PH-dependent polymer

Ashford M, Fell JT, Attwood D, Sharma H, Woodhead PJ. An in vivo investigation into the suitability of pH-dependent polymers for colonic targeting. Int J Pharm 1993 95 193-199. 

The excipients used in solid dispersions can be broadly classified as (a) polymeric and (b) non-polymeric excipients. Polymeric excipients are the primary excipients, whereas the non-polymeric ones are the auxiliary excipients. Polymeric excipients are further classified based on their charge into the following categories (a) nonionic or non-pH-dependent and (b) ionic or pH-dependent polymers. Further, nonionic polymers are classified as polyvinyllactam polymers and cellulose ethers. The ionic polymers are further classified as cationic and anionic polymers (Fig. 4.2). 

Solubility parameter calculated by Molecular Modeling Pro Plus from ChemSW Inc. Polymeric excipients are categorized into two main categories (1) nonionic/non-pH dependent polymers and (2) ionic/pH dependent polymers... 

Prodrug based strategy, coating with time or pH-dependent polymers. 

Ion-exchange resins swell in water to an extent which depends on the amount of crosslinking in the polymer, so that columns should be prepared from the wet material by adding it as a suspension in water to a tube already partially filled with water. (This also avoids trapping air bubbles.) The exchange capacity of a resin is commonly expressed as mg equiv./mL of wet resin. This quantity is pH-dependent for weak-acid or weak-base resins but is constant at about 0.6-2 for most strong-acid or strong-base types. 

Polymerization and curing rates of novolacs depend strongly on the acidity of the reaction mixture. Fig. 16 depicts the general pH dependence. Fig. 17 shows a partial structure for a hexa-cured novolac. Incorporation of amine is widely, though not universally, reported in hexa-cured novolac structures. In addition to the structure shown in Fig. 17, A, A -dibenzyl and A, A, A -tribenzylamine linkages have been reported [185-192]. The main by-products of hexa-curing conditions are water and ammonia, though formaldehyde is also produced. The structure and abundance of the amino portions of the cured polymer vary considerably with conditions. 

The stability of the enzyme-polymer complex and its dissociation upon the variation of pH depends on the structural and other physico-chemical properties of CP and enzyme molecule. Thus, a Biocarb-T heteroreticular biosorbent (Fig. 26) is characterized by a stability of its complex with ot-amylase (under the condition of its stabilization) in acid solutions and a complete dissociation of the complex during isolation of the active enzyme at pH 7-8. 

Chain scission is the ultimate fate of a stressed bond. At some value below the critical stress for chain rupture, bond angle deformation may result in an increase in reactivity. As stated in Sect. 3.1, mechanically activated hydrolysis of polymers containing ester groups can lead to the scission of the bond this concurrent reaction should be differentiated from homolytic chain scission, for example by looking at any pH-dependence as was found to be the case during shear degradation of DNA [84]. 

Several demonstrations of this concept have recently been published The first one is based on the pH dependence of redox transitions in oxide semiconductors that are connected with conductivity changes. If the bridging polymer layer in Fig. 6 is WO3 sputtered onto the electrode array or electrochemically deposited Ni(OH)j the transistor amplification is a function of the pH of the... 

FIGURE 2 pH dependance of the erosion rate of PCPP versus time. Discs of PCPP were formulated into 1.4-cm-diameter discs 1 mm thick by compression molding, and placed into 0.1 M phosphate buffers at various pH values at 37°C. The cumulative percentage of the polymer which degraded was measured by absorbance at 250 nm. 

Many synthetic water-soluble polymers are easily analyzed by GPC. These include polyacrylamide,130 sodium poly(styrenesulfonate),131 and poly (2-vinyl pyridine).132 An important issue in aqueous GPC of synthetic polymers is the effect of solvent conditions on hydrodynamic volume and therefore retention. Ion inclusion and ion exclusion effects may also be important. In one interesting case, samples of polyacrylamide in which the amide side chain was partially hydrolyzed to generate a random copolymer of acrylic acid and acrylamide exhibited pH-dependent GPC fractionation.130 At a pH so low that the side chain would be expected to be protonated, hydrolyzed samples eluted later than untreated samples, perhaps suggesting intramolecular hydrogen bonding. At neutral pH, the hydrolyzed samples eluted earlier than untreated samples, an effect that was ascribed to enlargement... 

New drug delivery systems are of great scientific and commercial interest. Amphiphilic networks composed of about 50/50 hydrophobic PIB and hydrophilic poly(2-(-dimethylamino)ethyl methacrylate) (DMAEMA) polymer segments were found to be biocompatible and to a large extent avascular (7). These PHM-PDMAEMA networks (i, in line with propositions of Weber and Stadler (2), and Sperling (J), denotes PDMAEMA chains linked by PIB chains) gave pH dependent... 

For suspensions primarily stabilized by a polymeric material, it is important to carefully consider the optimal pH value of the product since certain polymer properties, especially the rheological behavior, can strongly depend on the pH of the system. For example, the viscosity of hydrophilic colloids, such as xanthan gums and colloidal microcrystalline cellulose, is known to be somewhat pH- dependent. Most disperse systems are stable over a pH range of 4-10 but may flocculate under extreme pH conditions. Therefore, each dispersion should be examined for pH stability over an adequate storage period. Any... 

The electrochemistry of polyaniline is more complex than that of other conducting polymers and given the large number of possible structures for the material, it is not surprising that many possible reaction schemes have been suggested [181,182, 195-197,205], Many of the properties of the material are pH-dependent [173,174, 206], including the open circuit potential [207] which is most positive at pH 0, and this is further complicated by the fact that not all the polymer chains are necessarily in exactly the same state at any given time [197]. Above pH 3 polyaniline films do not show any electroactivity, but are not electroactive even at low pH with... 

On the basis of theoretical calculations Chance et al. [203] have interpreted electrochemical measurements using a scheme similar to that of MacDiarmid et al. [181] and Wnek [169] in which the first oxidation peak seen in cyclic voltammetry (at approx. + 0.2 V vs. SCE) represents the oxidation of the leucoemeraldine (1 A)x form of the polymer to produce an increasing number of quinoid repeat units, with the eventual formation of the (1 A-2S")x/2 polyemeraldine form by the end of the first cyclic voltammetric peak. The second peak (attributed by Kobayashi to degradation of the material) is attributed to the conversion of the (1 A-2S")x/2 form to the pernigraniline form (2A)X and the cathodic peaks to the reverse processes. The first process involves only electron transfer, whereas the second also involves the loss of protons and thus might be expected to show pH dependence (whereas the first should not), and this is apparently the case. Thus the second peak would represent the production of the diprotonated (2S )X form at low pH and the (2A)X form at higher pH with these two forms effectively in equilibrium mediated by the H+ concentration. This model is in conflict with the results of Kobayashi et al. [196] who found pH dependence of the position of the first peak. 

The effect of hydrophobicity of the polymer on the permeability of poly(2-hydroxyethyl methacrylate (HEMA)-co-methacrylic acid (MAAc) hydrogels was studied [12], The hydrophobicity was controlled by copolymerization with butyl methacrylate (BMA). The dependence of permeability on pH increased as the hydrophobicity increased even though the rate of diffusion decreased. Cross-link density of the hydrogel also contributed to pH-dependent permeability. 

The chemical nature of the main-chain linkages of step-growth polymers makes this class of polymers particularly reactive to a wide variety of chemical species. Solvolysis reactions break the C-X bond at the polymer linkage bonds. These types of reactions are often pH-dependent, so the stability of the polymer is highly dependent on the acidity or basicity of the prodegradant. 

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