Hydrophilic and hydrophobic modifications of colloidal silica particles for Pickering emulsions.

Colloidal silica particles, functionalized with hydrophilic and hydrophobic groups, have been studied for utilization in particle-stabilized emulsions, so called Pickering emulsions. The amounts of attached groups have been characterized using NMR spectroscopy and elemental analysis. A range of particles were prepared, with sizes from around 13 to 70nm in diameter. Hydrophilic functionalization of the silica sols was achieved by attaching methyl poly(ethylene glycol) (mPEG) silane to the silica particle surface. This provides a reduction of surface charge density, a pH dependent and controllable flocculation behavior and surface activity. The hydrophobic functionalization of the silica sols was accomplished by attaching organosilanes containing mainly propyl and methyl groups. The emulsification abilities were evaluated by preparing Pickering emulsions using particles, with varying degrees and combinations of surface functionalization, as stabilizers and comparing the obtained emulsion droplet size distributions. It was found that colloidal silica functionalized with hydrophobic groups produced emulsions with smaller droplets compared to using unmodified silica. The emulsification performance was further improved by the combination of both hydrophilic and hydrophobic groups. All particles having this heterogeneous modification were found to generate emulsions with high stability towards coalescence (from five weeks to 1.5 years).

Surface activity and flocculation behavior of polyethylene glycol-functionalized silica nanoparticles.

Colloidal silica nanoparticles have been functionalized with methyl polyethylene glycol silane (mPEG silane) and the PEGylated particles have been characterized with focus on exploring their surface chemical properties. The degree of surface functionalization was quantified using NMR diffusometry, and the measurements showed that the silane binds covalently to the silica surface. Samples with surface coverages ranging from 0.068 to 0.315 µmol silane/m(2) have been analyzed. The functionalized particles proved to be surface active and showed a significant reduction in surface charge and zeta potential with increasing degree of PEG functionalization. All samples showed colloidal stability at neutral pH and above within the range studied. At lower pH, the samples with low surface coverage displayed a reversible flocculation behavior, while samples with a high surface coverage and samples without functionalization remained stable. This suggests that steric stabilization is effective at low pH when the surface coverage is high enough; electrostatic stabilization is effective for samples without functionalization; and that inter-particle PEG-silica interactions cause flocculation of particles with too low degrees of PEG functionalization.

Evaluation of a combined linear-nonlinear approach for column characterization using modern alkaline-stable columns as model.

This study investigates if deeper understanding is achieved when combining nonlinear and linear chromatographic column characterization methods. As test systems, two hybrid columns (Phenomenex Gemini-NX C18 and Kromasil Eternity C18) and one classic one (Kromasil-C18) were selected. The nonlinear methods were based on firm adsorption theory and involved determination of adsorption isotherms followed by calculations with a new numerical tool, adsorption energy distribution, on probe components at different pH values. The linear methods involved the hydrophobic subtraction model and selected probe components retention factors as a function of pH. The combined analysis indicated that both complementary and confirmative information can be achieved regarding the actual model systems.

Improvement in the generation of adsorption isotherm data in the elution by characteristic points method--the ECP-slope approach.

The elution by characteristic points (ECP) method is a very rapid and precise method for determination of the phase system equilibrium of phase systems in broad solute concentration ranges. Thus, the method is especially suitable for rapid characterization of high efficient separation systems. One important source of error, the effects by the post-loop dispersion, was eliminated in a recent investigation. In this study, the systematic error caused by the selection of the integration starting point at concentration equal to 0 is eliminated. This is done by developing and validating a new procedure for isotherm data generation; the ECP-slope method. The method generates raw slope data of the adsorption isotherm instead of raw adsorption data by integrations as the classical ECP does. Both numerical and experimental data were used for the comparison of the classical ECP approach with the slope-ECP method.