Micelles polymeric surfactants

Water-soluble initiator is added to the reaction mass, and radicals are generated which enter the micelles. Polymerization starts in the micelle, making it a growing polymer particle. As monomer within the particle converts to polymer, it is replenished by diffusion from the monomer droplets. The concentration of monomer in the particle remains as high as 5—7 molar. The growing polymer particles require more surfactant to remain stable, getting this from the uninitiated micelles. Stage I is complete once the micelles have disappeared, usually at or before 10% monomer conversion. 

In suspension polymerization, the monomer is agitated in a solvent to form droplets, and then stabilized through the use of surfactants to form micelles. The added initiator is soluble in the solvent such that the reaction is initiated at the skin of the micelle. Polymerization starts at the interface and proceeds towards the center of the droplet. Polystyrene and polyvinyl chloride are often produced via suspension polymerization processes. 

Oheme and co-workers investigated335 in an aqueous micellar system the asymmetric hydrogenation of a-amino acid precursors using optically active rhodium-phosphine complexes. Surfactants of different types significantly enhance both activity and enantioselectivity provided that the concentration of the surfactants is above the critical micelle concentration. The application of amphiphilized polymers and polymerized micelles as surfactants facilitates the phase separation after the reaction. Table 2 shows selected hydrogenation results with and without amphiphiles and with amphiphilized polymers for the reaction in Scheme 61.335... 

When micelles are used, the CE technique becomes a micellar elec-trokinetic chromatography (MEKC) one. Natural surfactants, such as bile salts, digitonin and saponins, optically active synthetic surfactants, e.g., amino-acid derived ones, alkylglycoside-, tartaric acid- and steroidal glucoside-based surfactants, and high-molecular mass or polymerized surfactants, have been used as chiral selectors in In the lat-... 

Zhu et al. coupled OT-CEC to ESI/MS for the analysis of /i-blockers and benzodiazepines. The authors described the use of a polymeric surfactant as a stationary-phase coating that enabled minimal surfactant introduction in the MS compared to MEKC—ESI/MS, thus avoiding interferences from non-voIatile micelles in ESI/MS. ... 

Exploiting ATRP as an enabling technology, we have recently synthesised a wide range of new, controlled-structure copolymers. These include (1) branched analogues of Pluronic non-ionic surfactants (2) schizophrenic polymeric surfactants which can form two types of micelles in aqueous solution (3) novel sulfate-based copolymers for use as crystal habit modifiers (4) zwitterionic diblock copolymers, which may prove to be interesting pigment dispersants. Each of these systems is discussed in turn below. 

One of the possible alternative to micelles are spherical dendrimers of diameter generally ranging between 5 and 10 nm. These are highly structured three-dimensional globular macromolecules composed of branched polymers covalently bonded to a central core [214]. Therefore, dendrimers are topologically similar to micelles, with the difference that the strnctnre of micelles is dynamic whereas that of dendrimers is static. Thus, unlike micelles, dendrimers are stable nnder a variety of experimental conditions. In addition, dendrimers have a defined nnmber of fnnctional end gronps that can be functionalized to prodnce psendostationary phases with different properties. Other psendostationary phases employed to address the limitations associated with the micellar phases mentioned above and to modnlate selectivity include water-soluble linear polymers, polymeric surfactants, and gemini snrfactant polymers. 

Hirai T, Watanabe T, Komasawa I (2000) Preparation of semiconductor nanoparticle-polymer composites by direct reverse micelle polymerization using polymerizable surfactants. J Phys Chem B 104 8962-8966... 

Description of the different mimetic systems will be the starting point of the presentation (Sect. 2). Preparation and characterization of monolayers (Langmuir films), Langmuir-Blodgett (LB) films, self-assembled (SA) mono-layers and multilayers, aqueous micelles, reversed micelles, microemulsions, surfactant vesicles, polymerized vesicles, polymeric vesicles, tubules, rods and related SA structures, bilayer lipid membranes (BLMs), cast multibilayers, polymers, polymeric membranes, and other systems will be delineated in sufficient detail to enable the neophyte to utilize these systems. Ample references will be provided to primary and secondary sources. 

The pH value will control the condensation of silica, so the pH value should be adjusted to form monomer then oligomer of silica in order to obtain its condensation and polymerization around the micelles of surfactant Under acidic conditions, silica source such as... 

The aggregation numbers Nagg is determined as 27 for C1-(EO)53-C4-VB and 38 for Cr(EO)53-C7-VB micelles by analysis of fluorescence curves. A micelle formation mechanism is proposed for nonionic polymeric surfactants with weakly hydrophobic groups. At low concentrations of PEO macromonomers, large loosely aggregated structures involving the PEO chains are formed. At higher concentrations normal micelles form. These are star-shaped, with a hydrophobic core surrounded by a corona of PEO chains. 

Short chain amphiphiles can be incorporated into the backbone of the polymer chains. The resulting graft macromolecules are able to form both intrachain and interchain aggregates. Polymeric surfactants assemble into a variety of intrachain micelles. These polymeric surfactants and/or amphiphilic polymacromonomers can also form mixed aggregates which incorporate free monomeric (macromonomer with a very small hydrophobic group) surfactants. 

Colloidal semiconductor particles were in situ generated and coated by catalysts in reversed micelles, surfactant vesicles and polymerized surfactant vesicles. 

Florence (1983) provide a comprehensive reference for the use of surfactants in drug formulation development. The treatment by Florence (1981) of drug solubilization in surfactant systems is more focused on the question at hand and provides a clear description of surfactant behavior and solubilization in conventional hydrocarbon-based surfactants, especially nonionic surfactants. This chapter will discuss the conventional surfactant micelles in general as well as update the reader on recent practical/commercial solubilization applications utilizing surfactants. Other uses of surfactants as wetting agents, emulsiLers, and surface modiLers, and for other pharmaceutical applications are nc emphasized. Readers can refer to other chapters in this book for details on these uses of surfactant Polymeric surfactant micelles will be discussed in Chapter 13, Micellization and Drug Solubility Enhancement Part II Polymeric Micelles. 

Gadelle et al. (1995) investigated the solubilization of various aromatic solutes irbfftRSS-b-PEO (ABA)/PPO-bPEO-bPPO (BAB) triblock copolymers. According to the experimental results, they indicated two different solubilization processes. To understand better the mechanism for solubilization in the polymeric surfactant solutions, it was postulated that (1) the addition of apolar solutes promotes micellization of the polymeric surfactant molecules, (2) the central core of the polymeric micelles contains some water molecules, and (3) solubilization is initially a replacement process in which water molecules are displaced from the micellar core bythesolubilizate. Adetailed discussion of the solubilization process can be found in the next section and the pharmaceutical application section of this chapter. 

As with traditional surfactants, additives may inLuence the onset of micellization of polymeric surfactants and thus affect solubilization. These additives can include inorganic salts and sugars used to adjust isotonicity and even the solubilizate drug itself. In addition to micellization, these additives can inLuence the LCST or CP and even the structure of micelles formed. 

In terms of solubilization ability, Gadelle et al. (1995) showed that there were distinct differences between conventional surfactant micelles and polymeric surfactant micelles. Solubilization in block... 

Polymer-based delivery systems (Fig. 11.1) include polymer-protein conjugates, polymer-drug conjugates, micelles consisting of polymeric surfactants, and complexes of cationic polymers and DNA (polyplexes).26... 

The extremely low CMCs have been advantageous for several applications, since only traces of polymer are required to form micelles. High dilution effects, that are problematic in the case of classical surfactants, do not alter polymeric micelles. The surface activity at the air - water, of the amphiphilic block copolymer or polymeric surfactants must be different from the classical surfactants, because of their much lower diffusion coefficients and their much complex conformations. 

The surfactant properties of polymeric silicone surfactants are markedly different from those of hydrocarbon polymeric surfactants such as the ethylene oxide/propylene oxide (EO/PO) block copolymers. Comparable silicone surfactants often give lower surface tension and silicone surfactants often self-assemble in aqueous solution to form bilayer phases and vesicles rather than micelles and gel phases. The skin feel and lubricity properties of silicone surfactants do not appear to have any parallel amongst hydrocarbon polymeric surfactants. 

Diblock copolymers consisting of soluble and insoluble parts (Fig. 2b) act much as grafted chains once they are adsorbed on the surface. However, the thermodynamics of the initial solution, consisting primarily of micelles, and the conformation of the insoluble blocks on the surface affect the coverage in ways not well understood (e.g., Munch and Gast, 1988 Marques et al., 1988 Gast, 1989). Many dispersants or polymeric surfactants are synthesized in this way (Reiss et al, 1987). 

If the surfactant concentration in a macroemulsion is greatly increased, or if the monomer concentration is greatly reduced, a microemulsion results. Microemulsions are thermodynamically stable systems in which all of the monomer resides within the micelles. At high surfactant concentration, the micelles may form a bicontinuous network, rather than discrete micelles. Polymerization (with water- or oil-soluble initiator) of the monomer within a microemulsion is referred to as microemulsion polymerization. The particles produced in this way are extremely small, ranging from 10 to 100 nm. 

Furthermore in contrast to classical low molecular weight surfactants, polymeric surfactants produce a number of latex particles of the same order of magnitude as the number of initial micelles. This can be attributed to the lower diffusion rate of these polymeric surfactant molecules during the emulsion polymerization process (, Baah, F., University of Haute Alsace, unpublished). 

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