Micellization surface-active agents

Surface-active agents and hquids immiscible in water can form tiny dispersed units called reverse micelles. These can extract biochemicals from water or permit complexing or reacting in ways not possible in simple aqueous systems. 

The curve shown in Fig. 6 for sodium dodecyl sulfate is characteristic of ionic surfactants, which present a discontinuous and sharp increase of solubility at a particular temperature [80]. This temperature is known as the Krafft temperature. The Krafft temperature is defined by ISO as the temperature [in practice, a narrow range of temperatures] at which the solubility of ionic surface active agents rises sharply. At this temperature the solubility becomes equal to the critical micelle concentration (cmc). The curve of solubility vs. temperature intersects with the curve of the CMC vs. temperature at the Krafft temperature. 

The surface active agents (surfactants) may be cationic, anionic or non-ionic. Surfactants commonly used are cetyltrimethyl ammonium bromide (CTABr), sodium lauryl sulphate (NaLS) and triton-X, etc. The surfactants help to lower the surface tension at the monomer-water interface and also facilitate emulsification of the monomer in water. Because of their low solubility surfactants get fully dissolved or molecularly dispersed only at low concentrations and at higher concentrations micelles are formed. The highest concentration where in all the molecules are in dispersed state is known as critical micelle concentration (CMC). The CMC values of some surfactants are listed in table below. 

Surface-active agents used as adjuvants in pharmaceutical preparations to improve drug dissolution may affect the stability of /3-lactams. Thus, the presence of micelles of cetyl(trimethyl)ammonium bromide (CTAB) enhanced up to 50-fold the rate of alkaline hydrolysis of penicillins [140]. In the case of cephalosporins, micelle-promoted catalysis of the intramolecular degradation process (see Sect 5.2.2) was also observed [85][141], It has been proposed that the negatively charged penicillins and cephalosporins are attracted by the cationic micelles. This attraction increases substrate concentration in the micellar phase, in turn accelerating the rate of HO- ion attack. Ion exchange at the micellar surface and electrostatic stabilization of the transition state may also contribute to the increased rate [142][143],... 

The term mixed micelle refers to those micelles composed of two or more surface active agents. The sizes of micelles in a solution obey a distribution function that is characteristic of their chemical composition and the ionic nature of the solution in which they reside. 

At their critical micelle concentrations, surface active agents (such as sodium dodecyl sulfate, Triton X-100, lysolecithin, and bile salts) self-associate into spherical or rod-shaped structures. Because dilution to below the c.m.c. results in rapid disassembly or dissolution of these detergent micelles, micelles are in dynamic equilibrium with other dissolved detergent molecules in the bulk solution. 

Any conclusions about the organization of different components within the dispersions should take the ultrastructure of the systems into consideration. The surface-active agents that act as stabilizers for the nanoparticles are often able to form additional colloidal structures, such as vesicles or micelles, by self assembly. In addition to a potential importance in the formation and stability of the dispersions, such structures contain lipophilic domains that may represent alternative compartments for the localization of incorporated drugs. As a consequence, their presence may affect drug incorporation and release. 

However, emulsion polymerizations involve the formation of colloidal polymer particles that are essentially permanently suspended in the reaction medium. The reaction mechanism involves the migration of monomer molecules from liquid monomer droplets to sites of polymerization that originate in micelles consisting of surface-active agent molecules surrounding monomer molecules. Emulsion polymerizations are usually characterized by the requirement of surfactants during the initiation of the process and by the use of water-soluble initiators. This process also permits good control of the exothermic nature of the polymerization. 

In addition to lowering surface tension, surface-active agents contribute to emulsion stability by oriented adsorption at the interface and by formation of a protective film around the droplets. Apparently, the first molecules of a surfactant introduced into a two-phase system act to form a monolayer additional surfactant molecules tend to associate with each other, forming micelles, which stabilize the system by hydrophilic-lipophilic arrangements. This behavior has been depicted by Stutz et al. ( ) and is shown in Figures 1-5. 

The adsorption behavior of AB- or ABA-type block copolymers in which block A is polyelectrolytic and block B hydrophobic is very interesting. As expected, these polymers serve as dispersants, micelle-forming agents and surface-active agents. 

Micelles are colloidal dispersions that form spontaneously, under certain concentrations, from amphiphilic or surface-active agents (surfactants), molecules of which consist of two distinct regions with opposite afL nities toward a given solvent such as water (Torchilin, 2007). Micelles form when the concentration of these amphiphiles is above the critical micelle concentration (CMC). They consist of an inner core of assembled hydrophobic segments and an outer hydrophilic shell serving as a stabilizing interface between the hydrophobic core and the external aqueous environment. Micelles solubilize molecules of poorly soluble nonpolar pharmaceuticals within the micelle core, while polar molecules could be adsorbed on the micelle surface, and substances with intermediate polarity distributed along surfactant molecules in intermediate positions. 

Enhancement of the aqueous solubility by surfactants occurs as a result of the dual nature of the surfactant molecule. The term surfactant is derived from the concept of a surface-active agent. Surfactants typically contain discrete hydrophobic and hydrophilic regions, which allow them to orient at polar-nonpolar interfaces, such as water/air interfaces. Once the interface is saturated, th surfactants self-associate to form micelles and other aggregates, whereby their hydrophobic region are minimized and shielded from aqueous contact by their hydrophilic regions. This creates a discrete hydrophobic environment suitable forsolubilization of many hydrophobic compounds (Attwood and Florence, 1983 Li et al., 1999 Zhao et al., 1999). 

As expected, the influence of added nonelectrolytes can be quite different depending on whether the added compound is likely to be located in the micelles or in the in-termicellar solution. The effect of normal alcohols has been studied in detail for potassium dodecanoate the CMC is lowered for all alcohols studied but the effect increases considerably in going from ethanol to decanol (cf. Fig. 2.7). Hydrocarbons, like cyclohexane, n-heptane, toluene, and benzene, have been found to lower the CMC for many surfactants. Strongly hydrophilic substances, like dioxane and urea, have small and complex effects. At higher concentrations they markedly increase the CMC or even inhibit micelle formation. Addition of another similar surface-active agent generally gives a CMC in between the CMCs of the two surfactants. 

Critical micelle concentration. The concentration in solution at which a surface-active agent forms multimolecular aggregates which are in kinetic equilibrium with monomer. 

The physical properties of surface active agents differ from those of smaller or nonamphipathic molecules in one major aspect, namely, the abrupt changes in their properties above a critical concentration. This is illustrated in Fig. 1, in which a number of physical properties (surface tension, osmotic pressure, turbidity, solubilization, magnetic resonance, conductivity, and self-diffusion) are plotted as a function of concentration. All these properties (interfacial and bulk) show an abrupt change at a particular concentration, which is consistent with the fact that above this concentration, surface active ions or molecules in solution associate to form larger units. These association units are called micelles and the concentration at which this association phenomenon occurs is known as the critical micelle concentration (cmc). 

Throughout the discussion, the terms surface active agent, surfactant, and detergent are used interchangeably to refer to amphiphilic substances which form association colloids or micelles in solution. Amphiphilic substances or amphiphiles are molecules possessing distinct regions of hydrophobic and hydrophilic character. 

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