The intrinsic persistence length of carboxymethyl cellulose (CMC) is determined by size exclusion chromatography in combination with multiangle laser light scattering (SEC-MALLS) as well as from potentiometric titrations. Samples with degree of substitution (ds) ranging from 0.75 to 1.25 were investigated. The relation between molar mass M and radius of gyration Rg as obtained by SEC-MALLS is determined in 0.02, 0.1, and 0.2 mol L-1 NaNO3. Using the electrostatic wormlike chain theory a bare (intrinsic) persistence length Lp0 of CMC is assessed at 16 nm, irrespective of the degree of substitution. A somewhat lower value (12 nm) is obtained when Odijk's theory for the description of polyelectrolyte dimensions is applied. The difference between Lp0 assessed from both models is discussed briefly. Potentiometric titrations were carried out in NaCl solutions (ranging from 0.01 to 1 mol L-1). From the titrations the radius of the CMC backbone was obtained by application of the model of a uniformly charged cylinder. The radius amounts to 0.95 nm for CMC ds = 0.75, and increases to 1.15 nm for CMC with ds = 1.25. The pK for the intrinsic dissociation constant of the carboxyl groups (i.e., at zero degree of dissociation) amounted to 3.2. Lp0 was also deduced from potentiometric titrations. A model developed by Katchalsky and Lifson, which relates the dissociation behavior of a polyelectrolyte to the stiffness of its chain, was applied to CMC. From analyses of the potentiometric titrations an intrinsic persistence length of 6 nm was deduced. The difference between Lp0 assessed from SEC-MALLS and potentiometric titrations is discussed briefly.
Hoogendam, C. W., de Keizer, A., Cohen Stuart, M. A., Bijsterbosch, B. H., Smit, J. A. M., van Dijk, J. A. P. P., van der Horst, P. M., & Batelaan, J. G. (1998). Persistence length of carboxymethyl cellulose as evaluated from size exclusion chromatography and potentiometric titrations. Macromolecules, 31, 6297-6309. https://doi.org/10.1021/ma971032i