| Texto completo | |
| Autor(es): |
Venturinelli Jannuzzi, Sergio Augusto
[1]
;
Martins, Bianca
[1]
;
Felisberti, Maria Isabel
[1]
;
Barboza Formiga, Andre Luiz
[1]
Número total de Autores: 4
|
| Afiliação do(s) autor(es): | [1] Univ Campinas UNICAMP, Inst Chem, BR-13083970 Campinas, SP - Brazil
Número total de Afiliações: 1
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Journal of Physical Chemistry B; v. 116, n. 51, p. 14933-14942, DEC 27 2012. |
| Citações Web of Science: | 11 |
| Resumo | |
The combination of organic and inorganic molecular building blocks gives rise to hybrid supramolecular materials showing properties from both chemical domains. This work presents the synthesis of metallopolymers made from poly(4-vinylpyridine) (P4VP) and pentacyanoferrate(II) at various polymer repeating unit/{[}Fe(CN)(5)](3-) ratios (py/Fe) and focuses on the influence of each block on the properties of the other. The solvatochromic shift of the {[}Fe(CN)(5)](3-) moiety was investigated as a function of the py/Fe ratio and the water molar fraction (X-H2O) of the ethanol/water medium. Asymmetric solvation favoring ethanol was enhanced as the py/Fe ratio increased. The results lead to a modification of the well-established thermodynamical model for asymmetrical solvation and suggest the formation of water-rich domains within the polymer coils with a large number of {[}Fe(CN)(5)](3-) units. From the macromolecular perspective, the increase of {[}Fe(CN)(5)](3-) units resulted in higher values of intrinsic viscosity, which is rationalized by the increase of the polymer coil charge density and therefore the increase in hydrodynamic volume due to repulsive electrical forces. Evaluating the intrinsic viscosity of a sample with py/Fe = 25 in solvent mixtures with different water molar fractions, it was found that the hydrodynamic volume is maximized at intermediate X-H2O values, where both the ethanol-soluble uncomplexed polymer block and the water-soluble {[}Fe(CN)(5)](3-)-pendant units can be suitably solvated, preventing coil shrinkage. (AU) | |
| Processo FAPESP: | 10/09127-5 - Estudo da interação entre nanotubos de carbono com metalopolímeros de poli(4-vinilpiridina) e pentacianoferrato |
| Beneficiário: | Bianca Fernandes Martins |
| Linha de fomento: | Bolsas no Brasil - Iniciação Científica |
| Processo FAPESP: | 09/11903-6 - Estratégia supramolecular de modificação de polímeros com azul da Prússia e análogos |
| Beneficiário: | Sergio Augusto Venturinelli Jannuzzi |
| Linha de fomento: | Bolsas no Brasil - Mestrado |