Polysoap

The pioneering work on amphiphilic polyelectrolytes goes back to 1951, when Strauss et al. [25] first synthesized amphiphilic polycations by quaternization of poly(2-vinylpyridine) with n-dodecyl bromide. They revealed that the long alkyl side chains attached to partially quaternized poly(vinylpyridine)s tended to aggregate in aqueous solution so that the polymers assumed a compact conformation when the mole fraction of the hydrophobic side chains exceeded a certain critical value. Thus, Strauss et al. became the first to show experimentally the intramolecular micellation of amphiphilic polymers and the existence of a critical content of hydrophobic residues which may be compared to the critical micelle concentration of ordinary surfactants. They called such amphiphilic polyelectrolytes polysoaps [25],... 

Poly(3,3 ionene) 80 Polylysine 148 Polymethacrylic acid 54 Polypeptides 147 Polypropylene oxide 158 Polysoaps 63... 

Laschewsky, AMolecular Concepts, Self-Organisation and Properties of Polysoaps. Vol. 124,... 

Charged polysoaps (polymer micelles) combine within a molecule structural characteristics of the conventional micelles and polyelectrolytes, and supposedly adopt globular conformations in aqueous media with the hydrophobic region inside and charged groups outside as in water-soluble proteins. Thus,... 

The microenvironment of polysoaps estimated by the use of probes reflects the microenvironment where probes are bound. Strop et al. (1976) synthesized the copolymers involving the probe units [14] and [15] as comonomer, and directly estimated the microenvironments along the polymer chain. In all the... 

Coenzymes complement the catalytic action of the amino-acid functional groups. They are bound to apoenzymes (apoproteins) either covalently or non-covalently. It is interesting to note that non-covalently-bound coenzymes are polyanions at neutral pH as exemplified by the structures of glutathione (GSH) [17] and thiamine pyrophosphate [18]. Shinkai and Kunitake (1976b, 1977a) demonstrated the efficient binding of glutathione and coenzyme A (a polyphosphate) to cationic micelles and cationic polysoaps. Thus, the combina- ... 

This section describes the nucleophilic reactions—acyl transfer reactions mostly—promoted by micelles and polysoaps. The nucleophiles are imidazoles, oxyanions and thiols, the same catalytic groups found ubiquitously in the enzyme active site. These nucleophiles are remarkably activated in the anionic form in the presence of cationic micelles and cationic polysoaps. These results are explained by the concept of the hydrophobic ion pair (Kunitake et al.,... 

The enhanced reactivity of hydroxamate ions is in general applicable to base-catalyzed reactions. For example, base-catalyzed proton-abstraction from or-ketols (11) is efficiently promoted by combinations of hydroxamate + CTAB micelle or hydroxamate + cationic polysoap (Shinkai and Kunitake, 1976c, 1977d). The rate acceleration amounts to 3000-20 000-fold, and the rate... 

Coenzyme A (CoASH) and glutathione (GSH) have anionic charges in addition to the thiol group and are readily bound on to a cationic micelle or a cationic polysoap. It was discovered that the nucleophilicity of these coenzymes towards PNPA is markedly enhanced in the presence of cationic... 

These results are compatible with the proposition that the catalytic efficiency of the polysoap is related to the formation of the hydrophobic domain. 

The immobilization of flavin in the cationic polysoaps [57] also facilitates flavin-mediated oxidation reactions (Shinkai et al., 1978b,c, 1980b). Interestingly, [57] oxidizes NADH according to Michaelis-Menten-type kinetics... 

In previous sections, numerous examples of anion activation by cationic micelles and polysoaps were presented. The extent of rate augmentation— 102—lO -fold—cannot be rationalized in terms of concentration effects alone. We believe that these observations are explained most reasonably by the concept of the hydrophobic ion pair (Kunitake et al., 1976a). According to this concept, anionic reagents are activated probably due to desolvation when they form ion pairs with an ammonium moiety in a hydrophobic microenvironment. The activation of anionic species in the cationic micellar phase... 

As mentioned repeatedly, a variety of anionic reagents are highly activated in the hydrophobic microenvironment of cationic micelles and polysoaps. The range of anionic reagents studied in the past includes imidazole, hydroxide, thiolates, oximates, hydroxamates, carboxylates and carbanions. Polyanionic coenzymes are similarly activated. These results can be interpreted in a unified way by the concept of hydrophobic ion pairs, and the major source of activation seems to be concentration and desolvation of the anionic reagent in the... 

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). 

Fig. 6.3 Different types of micelles and micelle analogous structures a) amphiphilic block copolymers, b) star-like polymers with a hyperbranched core, c) polysoaps.

As an extension of the perspective of micelle formation by amphiphihc block copolymers the following part will focus on two other types of polymers. The micellar structures that will discussed are (i) micelles and inverse micelles based on a hyperbranched polymers and (ii) polysoaps, that are copolymers composed of hy-drophihc and amphiphihc or hydrophobic monomers. Whereas the first class of polymers is stiU very new and only few examples exist of the synthesis and appH-cation of such stracture in catalysis, the synthesis and aggregation characteristics of polysoaps has already been intensively discussed in the hterature. 

A second interesting class of amphiphilic polymers is the polysoaps or miceUar polymers as they are often referred to. Such polymers are composed of hydrophilic and hydrophobic fragments leading to various molecular architectures that have been discussed in detail by A. Laschewsky [78]. The precise structure of the resulting micelles, that is, whether they are intra- or intermolecular assembhes, is still subject to discussion because the polymer structure is so versatile. Possible micellar structures are depicted in Fig. 6.8. The most interesting feature of such polymers with respect to their application in catalysis is (i) their remarkable abil-... 

Fig. 6.8 Possible shapes of polymeric micelles" formed by polysoaps, (a) local micelle (b) regional micelle (c) molecular micelle".

Although much work has already been devoted to the use of polysoaps in micellar cataylsis application, in particular as models for esterases [79] and systems for photochemical catalyzed reactions [80], only a few reports have appeared on the use of such polymer supports in transition metal catalysis. 

Thus, G. Oehme et al. employed two types of polysoaps in the micellar catalytic asymmetric hydrogenation of cinnamic acid acetamidates as amino acid precursors [81, 82]. 

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. 

Hydrogenation was less fast in the presence of polysoap PSl and PS2 compared with SDS which has been explained by diffusion Hmitation of the polymer-... 

Fig. 6.9 Two examples for linear polysoaps used in the asymmetric hydrogenation [75].

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