona acetona...
This work presents the study of structural and thermodynamic properties of acetone (ACT) - N-methylformamide (NMF) mixtures using Monte Carlo simulation. The study has been performed in order to better understand the molecular mechanisms involved in the enzyme’s stabilization in no aqueous media, since there is a significant increase in the use of biocatalysis in pharmaceutical and chemical industries in recent years. The structural results obtained for the pure liquids were compared with those obtained by neutron diffraction with isotopic substitution and subsequent refinement by the EPSR (empirical potential refinement) method. The simulations were performed in the isothermal-isobaric ensemble with a temperature of 298 K and 1 atm. The intermolecular energy was calculated using the classical 6-12 Lennard-Jones plus Coulomb pair potential. The theoretical values obtained for the heat of vaporization and density are in good agreement with the experimental data for pure liquids. There was a good agreement between experimental and theoretical structure of liquids (especially for NMF). In the pure liquids’ analysis was found structural and thermodynamic differences among them, mainly due to the presence of hydrogen bonds in the NMF and the lack of it in the ACT. In the mixture, the interaction energy between the NMF molecules is larger than between the ACT molecules, also a consequence of the presence of hydrogen bonds in the first ones. It was also found the formation of hydrogen bonds between the two liquids, with an increase in the strength of hydrogen bond interaction between the NMF molecules as ACT was added due to some sort of solvophobic effect. The concentration’s influence on the dipolar correlation between the molecules of the liquid has been explored with discussion of the structure in the solvation shells in the mixture... (Complete abstract click electronic access below)
This work presents the study of structural and thermodynamic properties of acetone (ACT) - N-methylformamide (NMF) mixtures using Monte Carlo simulation. The study has been performed in order to better understand the molecular mechanisms involved in the enzyme’s stabilization in no aqueous media, since there is a significant increase in the use of biocatalysis in pharmaceutical and chemical industries in recent years. The structural results obtained for the pure liquids were compared with those obtained by neutron diffraction with isotopic substitution and subsequent refinement by the EPSR (empirical potential refinement) method. The simulations were performed in the isothermal-isobaric ensemble with a temperature of 298 K and 1 atm. The intermolecular energy was calculated using the classical 6-12 Lennard-Jones plus Coulomb pair potential. The theoretical values obtained for the heat of vaporization and density are in good agreement with the experimental data for pure liquids. There was a good agreement between experimental and theoretical structure of liquids (especially for NMF). In the pure liquids’ analysis was found structural and thermodynamic differences among them, mainly due to the presence of hydrogen bonds in the NMF and the lack of it in the ACT. In the mixture, the interaction energy between the NMF molecules is larger than between the ACT molecules, also a consequence of the presence of hydrogen bonds in the first ones. It was also found the formation of hydrogen bonds between the two liquids, with an increase in the strength of hydrogen bond interaction between the NMF molecules as ACT was added due to some sort of solvophobic effect. The concentration’s influence on the dipolar correlation between the molecules of the liquid has been explored with discussion of the structure in the solvation shells in the mixture... (Complete abstract click electronic access below)
Descrição
Palavras-chave
Acetona - Propriedades estruturais e termodinâmicas, Acetone - Structural and thermodynamic properties
Como citar
ALMEIDA, Glauco Garrido. Estudo de N-metilformamida em meio não aquoso. O caso NMF-acetona. 2011. 83 f. Dissertação (mestrado) – Universidade Estadual Paulista, Faculdade de Engenharia de Ilha Solteira, 2011.