Polyelectrolyte complexes of glycol chitosan with some polysaccharides. I. Mixing ratio and dielectric properties

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Abstract
The formation of polyelectrolyte complexes of glycol chitosan (GlChi) with sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) has been studied. The number of ionizable groups per pyranose ring and the degree of dissociation as a function of pH in the polycation and polyanions have been determined using conductometric and potentiometric titrations. The formation of the complexes at different pH values has been followed by turbidity measurements. It is found that stoichiometric complexes of the polycation with CMC, (GalUA)n, and AlgA are formed at a mixing ratio of 0.5, indicating that the conformation may correspond to chains of equal lengths. In the case of the complex of GlChi with DS, the stoichiometric composition corresponds to a mixing ratio of 0.62. Thin transparent films of the complexes have been obtained by dehydration under reduced pressure on a layer of mercury. The dielectric constant ε′ and loss ε″ of thin films of these complexes have been measured in the range of frequencies of 1–100 kHz at different temperatures above and below room temperature. The GlChi–DS complex shows very little change in the values of ε′ and ε″ with frequency or temperature. On the other hand, films of GlChi–CMC and GlChi–(GalUA)n complexes show a significant increase in ε′ and ε″ as the temperature is increased above room temperature. The increase is more prominent at low frequencies. This behavior is attributed to the Maxwell‐Wagner interfacial polarization. In the case of GlChi–AlgA film, the values of ε′ and ε″ increase enormously as the temperature increases. This behavior is similar to the increase in ε′ and ε″ observed by Michels et al. [(1965) J. Phys. Chem. 69, 1456–1465] as the salt concentration increases in another polyelectrolyte complex studied by them. The electric double‐layer mechanism proposed by Schwarz [(1962) J. Phys. Chem. 66, 2636–2642] to account for the dielectric properties of biocolloids is shown to account quantitatively for the observations on the GlChi–AlgA film.