Surfactants, polymerizable

While most vesicles are formed from double-tail amphiphiles such as lipids, they can also be made from some single chain fatty acids [73], surfactant-cosurfactant mixtures [71], and bola (two-headed) amphiphiles [74]. In addition to the more common spherical shells, tubular vesicles have been observed in DMPC-alcohol mixtures [70]. Polymerizable lipids allow photo- or chemical polymerization that can sometimes stabilize the vesicle [65] however, the structural change in the bilayer on polymerization can cause giant vesicles to bud into smaller shells [76]. Multivesicular liposomes are collections of hundreds of bilayer enclosed water-filled compartments that are suitable for localized drug delivery [77]. The structures of these water-in-water vesicles resemble those of foams (see Section XIV-7) with the polyhedral structure persisting down to molecular dimensions as shown in Fig. XV-11. 

Surfactants provide temporary emulsion droplet stabilization of monomer droplets in tire two-phase reaction mixture obtained in emulsion polymerization. A cartoon of tliis process is given in figure C2.3.11. There we see tliat a reservoir of polymerizable monomer exists in a relatively large droplet (of tire order of tire size of tire wavelengtli of light or larger) kinetically stabilized by surfactant. 

Very large solvent effects arc also observed for systems where the monomers can aggregate either with themselves or another species. For example, the apparent kp for polymerizable surfactants, such as certain vinyl pyridinium salts and alkyl salts of dimethylaminoalkyl methacrylates, in aqueous solution above the critical micelle concentration (cmc) are dramatically higher than they are below the cmc in water or in non-aqueous media.77 This docs not mean that the value for the kp is higher. The heterogeneity of the medium needs to be considered. In the micellar system, the effective concentration of double bonds in the vicinity of the... 

Akelah andMoet [62] followed a modified approach to prepare PS-clay intercalated nanocomposites using a solvent to facilitate intercalation. MMT was ion exchanged using a polymerizable surfactant, vinylbenzyltrimethylammonium chloride. Acetonitrile was found to be the most effective solvent, producing a d-spacing of 2.45 mn versus 2.22 and... 

An extraordinary way of stabilizing RUO2-coated CdS colloids for H2 generation was chosen by Fendler and co-workers The colloidal particles were generated in situ in surfactant vesicles of dioctadecyldimethylammonium chloride and dihexa-decyl phosphate. Thiophenol as a membrane permeable electron donor acted as a sacrificial additive. Later, a surface active re-usable electron donor (n-C,gH3,)2N — (CHj)—CH2—CHj—SH, Br was incorporated into the vesicles. Its R—SS—R oxidation product could be chemically reduced by NaBH to regenerate the active electron donor. The H2 yields in these systems were only 0.5 %. However, yields up to 10% were later reported for a system in which CdS was incorporated into a polymerizable styrene moiety, (n-C,jH3jC02(CH2)2) N (CH3) (CH2CgH4CH=CH2>, CP, and benzyl alcohol was used as the electron donor. 

Microgels which have been prepared in emulsions or microemulsion have a more compact structure than those obtained by polymerization in solution. For microemulsion copolymerization, preferentially self-emulsifying comonomers, such as unsaturated polyesters, are used as polymerizable surfactants, because no emulsifier must be removed after the reaction. By choosing suitable monomer combinations the composition, size and structure of microgels can be widely varied, thus adjusting these macromolecules to special applications. 

Taniguchi T, Takeuchi N, Kobaru S, Nakahira T (2008) Preparation of highly monodisperse fluorescent polymer particles by miniemulsion polymerization of styrene with a polymerizable surfactant. J Colloid Interface Sci 327 58-62... 

The first type is a standard polysoap derived from a polymerizable surfactant leading to poly(sodium 11-acryloyloxyundecane-l-sulfonate) PSl whereas the second polysoap is an alternating copolymer of maleic acid anhydride and acrylamide leading to a polymer with carboxylic acid groups and hydrophobic n-alkylamide groups PS2 (see Fig. 6.9). The organometaUic catalyst was not covalently bound to the polysoaps in the catalytic experiments. 

Another approach to producing latexes with chemically bound surface-active groups is to use a reactive surfactant—a surfactant with a polymerizable double bond, such as sodium dodecyl allyl sulfosuccinate [Wang et al., 2001a,b,c]. Copolymerization of the reactive surfactant with the monomer of interest binds the surface active groups into the polymer chains. 

K. Stabler, J. Selb, F. Candau, Multicompartment polymeric micelles based on hydrocarbon and fluorocarbon polymerizable surfactants, Langmuir 15 (1999) 7565-7576. 

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... 

In 1985 Tyminski etal. [55, 56] reported that two-component lipid vesicles of a neutral phospholipid, e.g. DOPC, and a neutral polymerizable PC, bis-DenPC (15), formed stable homogeneous bilayer vesicles prior to photopolymerization. After photopolymerization of a homogeneous 1 1 molar lipid mixture, the lipid vesicles were titrated with bovine rhodopsin-octyl glucoside micelles in a manner that maintained the octyl glucoside concentration below the surfactant critical micelle concentration. Consequently there was insufficient surfactant to keep the membrane protein, rhodopsin, soluble in the aqueous buffer. These conditions favor the insertion of transmembrane proteins into lipid bilayers. After addition and incubation, the bilayer vesicles were purified on a... 

Monolayers are best formed from water-insoluble molecules. This is expressed well by the title of Gaines s classic book Insoluble Monolayers at Liquid-Gas Interfaces [104]. Carboxylic acids (7-13 in Table 1, for example), sulfates, quaternary ammonium salts, alcohols, amides, and nitriles with carbon chains of 12 or longer meet this requirement well. Similarly, well-behaved monolayers have been formed from naturally occurring phospholipids (14-17 in Table 1, for example), as well as from their synthetic analogs (18,19 in Table 1, for example). More recently, polymerizable surfactants (1-4, 20, 21 in Table 1, for example) [55, 68, 72, 121], preformed polymers [68, 70, 72,122-127], liquid crystalline polymers [128], buckyballs [129, 130], gramicidin [131], and even silica beads [132] have been demonstrated to undergo monolayer formation on aqueous solutions. 

Incorporation of polymerizable moieties into surfactants or into their counterions has permitted the formation of polymerized or polymer-coated... 

SUVs or MLVs formed from monomeric surfactants containing polymerizable moieties either in their headgroups or in their bilayers which are subsequently polymerized. SUVs prepared from surfactants which contain polymerizable headgroups can be polymerized both at the inner and at the outer surfaces or selectively at one of these surfaces. 

Aqueous dispersions of polymerizable lipids and surfactants can be polymerized by UV irradiation (Fig. 18). In the case of diacetylenic lipids the transition from monomeric to polymeric bilayers can be observed visually and spectroscopically. This was first discussed by Hub, 9) and Chapman 20). As in monomolecular layers (3.2.2) short irradiation brings about the blue conformation of the poly(diacetylene) chain. In contrast, upon prolonged irradiation or upon heating blue vesicles above the phase transition temperature of the monomeric hydrated lipid the red form of the polymer is formed 23,120). The visible spectra of the red form in monolayers and liposomes are qualitatively identical (Fig. 19). 

J. H. Fendler 94) has enlarged the number of polymerizable amphiphiles with the synthesis of a variety of novel surfactants and also introduced the styrene moiety (57) as another useful polymerizable unit12). Small unilamellar vesicles from mixtures of DPPC with (8) maintained their morphology after polymerization for months,... 

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