Emulsions complexity

Liu, F., Yang, J.P., Huang, L. and Liu, D. (1996a) Effect of non-ionic surfactants on the formation of DNA/emulsion complexes and emulsion-mediated gene transfer. Pharm. Res., 13, 1642-1646. 

PT through ELM 3 - No immobilizing wall - Comparatively high fluxes can be achieved - Small volume of membrane phase - Limited stability of emulsion - Swelling of emulsion - Complexity of the process - Resistance of the adsorption film of surfactant... 

Microbiological preservation was achieved by the inclusion of BKC, the only preservative found to be safe and effective. It was selected in spite of a known interaction between the drug anion and the benzalkonium cation, producing an insoluble emulsion complex of a yellow-brown colour, removed by filtration during manufacture. However, to compensate for the loss of BKC resulting from the filtration process, an excess was added during manufacture, so that 0.01 percent w/v remains in solution after removal of the complex. 

As shown in Figure 5.12, these authors prepared a model for capsule formation. When SDS is added to the oil/water emulsion, complexation occurs between SDS and the oppositely charged polyelectrolyte (gelatin). This complex deposits at the oil droplet/water interface in the form of a primary layer (Fig. 5.12, B). Addition of the second polyelectrolyte (gum arabic) to the system induces further complexation between the two polyelectrolytes and covering of the primary layer surface. It is observed that the addition of surfactant (SDS) increases the encapsulation yield (Fig. 5.13). 

The foregoing survey gives an indication of the complexity of emulsion systems and the wealth of experimental approaches available. We are limited here, however, to some selected aspects of a fairly straightforward nature. 

The energetics and kinetics of film formation appear to be especially important when two or more solutes are present, since now the matter of monolayer penetration or complex formation enters the picture (see Section IV-7). Schul-man and co-workers [77, 78], in particular, noted that especially stable emulsions result when the adsorbed film of surfactant material forms strong penetration complexes with a species present in the oil phase. The stabilizing effect of such mixed films may lie in their slow desorption or elevated viscosity. The dynamic effects of surfactant transport have been investigated by Shah and coworkers [22] who show the correlation between micellar lifetime and droplet size. More stable micelles are unable to rapidly transport surfactant from the bulk to the surface, and hence they support emulsions containing larger droplets. 

The importance of steric factors in the formation of penetration complexes is made evident by the observation that although sodium cetyl sulfate plus cetyl alcohol gives an excellent emulsion, the use of oleyl alcohol instead of cetyl alcohol leads to very poor emulsions. As illustrated in Fig. XIV-3, the explanation may lie in the difficulty in accommodating the kinked oleyl alcohol chain in the film. 

The HLB system has made it possible to organize a great deal of rather messy information and to plan fairly efficient systematic approaches to the optimiza-tion of emulsion preparation. If pursued too far, however, the system tends to lose itself in complexities [74]. It is not surprising that HLB numbers are not really additive their effective value depends on what particular oil phase is involved and the emulsion depends on volume fraction. Finally, the host of physical characteristics needed to describe an emulsion cannot be encapsulated by a single HLB number (note Ref. 75). 

The diluent portion also determines the form, or physical appearance, of the flavor, ie, Hquid, powder, or paste. Liquid flavor forms include water-soluble, oil-soluble, and emulsion forms powder flavor forms include plated (including dry solubles), extended, occluded, inclusion complexes, and other encapsulated forms and paste flavor forms include fat, protein, and carbohydrate-based paste. 

The newly formed short-chain radical A then quickly reacts with a monomer molecule to create a primary radical. If subsequent initiation is not fast, AX is considered an inhibitor. Many have studied the influence of chain-transfer reactions on emulsion polymerisation because of the interesting complexities arising from enhanced radical desorption rates from the growing polymer particles (64,65). Chain-transfer reactions are not limited to chain-transfer agents. Chain-transfer to monomer is ia many cases the main chain termination event ia emulsion polymerisation. Chain transfer to polymer leads to branching which can greatiy impact final product properties (66). 

Process Modeling. The complexity of emulsion polymerization makes rehable computer models valuable. Many attempts have been made to simulate the emulsion polymerization process for different monomer systems (76—78). 

Complex Coacervation. This process occurs ia aqueous media and is used primarily to encapsulate water-iminiscible Hquids or water-iasoluble soHds (7). In the complex coacervation of gelatin with gum arabic (Eig. 2), a water-iasoluble core material is dispersed to a desired drop size ia a warm gelatin solution. After gum arabic and water are added to this emulsion, pH of the aqueous phase is typically adjusted to pH 4.0—4.5. This causes a Hquid complex coacervate of gelatin, gum arabic, and water to form. When the coacervate adsorbs on the surface of the core material, a Hquid complex coacervate film surrounds the dispersed core material thereby forming embryo microcapsules. The system is cooled, often below 10°C, ia order to gel the Hquid coacervate sheU. Glutaraldehyde is added and allowed to chemically cross-link the capsule sheU. After treatment with glutaraldehyde, the capsules are either coated onto a substrate or dried to a free-flow powder. 

Less stable parts of the sludge can be treated by holding in tanks for extended periods of time to allow the weaker emulsion to break and separate a clean product. The mote stable sludges can be broken by mechanical action in filters or centrifuges, by recycle to the furnace for redistillation, or by redistillation in auxiliary units. Chemical attack via oxidation or complexing agents that break the emulsion has also been employed. 

Emulsion Polymerization. When the U.S. supply of natural mbber from the Far East was cut off in World War II, the emulsion polymerization process was developed to produce synthetic mbber. In this complex process, the organic monomer is emulsified with soap in an aqueous continuous phase. Because of the much smaller (<0.1 jira) dispersed particles than in suspension polymerization and the stabilizing action of the soap, a proper emulsion is stable, so agitation is not as critical. In classical emulsion polymerization, a water-soluble initiator is used. This, together with the small particle size, gives rise to very different kinetics (6,21—23). 

Most commercial aluminum formate is monobasic aluminum diformate because of the difficulties involved in triformate preparation. The main appHcation is in textile waterproofing. Aluminum formate reacts with casein to form a water-soluble complex, which can emulsify paraffin and certain other waxes. Fabrics immersed in these emulsions are rendered water repellent (26—28). 

Sihcone products dominate the pressure-sensitive adhesive release paper market, but other materials such as Quilon (E.I. du Pont de Nemours Co., Inc.), a Werner-type chromium complex, stearato chromic chloride [12768-56-8] are also used. Various base papers are used, including polyethylene-coated kraft as well as polymer substrates such as polyethylene or polyester film. Sihcone coatings that cross-link to form a film and also bond to the cellulose are used in various forms, such as solvent and solventless dispersions and emulsions. Technical requirements for the coated papers include good release, no contamination of the adhesive being protected, no blocking in roUs, good solvent holdout with respect to adhesives appHed from solvent, and good thermal and dimensional stabiUty (see Silicon COMPOUNDS, silicones). 

Neutral or alkaline salts, eg, KCl, K SO, K CO, or Na PO, are often present in synthetic latices in quantities of - <1%, based on the weight of the mbber. During emulsion polymerization the salts help control viscosity of the latex and, in the case of alkaline salts, the pH of the system. Many polymerizations are carried out at high pH, requiring the use of fixed alkaH, eg, KOH or NaOH. Very small amounts of ferrous salts can be employed as a component of the initiator system, in which case a sequesteriag agent, eg, ethyldiaminotetraacetic acid (EDTA) may be iacluded to complex the iron. Water-soluble shortstops, eg, potassium dithiocarbamate, may also be iacluded ia very small amounts (ca 0.1 parts). 

Sulfur Complexes. Silver compounds other than sulfide dissolve in excess thiosulfate. Stable silver complexes are also formed with thiourea. Except for the cyanide complexes, these sulfur complexes of silver are the most stable. In photography, solutions of sodium or ammonium thiosulfate fixers are used to solubilize silver hahdes present in processed photographic emulsions. When insoluble silver thiosulfate is dissolved in excess thiosulfate, various silver complexes form. At low thiosulfate concentrations, the principal silver species is Ag2(S203) 2j high thiosulfate concentrations, species such as Ag2(S203) 3 are present. Silver sulfide dissolves in alkaline sulfide solutions to form complex ions such as Ag(S 2 Ag(HS) 4. These ions are... 

Body washes are another more recent introduction into the marketplace. These products have become a mainstay in the European market and, in only a few years, have grown to be a significant fraction of the U.S. market. Body washes can be simple formulas similar to those used for Hquid handsoaps or complex 2-in-l oil-in-water emulsion, moisturizing formulations. These products contain a wide range of synthetic surfactants not typically found in bar... 

Emulsion Polymerization. Emulsion and suspension reactions are doubly heterogeneous the polymer is insoluble in the monomer and both are insoluble in water. Suspension reactions are similar in behavior to slurry reactors. Oil-soluble initiators are used, so the monomer—polymer droplet is like a small mass reaction. Emulsion polymerizations are more complex. Because the monomer is insoluble in the polymer particle, the simple Smith-Ewart theory does not apply (34). 

The kinetics of vinyl acetate emulsion polymeriza tion in the presence of alkyl phenyl ethoxylate surfactants of various chain lengths indicate that part of the emulsion polymerization occurs in the aqueous phase and part in the particles (115). A study of the emulsion polymerization of vinyl acetate in the presence of sodium lauryl sulfate reveals that a water-soluble poly(vinyl acetate)—sodium dodecyl sulfate polyelectrolyte complex forms, and that latex stabihty, polymer hydrolysis, and molecular weight are controlled by this phenomenon (116). 

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