Uncharged Polymer

The bovine serum albumin molecule is known to be nearly spherical and uncharged in a solution of pH 5.37. A plot of n/c2 versus C2 for this polymer at 25°C is linear and has an intercept corresponding to M = 69,000. The slope of the line is 1.37 X 10" Torr liter g . Use this slope to estimate the radius of this spherical molecule. 

In this chapter, and throughout this entire book for that matter, we have been concerned with uncharged polymers. We shall conclude this chapter with a brief discussion of the osmostic pressure of charged polymer molecules. 

A value for the molecular weight which is low by a factor z + 1 is obtained for salt-free solutions if the experimental results are analyzed as if the polymer were uncharged. 

TTiis ion exclusion effect can sometimes be exploited beneficially. For example, by purposefully choosing a column with some carboxyl groups and a pH that ionizes them (greater than approximately 6.5), it may allow separation of a charged and an uncharged polymer that have the same hydrodynamic size. Alternatively, one may be able to fine-tune elution of a polymer by adjusting pH. 

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. 

The swelling pressure of polyelectrolyte gels is usually considered as a sum of the network (jtnct) and ionic contributions (nion) [4, 99, 101, 113, 114]. The former describes the uncharged gel while taking into account the interaction between the polymer segments and the solvent as well as the network elasticity [4] ... 

Polyacrylamides are nonionic polymers, usually with much higher molecular weights (MW from 100,000 up to 12 or 15 M). They often are copolymerized with polyacrylates. Depending on the MW ratios employed, they may act as colloidal dispersants, sludge conditioners, or flocculants. Nonionics such as polyacrylamides (and isobutylenes) are particularly useful at dispersing uncharged particles. 

The foregoing examples show that hollow polymer capsules with varying composition and sizes of ca. 2-20 micrometers can be produced, either by templating charged (latex particles and biocrystals) or uncharged (organic microcrystals), and that different core removal procedures can be employed. Nanometer-size polymer capsules have also been produced by employing smaller particle templates [107]. 

The overall objective of this chapter is to review the fundamental issues involved in the transport of macromolecules in hydrophilic media made of synthetic or naturally occurring uncharged polymers with nanometer-scale pore structure when an electric field is applied. The physical and chemical properties and structural features of hydrophilic polymeric materials will be considered first. Although the emphasis will be on classical polymeric gels, discussion of polymeric solutions and nonclassical gels made of, for example, un-cross-linked macromolecular units such as linear polymers and micelles will also be considered in light of recent interest in these materials for a number of applications... 

The results of osmotic pressure measurements are shown in Fig. 145 for poly-(4-vinyl-N-butylpyridinium bromide) in alcohol, and for the parent uncharged polymer, poly-(4-vinylpyridine), likewise in alcohol. The value of /c for the former (note difference in scales) is much larger than for the latter, and it increases with dilution. The... 

The majority of optical sensors for neutral (uncharged) species is based on indicators which selectively interact with the analyte and additionally give optical signal changes. Since the diffusion of neutral analytes is not as strongly affected by the polymer matrix as it is in the case of ions, all types of polymer matrices can be used. 

A different pH-triggered deshielding concept with hydrophilic polymers is based on reversing noncovalent electrostatic bonds [78, 195, 197]. For example, a pH-responsive sulfonamide/PEl system was developed for tumor-specific pDNA delivery [195]. At pH 7.4, the pH-sensitive diblock copolymer, poly(methacryloyl sulfadimethoxine) (PSD)-hZocA -PEG (PSD-b-PEG), binds to DNA/PEI polyplexes and shields against cell interaction. At pH 6.6 (such as in a hypoxic extracellular tumor environment or in endosomes), PSD-b-PEG becomes uncharged due to sulfonamide protonation and detaches from the nanoparticles, permitting PEI to interact with cells. In this fashion PSD-b-PEG is able to discern the small difference in pH between normal and tumor tissues. 

For h < 26, the situation is much more complex. One not only needs to know 4>(z) for each layer, but how 4>(z) changes as the two particles approach, i.e. 4>(z,h) this may well depend on the time-scale of the approach, i.e. the equilibrium path may not be followed. Scheutjens and Fleer (25) in an extension of their model for polymer adsorption have analysed the situation for two interacting uncharged parallel, flat plates carrying adsorbed, neutral homopolymer, interacting under equilibrium conditions. Only a semi-quantitative picture will be presented here. 

Fig. 10 Aggregation numbers 2 as function of degree of polymerization of insoluble block for uncharged block copolymers. Open symbols different diblock-, triblock-, graft-, and star polymers. Filled symbols low-MW surfactants. Reprinted with permission from [211]. Copyright (2002) Wiley...

At low concentrations, when uncharged polymers are dissolved in a solvent in which they do not crosslink or entangle, they possess a viscoelastic response through hydrodynamic and entropic effects. We can begin by considering an isolated chain in its quiescent state. The chain will be in constant motion. In the absence of any specific interactions, the chain will evolve to its maximum entropy state. We can represent the chain as N links or submolecules each with a length b. These links are formed from a few monomer units of the chain. The root mean square end-to-end length of the chain is... 

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