Water-soluble nonionic amphiphiles

Poly(A-vinylamides) are another class of synthetic thermo-responsive polymers. Two of the most common polymers of this class are poly(Al-vinylpyrrolidone) (PVP) and poly(A-vinylcaprolactam) (PVCL) (Figure 1.3). PVCL is a water-soluble nonionic amphiphilic polymer with its basic unit comprising a seven-membered cyclic amide with a polar hydrophilic carboxyl group and an amide group connected directly to a hydrophobic vinyl chain. 

Some other C—C bond coupling reactions in micellar systems should be mentioned here. Monflier et al. [72] described, in both papers and patents, the telome-rization of 1,3-butadiene into octadienol in a micellar system by means of a palladium-phosphine catalyst. Water-soluble and amphiphilic phosphines have been used and the surfactants were widely varied. The authors have shown that the promoting effect of surfactants appeared above the CMCs of the surfactants, and they conclude that micellar aggregates were present in the reaction mixture. Cationic, anionic, and nonionic surfactants gave this micellar effect but the combination of the highly water-soluble TPPTS and the surfactant dodecyldimethylamine hydrocarbonate was found to be best. A speculation about the location of reactants shows that the reaction probably occurs in the interface between the micellar pseudophase and water. 

Nonionic amphiphilic block copolymers in aqueous solution are typically formed of a water-soluble hydrophilic block, e.g., PEO, PMVE, PNIPAM, linked to a hydrophobic block, e.g., PPO, PBO, PS, PMMA. 

Nonionic surfactants are one of the most important and largest surfactant groups. They are amphiphilic molecules composed, in most cases, of poly(ethylene oxide) (PEO) blocks as the water-soluble fragment and fatty alcohols, fatty acids, alkylated phenol derivatives, or various synthetic polymers as the hydrophobic part [1], This class of surfactants is widely used as surface wetting agents, emulsifiers, detergents, phase-transfer agents, and solubilizers for diverse industrial and biomedical applications [2],... 

PVP is a nonionic water-soluble polymer that interacts with water-soluble dyes to form water-soluble complexes with less fabric substantivity than the free dye. Additionally, PVP inhibits soil redeposition and is particularly effective with synthetic fibers and synthetic cotton blends. The polymer comprises hydrophilic, dipolar imido groups in conjunction with hydrophobic, apolar methylene and methine groups. The combination of dipolar and amphiphilic character make PVP soluble in water and organic solvents such as alcohols and partially halogenated alkanes, and will complex a variety of polarizable and acidic compounds. PVP is particularly effective with blue dyes and not as effective with acid red dyes. 

The impact of different surfactants (SDS, DOSS, CTAB and hexadimethrine bromide, bile salts °), nonionic and mixed micelles, and additives (neutral and anionic CDs," " tetraalkylammonium salts, organic solvents in EKC separations has been demonstrated with phenol test mixtures. In addition, phenols have been chosen to introduce the applicability of more exotic EKC secondary phases such as SDS modified by bovine serum albumin, water-soluble calixarene, " starburstdendrimers, " " cationic replaceable polymeric phases, ionenes, amphiphilic block copolymers,polyelectrolye complexes,and liposome-coated capillaries. The separation of phenols of environmental interest as well as the sources and transformations of chlorophenols in the natural environment have been revised. Examples of the investigation of phenols by EKC methodologies in aquatic systems, soil," " and gas phase are compiled in Table 31.3. Figure 31.3 illustrates the electromigration separation of phenols by both CZE and EKC modes. 

A synthesis of fluorolipopeptides by the modular methodology (Scheme 32) leads to the nonionic amphiphilic structures 38 [86,87]. Because derivatives 38 are poorly soluble in water, their surfactant properties have been determined in formamide [88]. Hemolytic tests carried out with some of these compounds indicate no activity toward red blood cells they show, however, a marked toxicity for hybridoma cells [89]. 

Sirolimus is insoluble in water, having poor systemic bioavailability estimated at 18% following ingestion of the tablet. The polymers, polyethylene glycol 8000, polyethylene glycol 20000, and poloxamer 188 (a nonionic amphiphilic copolymer surfactant) augment water solubility and miscibility of SRL tablets [1]. Though SRL tablets are taken just once daily, this does not constitute an extended- or delayed-release formulation per se, as the half-life of SRL is approximately 60 hours. 

An important area where interfacial phenomena play a significant role is that of microemulsions [3]. These systems consist of oil, water and amphiphile(s) that are thermodynamically stable. The driving force for microemulsion formation is the ultra-low interfacial tension (< 10 mNm ) which is mostly produced by the use of two amphiphiles (surfactants) of different nature, one predominantly water soluble (like an anionic or nonionic surfactant) and one predominantly oil soluble (like a medium chain alcohol, pentanol or hexanol). It is clear that the properties of the interfacial film determine microemulsion formation. 

Polymers with which we will deal throughout this chapter are water soluble. They can be either ionic or nonionic. Some of them are synthetic, others are of biological origin (proteins, for instance). Both homopolymers and heteropolymers exist. Some polymers own amphiphilic monomers that induce surface-active properties to the whole polymeric structure. Water plays a very important role in determining the polymer properties in solution. The properties are also greatly modified by the addition of salts or by a pH modification. Frequently encountered nonionic polymers in polymer-surfactant interactions and their subsequent adsorption behavior at solid surfaces are poly(ethylene oxide) (PEO), poly(vinyl pyrrolidone) (PVP), polyacrylamide, and poly(vinyl alcohol). 

Several references were made above to the term phase inversion temperature. With the exceptions of Eqs. (9.17) and (9.18), however, no specific reference was made to the effect of temperature on the HLB of a surfactant. From the discussions in Chapter 4, it is clear that temperature can play a role in determining the surface activity of a surfactant, especially nonionic amphiphiles in which hydration is the principal mechanism of solubilization. The importance of temperature effects on surfactant solution properties, especially the solubility or cloud point of nonionic surfactants, led to the evolution of the concept of using that property as a tool for predicting the activity of such materials in emulsions. Since the cloud point is defined as the temperature, or temperature range, at which a given amphiphile loses sufficient solubility in water to produce a normal surfactant solution, it was assumed that such a temperature-driven transition would also be reflected in the role of the surfactant in emulsion formation and stabilization. 

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