Functional Polysoaps

A number of reports deal with functionalized polysoaps, including the incorporation of chromophores, mesogens, redox-active moieties and electrically conductive groups (Fig. 16). Three basic intentions can be identified i) the functional unit serves as probe to monitor certain properties of the parent polysoap ii) the polysoap provides a suitable matrix for the functional unit, e.g. by compartmentalization, clustering, orientation etc. iii) the combination of functional unit and polysoap creates new collective features in the system, e.g. improving or modifying the self-organization. 

Incorporations of probe molecules and chromophores are the most widespread functionalizations with various goals aimed at. As mostly limited degrees of functionalization are wanted, such polysoaps are conveniently prepared either by copolymerization [331] or by grafting reactions onto polysoaps or polysoap precursors. 

The majority of studies aim at labelling of polysoaps, to study their behaviour as discussed in Sects. 3 and 4. UV/visible-probes, fluorescence probes and ESR probes have been attached. For example azo dyes were used as labels taking advantage of their trans-cis photoisomerization [203, 217, 260], More frequently fluorescent labels have been fixed such as dansyl [174,175,177,287], naphthyl [211, 259], anthracenyl [183, 189] or pyrenyl groups [204, 259], For ESR studies, e.g. nitroxy labelled polysoaps based on poly(ethyleneimine) are described [145]. 

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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- ... 

Fig. 3-3. First-order rate constant (kobs) hydrolysis of p-nitrophenyl hexanoate pk>tted as a function of the concentration of polysoaps (PVP-LiJ), pH 9.95-10.1.

Fig. 34. Aggregation number N in polymeric micelles of polysoap polyfsodium maleate-a/t-decylvinylether) 33 as function of the degree of neutralization a by NaOH at 25 °C, derived from fluorescence quenching. (Data from [196])...

Fig. 44. Maximum clearing temperature of liquid crystalline phases of a non-ionic polysoap 80 as function of the degree of polymeriza tion O cubic Ij phase, x hexagonal H, phase, lamellar L phase. (Data from [451] see also [126])...

Formulation (7,8) supposes implicitly that the polysoap is unionized in n-octanol (cf to Appendix 1). In order to substantiate this point further, the conductance of the organic phase was also measured as a function of a as shown in Figure 7. The degree of ionization at different a s for hydrogen (aj jj) and for metal (otj ) was determined from the equivalent conductance (see Appendix II). Table HI summarizes these results. 

The intrinsic viscosity [q] (ml/g) of the polysoap in the organic phase is given as a function of a in Figure 8. A marked dependence of [ti] on the nature of the ion and opposite to the trend of the thermodynamic constant (which increases in the direction Na>K>Cs, cf. Figure 5) is displayed. Qualitatively, one may say that the occurrence of intramolecular polymer-polymer bonds is greater for the ions the most in need of hydration. 

Gantrez resins and other alkyl vinyl ether-MA copolymers, after substantial study, have also been found to be potentially useful as polysoaps, with excellent dispersant strength or emulsifying power. Ester derivatives of the materials function very effectively as polymerization dispersants. 

Anton P, Koeberle P, Laschewsky A (1992) Stractme and properties of zwitterionic polysoaps functionalization by redox-switchable moieties. Progr Colloid Polym Sci 89 56-59... 

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