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1.
Langmuir ; 27(20): 12486-98, 2011 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-21894983

RESUMO

Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3 min. Molecular interpretations of the observed trends are proposed when possible. Surprisingly, in the course of our study we found experimentally that the drop shape analysis method (DSA method) shows a systematically lower surface elasticity, in comparison with the other two methods used: Langmuir trough and capillary pressure tensiometry with spherical drops. The possible reasons for the observed discrepancy are discussed, and the final conclusion is that the DSA method has specific problems and may give incorrect results when applied to study the dynamic properties of systems with high surface elasticity, such as adsorption layers of saponins, lipids, fatty acids, solid particles, and some proteins. The last conclusion is particularly important because the DSA method recently became the preferred method for the characterization of fluid interfaces because of its convenience.


Assuntos
Saponinas/química , Tensoativos/química , Adsorção , Modelos Moleculares , Estrutura Molecular , Reologia , Propriedades de Superfície
2.
Phys Rev Lett ; 101(25): 252502, 2008 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-19113701

RESUMO

High-precision mass and charge radius measurements on ;{17-22}Ne, including the proton-halo candidate 17Ne, have been performed with Penning trap mass spectrometry and collinear laser spectroscopy. The 17Ne mass uncertainty is improved by factor 50, and the charge radii of ;{17-19}Ne are determined for the first time. The fermionic molecular dynamics model explains the pronounced changes in the ground-state structure. It attributes the large charge radius of 17Ne to an extended proton configuration with an s;{2} component of about 40%. In 18Ne the smaller radius is due to a significantly smaller s;{2} component. The radii increase again for ;{19-22}Ne due to cluster admixtures.

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