Emulsion multilayered

Of special interest in liquid dispersions are the surface-active agents that tend to accumulate at air/ liquid, liquid/liquid, and/or solid/liquid interfaces. Surfactants can arrange themselves to form a coherent film surrounding the dispersed droplets (in emulsions) or suspended particles (in suspensions). This process is an oriented physical adsorption. Adsorption at the interface tends to increase with increasing thermodynamic activity of the surfactant in solution until a complete monolayer is formed at the interface or until the active sites are saturated with surfactant molecules. Also, a multilayer of adsorbed surfactant molecules may occur, resulting in more complex adsorption isotherms. 

Pidgeon, C., Hunt, A.H., and Dittrich, K. (1986) Formation of multilayered vesicles from water/organic-solvent (W/O) emulsions theory and practice. Pharm. Res. 3, 23-34. 

Artificial control of the monomer concentrations is possible by changing the monomer feed methods, which includes multishot, stage feed (19), and continuous feed. A multishot emulsion polymerization is expected to form multilayered particles if the monomers are chosen properly. When the layers are sufficiently thin, the particles exhibit unique thermal and mechanical properties. The stage feed system is shown in Figure 11.1.6. It makes it possible to produce particles having gradient composition of different monomer units. 

McClements, 2006 Anal et al., 2008). Different combinations of proteins and polysaccharides (e.g., P-lactoglobulin + pectin, carrageenan or alginate casein + pectin) have been investigated within the context of multilayer emulsion stabilization (Guzey and McClements, 2006). It seems that the main technical challenge associated with the utilization such complex formation for layer-by-layer emulsion stabilization is the avoidance of bridging flocculation (McClements, 2005, 2006). 

Guzey, D., McClements, D.J. (2006). Formation, stability and properties of multilayer emulsions for application in the food industry. Advances in Colloid and Interface Science, 128-130,227-248. 

Ogawa, S., Decker, E.A., McClements, D.J. (2004). Production and characterization of O/W emulsions containing droplets stabilized by lecithin-chitosan-pectin multilayered membranes. Journal of Agricultural and Food Chemistry, 52, 3595-3600. 

There are many other examples of the potential use of mixed systems of chitosan + surfactants to be found in the recent research literature. For instance, it has been established that chitosan-surfactant interactions can be successfully used for preparing emulsions stabilized by multilayer adsorbed films (Mun et al., 2006 Chuah et al., 2009). 

When a biopolymer mixture is either close to phase separation or lies in the composition space of liquid-liquid coexistence (see Figure 7.6a), the effect of thermodynamically unfavourable interactions is to induce biopolymer multilayer formation at the oil-water interface, as observed for the case of legumin + dextran (Dickinson and Semenova, 1992 Tsapkina et al, 1992). Figure 7.6b shows that there are three concentration regions describing the protein adsorption onto the emulsion droplets. The first one (Cprotein< 0.6 wt%) corresponds to incomplete saturation of the protein adsorption layer. The second concentration region (0.6 wt% < 6 proiem < 6 wt%) represents protein monolayer adsorption (T 2 mg m 2). And the third region (Cprotein > 6 wt%) relates to formation of adsorbed protein multilayers on the emulsion droplets. 

In accord with experiments on emulsions (Husband et al., 1997), the molecular configurations deduced from SCF calculations have demonstrated the crucial role of the cluster ( blob ) of 5 charged phosphoserine residues in p-casein in maintaining the steric stabilizing layer, whilst also preventing interfacial precipitation (multilayers). The mobility of this blob was demonstrated experimentally by P NMR measurements on P-casein-stabilized emulsions (ter Beek et al., 1996). It was inferred that, when the effective charge on the blob is reduced (by dephosphorylation) or screened (by salt addition), the macromolecular spring relaxes... 

Traditionally, monolayer and multilayer adsorption have been used in detergency, mineral processing, flotation, stability of food and pharmaceutical emulsions, and the like, and, as a consequence, the topics of this chapter have been a central part of colloid science. In recent years, however, research on monolayer and multilayer deposition has mushroomed rapidly because of significant new opportunities. 

Displacement of the protein from the adsorbed layer in o/w thin films shows very different behavior from its a/w counterpart. Although displacement of protein from the o/w interfaces initiates at approximately the same solution composition (i.e., R = 0.1), there is little evidence for the stepwise displacement observed in the a/w thin films. This observation is further confirmation of the monolayer versus multilayer structure at the o/w and a/w thin films. The displacement of /3-lg has also been investigated in oil-in-water emulsions of n-tetradecane [46,47], In these reports it was shown that the protein was not completely displaced until R = 10, which was considerably higher than R = 1 - 2 in Figure 22. This will be discussed further below. 

Our understanding of the influence of competitive adsorption on emulsion stability is less secure. Recent work has identified several marked differences between the adsorbed layer properties atair/water and oil/water interfaces (e.g., multilayer versus monolayer formation). Advancing our knowledge of the stabilization of emulsions by protein merits further investigation, since emulsions comprise a major sector of processed foods. If competitive adsorption of surfactants influences the stability of protein emulsions in a similar manner to foams, use of the strategies outlined above may be appropriate for controlling destabilization. 

Vaseline emulsion Wax emulsion Hollow fibers Polyethylene bag Multilayer strip... 

Surfactants also reduce the coalescence of emulsion droplets. The latter process occurs as a result of thinning and disruption of the liquid film between the droplets on their close approach. The latter causes surface fluctuations, which may increase in amplitude and the film may collapse at the thinnest part. This process is prevented by the presence of surfactants at the O/W interface, which reduce the fluctuations as a result of the Gibbs elasticity and/or interfacial viscosity. In addition, the strong repulsion between the surfactant layers (which could be electrostatic and/or steric) prevents close approach of the droplets, and this reduces any film fluctuations. In addition, surfactants may form multilayers at the O/W interface (lamellar liquid crystalline structures), and this prevents coalescence of the droplets. 

The coalescence or complete separation of an emulsion occurs when two particles approach each other and no barrier exists between them. This process is avoided by producing a strong condensed mixed monolayer film or a multilayer coating around the droplets. A stable W/O emulsion is produced from surfactants or a mixture of surfactants that have very long hydrocarbon chains. 

Oil-in-water emulsions lend themselves readily to the delivery of oils and oil-soluble bioactives. The surfactant or biopolymer provides a means of isolating and protecting the lipophihc cores. Many types of materials with emulsifying capacity have been used to encapsulate oils and oil-soluble bioactives in single and multiple emulsion systems. Multilayered interfaces have also been used to improve the robustness of microcapsules. 

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