Polymers polyanions

J. Hen. Sulfonate-containing polymer/polyanionic cellulose combination for high temperature/high pressure filtration control in water base drilling fluids. Patent US 5(X)8025,1991. 

The polymers used in DDSs may be classified using different criteria. According to the charge they bear, they may be divided into neutral polymers, anionic polymers (polyanions) and cationic polymers (polycations). This chapter is devoted to the DDSs containing cationic polymers of pharmaceutical interest. 

CMC hydrates rapidly and forms clear solutions. Viscosity buUding is the single most important property of CMC. DUute solutions of CMC exhibit stable viscosity because each polymer chain is hydrated, extended, and independent. The sodium carboxylate groups are highly hydrated, and the ceUulose molecule itself is hydrated. The ceUulose molecule is linear, and conversion of it into a polyanion (polycarboxylate) tends to keep it in an extended form by reason of coulombic repulsion. This same coulombic repulsion between the carboxylate anions prevents aggregation of the polymer chains. Solutions of CMC are either pseudoplastic or thixotropic, depending on the type. 

S-Poly(L-malic acid) ionizes readily in water giving rise to a highly soluble polyanion. Thus, a 2% solution of the free acid of the polymer from Aureobasidium sp. A-91 showed a pH 2.0 [5]. The ionic constants have been determined to be pKa = 3.6 for the polymer from Aureo-basidumsp. A-9 [5] and pKa (25°C) = 3.45 for/3-poly(L-malic acid) of Mw 24 kDa from F. polycephalum (Valussi and Cesaro, unpublished results) Thus, the polymer is highly charged under physiological conditions (pH 7.0). 

Hydrophobization of Polyanionic Polymers to Achieve Higher Biological Activity... 

Since the pioneer work by Merigan in 1967 [1], many kinds of synthetic or natural polyanionic polymers have been examined for their biological activities [2-8], such as cytotoxicity, antiviral activity, antitumor activity, and immunomodulating activity. Although the biological results were interesting, the extent of activity for clinical application was still low. 

Several mechanisms between drug-encapsulated liposomes and cells was presented [9,10]. Sunamoto and coworkers [11] applied the liposomal technique for improving the biological activity of polyanionic polymers. 

We modified polyanionic polymers by use of a grafting reaction of hydrophobic groups onto the polymers. After an extensive evaluation for the affinity of the hy-drophobically modified (hydrophobized) polymers to cell membrane, the immuno-stimulating activity of polymers was investigated by in vitro or ex vivo experiments. Consequently, the increased biological activity was found in the hydrophobized polymer, indicating that... 

Based on the data in Figs. 2 and 4, it appears that the affinity of the polyanionic polymer for cell membrane can be increased by the hydrophobization of polymers. 

Figure 3 The principle for the evaluation of the interaction between modified or unmodified polyanionic polymer and liposomal membrane.

There was no distinct difference between polymers having different molecular weights. From the data in Figures 2, 4, 5, and 6, it seems to be established that the affinity of polyanionic polymers for cell membrane is adjustable by a simple grafting of hydrophobic groups. 

Based on these observations in Figs. 8 and 9, it is suggested that the hydrophobic group modification (hy-drophobization) is an effective method for improving the immuno-stimulating activity of polyanionic polymers. 

Nondispersed Inhibited Systems. In these systems, the nondispersed character of the fluids is reinforced by some inhibition system, or combination of systems, such as (1) calcium ions, lime or gypsum (2) salt-sodium chloride or potassium chloride (3) polymers such as Polysaccharides, polyanionic cellulose, hydrolyzed polyacrylamide. 

Since multiple electrical and optical functionality must be combined in the fabrication of an OLED, many workers have turned to the techniques of molecular self-assembly in order to optimize the microstructure of the materials used. In turn, such approaches necessitate the incorporation of additional chemical functionality into the molecules. For example, the successive dipping of a substrate into solutions of polyanion and polycation leads to the deposition of poly-ionic bilayers [59, 60]. Since the precursor form of PPV is cationic, this is a very appealing way to tailor its properties. Anionic polymers that have been studied include sulfonatcd polystyrene [59] and sulfonatcd polyanilinc 159, 60]. Thermal conversion of the precursor PPV then results in an electroluminescent blended polymer film. 

Some microbial exopolysaccharides contain the inorganic substituents phosphate and sulphate. Phosphate has been found in exopolysaccharide from bacteria of medical importance, including Escherichia coli. Sulphate is far less common than phosphate and has only been found in spedes of cyanobaderia. In addition to these inorganic components, which form part of the structure of some exopolysaccharides, all polyanionic polymers will bind a mixture of cations. Exopolysaccharides are, therefore, purified in the salt form. The strength of binding of the various cations depend on the exopolysaccharide some bind the divalent cations calrium, barium and strontium very strongly, whereas others prefer certain monovalent cations, eg Na ... 

Ladenheim and Morawetz [23] also showed that the reactivity of the carboxylate units in partially ionized poly(methacrylic acid) (PMA) toward BrCH2COO in the bromine displacement reaction was greatly diminished, while the reaction proceeded at an appreciable rate with uncharged p-bromoacetamide [23]. This inhibition of the reaction of the polyanion with a small anionic reagent can be attributed to the electrostatic repulsion between the polymer and the reagent. 

This finding may be rationalized for the following reasons. The total length of the Me pendant moiety from the cylinder axis is approximately 15 A when the dye moiety is stretched out from the polymer main chain. Since the dye moiety is linked to the main chain via a flexible chemical bond, it may be able to reside at any distance between 3 and 15 A from the cylinder axis. Thus, on average the Me residues would experience the polyanion microenvironment at a distance of about 10 A. 

A similar example is the formation of nonstoichiometric interpolymeric complexes between mutually complementary polyelectrolytes — polycation and polyanion [69,70], They behave like true polymer networks and are capable of swelling the interpolymeric complexes between PAAc and polyethylene piperazine swells, for instance, 16-18 times [70], Also advantageous in this case is the possibility to carry out this type of crosslinking in open systems, such as soil. 

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