A novel approach to the emulsion encapsulation was developed by combining the advantages of direct encapsulation of a liquid colloidal core with the accuracy and multifunctionality of layer-by-layer polyelectrolyte deposition. Experimental data obtained for the model oil-in-water emulsion confirm unambiguously the alternating PE assembly in the capsule shell as well as the maintenance of the liquid colloidal core. Two different mechanisms of capsule destruction upon interaction with the solid substrate were observed and qualitatively explained. The proposed method can be easily generalized to the preparation of oil-filled capsules in various oil/water/polyelectrolyte systems important in the field of pharmacy, medicine, and food industry.
The thermodynamic model of a 2D solution developed earlier for protein monolayers at liquid interfaces is generalized for monolayers composed of micro- and nanoparticles. Surface pressure isotherms of particle monolayers published in the literature for a wide range of particles sizes (between 75 microm and 7.5 nm) are described by the theoretical model with one modification. The calculations of surface pressure pi on area A provide satisfactory agreement with the experimental data. The theory also yields reasonable cross-sectional area values of the solvent molecule water in the range between 0.12 and 0.18 nm2, which is almost independent of particle size. Also, the area per particle in a closely packed monolayer obtained from the theory is quite realistic.
The dynamic surface elasticity, dynamic surface tension, and ellipsometric angles of mixed aqueous poly(diallyldimethylammonium chloride)/sodium dodecylsulfate solutions (PDAC/SDS) have been measured as a function of time and surfactant concentration. This system represents a typical example of polyelectrolyte/surfactant complex formation and subsequent aggregation on the nanoscale. The oscillating barrier and oscillating drop methods sometimes led to different results. The surface viscoelasticity of mixed PDAC/SDS solutions are very close to those of mixed solutions of sodium polystyrenesulfonate and dodecyltrimethylammonium bromide but different from the results for some other polyelectrolyte/surfactant mixtures. The abrupt drop in surface elasticity when the surfactant molar concentration approaches the concentration of charged polyelectrolyte monomers is caused by the formation of microparticles in the adsorption layer. Aggregate formation in the solution bulk does not influence the surface properties significantly, except for a narrow concentration range where the aggregates form macroscopic flocks. The mechanism of the observed relaxation process is controlled by the mass exchange between the surface layer and the flocks attached to the liquid surface.
Tensiometry (the pendant drop technique), interfacial shear rheology, and ellipsometry have been used to study the effect of polar lipids that are generated during fat digestion on the behavior of lipases at the oil-water interface. Both Sn-1,3 regiospecific and nonregiospecific lipases have been used, and a noncatalytically active protein, beta-lacloglobulin, has been used as reference in the interfacial shear rheology experiments. The results from the pendant drop measurements and the interfacial rheology studies were in agreement with each other and demonstrated that the Sn-2 monoglyceride, which is one of the lipolysis products generated when a Sn-1,3 regiospecific lipase catalyzes triglyceride hydrolysis, is very interfacially active and efficiently expels the enzyme from the interface. Ellipsometry conducted at the liquid-liquid interface showed that the lipase forms a sublayer in the aqueous phase, just beneath the monoglyceride-covered interface. Sn-1/3 monoglycerides do not behave this way because they are rapidly degraded to fatty acid and glycerol and the fatty acid (or the fatty acid salt) does not have enough interfacial activity to expel the lipase from the interface. Since the lipases present in the gastrointestinal tract are highly Sn-1,3 regiospecific, we believe that the results obtained can be transferred to the in vivo situation. The formation of stable and amphiphilic Sn-2 monoglycerides can be seen as a self-regulatory process for fat digestion.
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