Structure of cationic polymers

The structure of cationic polymers of spiro [2.n] alkanes is too hindered to allow the formation of high-molecular-weight polymer. The termination step occurs rapidly, probably by rearrangement, loss of a proton, and formation of a double bond, the existence of which is confirmed by a vinyl hydrogen NMR signal at about 8 =5.2 ppm. 

Figure 1 Chemical structures of cationic polymers used for gene delivery as well as potential grafting with semitelechelic macromolecules.

Tang MX, Szoka FC (1997) The influence of polymer structure on the interactions of cationic polymers with DNA and morphology of the resulting complexes. Gene Ther 4 823-832... 

Fig. 24 Calculated structures of cationic phenoxy-amine complexes in the absence of 1-hexene (a), in the presence of 1-hexene (1-hexene-coordinated state) (b), and for transition state (c) (polymer chain model methyl group). Reproduced with permission from Saito et al. [27]. Copyright 2006, American Chemical Society...

Solid-state polymerization of D3, initiated by 7-irradiation, has been known for a long time. The reaction proceeds according to the cationic polymerization mechanism.3,5 Solid-state anionic polymerization of hexaphenylcyclotrisi-loxane in the presence of KOH or potassium oligosiloxanolate was recently reported. The crystalline structure of the polymers obtained in high yield in the heterogenous reaction was determined.1... 

As was shown, the planar conductivity of the film can be increased by immersing the substratum with the film in the ethanol-water (1 1) solution of LiNOs (0.1 mol/liter) for a short time. Then the film should be washed in water and allowed to dry. After such treatment the conductivity becomes 500 times greater and reaches the value 6x10 (Q/cm)". This increase may be due to the fact that in considering the second general model of the structure of this polymer it could be assumed that some additional quantity of Li cations might be absorbed into the ionic sphere of SO- groups, so that the total amount of Li in the electrolytic layers increases, and the conductivity then also increases. 

Thus, there are three possible pathways for the radiation degradation of polymer molecules neutral radical, cation-radical and/or anion-radical intermediates. Interest in the formation of these three types of reaction intermediates has fluctuated over the years with the utilization of different techniques and with the particular interests of different investigators. It is likely that all three species will be produced, but their relative importance in the degradation mechanism will depend on the chemical structure of the polymer. Evidence for their involvement will depend on the experimental methods used and the temperature and time scale of observation. In this paper we illustrate our investigations of many of the fundamental aspects of the radiation degradation of polymers through studies of series of polymers and copolymers. 

The structure of cationic lipids and polymers is readily amenable to chemical modification [35, 36] allowing the exploration of a virtually unlimited number of combinations and strategies at the mercy of chemists creative abilities. Various reviews have been focused on cationic lipids, dendrimers and polymers in terms of their chemical structures and their transfection properties [36—41], in an attempt to shed some light on the chemical requirements necessary to mediate gene delivery. The focus of this chapter will be to explore these carriers from a synthetic perspective, with a description of the chemical strategies used for the preparation via synthetic organic chemistry (excluding polymer synthesis) of cationic lipids and dendrimers. 

The biocatalyst a-chymotrypsin s ability to hydrolyze 20 is inhibited in the presence of copolymer 19a loaded with 0.2 mol% of the triphenyl carbinol units. 47b Photoirradiation of 19a results in heterolytic bond cleavage and the formation of the cationic copolymer 19b. In this polymer structure, the biocatalyzed hydrolysis of 20 is activated (V = 1.0 pM min-1). The polymer-induced photostimulated activation and deactivation of a-chymotrypsin in the different membrane environments correlates with the permeability and transport properties of the substrate 20 through the different structures of the polymer membranes.1471 Flow dialysis experiments showed that the polymer states 17a, 18a, and 19a are nonpermeable to 20, and hence the biocata-lytic functions of the immobilized enzyme are blocked. The polymer structures 17b,... 

Topical application of an ionic polymer forms a diffusion electric double layer on the surface of the skin. We evaluated the effects of topical application of ionic polymers on the recovery rate of the skin barrier after injury. Application of a nonionic polymer did not affect the barrier recovery. Application of sodium salts of anionic polymers accelerated the barrier recovery, while that of cationic polymers delayed it. Topical application of a sodium-exchange resin accelerated the barrier recovery, but application of a calcium-exchange resin had no effect, even when the resins had the same structure. Application of a chloride-exchange resin delayed barrier recovery. Thus, topical application of ionic polymers markedly influenced skin barrier homeostasis (Figure 15.2). 

Lewis acids readily isomerize both 1,3-dioxolanes and 1,3-oxathiolanes in ether solution. The reaction proceeds by coordination with the oxygen atom in the latter case since 1,3-dithiolanes do not isomerize under the same conditions. With trityl carbonium ion, an oxidative cleavage reaction takes place as shown in Scheme 6. Hydride extraction from the 4-position of 2,2-disubstituted 1,3-dioxolanes leads to an a-ketol in a preparatively useful reaction. 1,3-Oxathiolanes are reported to undergo similar cleavage but no mention of products other than regeneration of the ketone has been made (71CC861). Cationic polymerization of 1,3-dioxolane has been initiated by a wide variety of proton acids, Lewis acids and complex catalytic systems. The exact mechanism of the polymerization is still the subject of controversy, as is the structure of the polymer itself. It is unclear if polymerization... 

An artificial rubber may be made by cationic polymerization of isobutene using acid initiation with BF3 and water. What is the mechanism of the polymerization, and what is the structure of the polymer ... 

Some monomers isomerize during cationic polymerization. The net result is that the structure of the polymer repeating unit is not the same as that of the monomer. This occurs if the carbocation which is formed by initial attack on the monomer can isomerize to a more stable form. Isomerization is more prevalent in cationic than in anionic or free radical polymerizations because carbenium or oxonium ions rearrange easily. 

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