resumo
The solvatochromic parameters characterizing the solvent dipolarity/polarizability (pi*), solvent hydrogen-bond donor acidity (alpha), and solvent hydrogen-bond acceptor basicity (beta) of aqueous media were measured in the coexisting phases of aqueous Dextran-Ficoll, Dextran-Ucon, Dextran-PEG, PEG-Ucon, Ficoll-Ucon, and Ficoll-PEG two-phase systems (ATPS). Ionic composition of each ATPS included 0.15 M KCl, 0.15 M KBr, 0.15 M NaBr, 0.1 M Na2SO4, and 0.1 M Li2SO4 in 0.01 M sodium phosphate buffer (NaPB), pH 7.4; and 0.01 M and 0.11 M sodium phosphate buffer, pH 7.4. Partition ratios of sodium salts of dinitrophenylated (DNP) amino acids with aliphatic side-chains (glycine, alanine, norvaline, norleucine, and alpha-amino-n-caprylic acid) were measured in all ATPSs, and the results were evaluated in terms of the differences between the relative hydrophobicity (parameter E) and the electrostatic properties (parameter C) of the aqueous media of the coexisting phases. It was established that parameter E is described by a linear combination of the differences between the solvent dipolarity/polarizability (Delta pi*) and between the solvent hydrogen-bond acidity (Delta alpha)of the media in the coexisting phases. Parameter C depends on the phase forming polymer pair and is shown to be described by a linear combination of three parameters: the differences between the solvent hydrogen-bond acidity (Delta alpha) and between the solvent hydrogen-bond basicity (Delta beta) of the media in the coexisting phases, and a measure of the effect of a given salt additive on the hydrogen bonds in water. This effect was represented by a parameter (Kb-l), characterizing the equilibrium between populations of hydrogen bonds with a bent hydrogen bond conformation and with linear hydrogen bond conformation affected by a given salt additive. (C) 2012 Elsevier B.V. All rights reserved.
palavras-chave
SOLVATION ENERGY RELATIONSHIP; BIPHASIC SYSTEMS; WATER-STRUCTURE; METHYLENE GROUP; LIQUID WATER; IONS; HYDRATION
categoria
Biochemistry & Molecular Biology; Chemistry
autores
Madeira, PP; Bessa, A; Alvares-Ribeiro, L; Aires-Barros, MR; Reis, CA; Rodrigues, AE; Zaslavsky, BY
nossos autores
Pedro António Palma Madeira
Investigador Júnioragradecimentos
Financial support for this work was in part provided by national research grant PTDC/EQU-EQU/112812/2009 for which the authors are thankful. A. Bessa acknowledges the scholarship within the Project PTDC/EQU-EQU/112812/2009 from Fundacao para a Ciencia e a Tecnologia (FCT). P.P. Madeira acknowledges the financial support (grant SFRH/BPD/45055/2008) from FCT.