Amphiphilic polymers with polymerization

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... 

Diacyllipid-polyethyleneoxide conjugates have been introduced into the controlled drug delivery area as polymeric surface modiLers for liposomes (Klibanov et al., 1990). Being incorporated into the liposome membrane by insertion of their lipidic anchor into the bilayer, such molecules can ster-ically stabilize the liposome against interaction with certain plasma proteins in the blood that results in signiLcant prolongation of the vesicle circulation time. The diacyllipid-PEO molecule itself represents a characteristic amphiphilic polymer with a bulky hydrophilic (PEO) portion and a very short but extremely hydrophobic diacyllipid part. Typically, for other PEO-containing amphiphilic block... 

Linear amphiphilic polymers with carboxyl groups were also available via sequential cationic polymerization of a fimctional vinyl ether and an alkyl derivative [6]. The sequential living cationic polymerization of diethyl 2-(vinyloxy)ethylmalonate [VOEM CHf=CHOCH2CH2CH(COOCH2CH3)2]... 

Yin et al. [73,74] prepared new microgel star amphiphiles and stndied the compression behavior at the air-water interface. Particles were prepared in a two-step process. First, the gel core was synthesized by copolymerization of styrene and divinylbenzene in diox-ane using benzoylperoxide as initiator. Microgel particles 20 run in diameter were obtained. Second, the gel core was grafted with acrylic or methacryUc acid by free radical polymerization, resulting in amphiphilic polymer particles. These particles were spread from a dimethylformamide/chloroform (1 4) solution at the air-water interface. tt-A cnrves indicated low compressibility above lOmNm and collapse pressnres larger than 40 mNm With increase of the hydrophilic component, the molecnlar area of the polymer and the collapse pressure increased. 

This subject can be considered in terms of five different types of molecules or materials (a) biologically inert, water-insoluble polymers (b) water-insoluble polymers that bear biologically active surface groups (c) water-swellable polymeric gels, or amphiphilic polymers that function as membranes (d) water-insoluble but bioerodable polymers that erode in aqueous media with concurrent release of a linked or entrapped bioactive molecule and (e) water-soluble polymers that bear bioactive agents as side groups. 

The reason for Nafion LB-film fabrication was the wish to obtain the highly ordered systems from perfluorinated ion exchange polymer with multilayered structure, where the ionic layers (conductors) would alternate with fluorocarbon polymer layers (insulators), and to investigate the properties of such films.74 This polymer contains a hydrophobic fluorocarbon polymeric chain and hydrophilic ionic groups, so it is sufficiently amphiphilic it has a comblike structure that makes it a suitable polymer for LB-film deposition. 

Figure 1 Schematic structures of micelle and liposome, their formation and loading with a contrast agent, (a) A micelle is formed spontaneously in aqueous media from an amphiphilic compound (1) that consists of distinct hydrophilic (2) and hydrophobic (3) moieties. Hydrophobic moieties form the micelle core (4). Contrast agent (asterisk gamma- or MR-active metal-loaded chelating group, or heavy element, such as iodine or bromine) can be directly coupled to the hydrophobic moiety within the micelle core (5), or incorporated into the micelle as an individual monomeric (6) or polymeric (7) amphiphilic unit, (b) A liposome can be prepared from individual phospholipid molecules (1) that consists of a bilayered membrane (2) and internal aqueous compartment (3). Contrast agent (asterisk) can be entrapped in the inner water space of the liposome as a soluble entity (4) or incorporated into the liposome membrane as a part of monomeric (5) or polymeric (6) amphiphilic unit (similar to that in case of micelle). Additionally, liposomes can be sterically protected by amphiphilic derivatization with PEG or PEG-like polymer (7) [1].

Many micellar catalytic applications using low molecular weight amphiphiles have already been discussed in reviews and books and will not be the subject of this chapter [1]. We will rather focus on the use of different polymeric amphiphiles, that form micelles or micellar analogous structures and will summarize recent advances and new trends of using such systems for the catalytic synthesis of low molecular weight compounds and polymers, particularly in aqueous solution. The polymeric amphiphiles discussed herein are block copolymers, star-like polymers with a hyperbranched core, and polysoaps (Fig. 6.3). 

The conversion of dextran with 1,2-epoxy-3-phenoxypropane, epoxyoctane or epoxydodecane may be exploited for the preparation of amphiphilic dextran derivatives. Polymeric surfactants prepared by hydrophobic modification of polysaccharides have been widely studied, starting with the pioneering work of Landoll [261]. Neutral water-soluble polymeric surfactants can be obtained by reaction of dextran with 1,2-epoxy-3-phenoxypropane in 1 M aqueous NaOH at ambient temperature (Fig. 35, [229,233]). The number n of hydrophobic groups per 100 Glcp units varies between 7 and 22 depending on the reaction conditions. 2-Hydroxy-3-phenoxy propyl dextran ethers (DexP) behave like classical associative polymers in aqueous solution. In dilute solution, the intrinsic viscosity decreases significantly whereas... 

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