A Study of the Chain Stiffness and Extension of Alginates, in Vitro Epimerized Alginates, and Periodate-Oxidized Alginates Using Size-Exclusion Chromatography Combined with Light Scattering and Viscosity Detectors

A series of alginates isolated from the stem and leaf of a brown algae (Laminaria hyperborea), bacterial mannuronan, in vitro epimerized mannuronans, and periodate oxidized alginates were analyzed by size-exclusion chromatography (SEC) combined with online multiangle laser light scattering (MALS) and viscometry (collectively abbreviated SMV). Selected samples were also analyzed off-line using low-angle laser light scattering and capillary viscometry. Excellent agreement between the two methods was obtained for properly purified samples. In contrast, abnormal results were obtained for some industrial samples due to the presence of particulate material. Naturally occurring alginates and in vitro epimerized mannuronans were found to obey essentially the same R_G−M and [η]−M relations, and hence, the same Mark−Houwink−Sakurada (MHS) equations (valid for I = 0.10 M):  20 000 g/mol < M < 100 000 g/mol, [η] = 0.0054 ·M^1.00; 100 000 g/mol < M < 1 000 000 g/mol, [η] = 0.071 ·M^0.89. Application of the wormlike chain model to the [η]−M data obtained by SMV yielded persistence lengths (q) of 15 nm for all alginates at an ionic strength of 0.17 M. Intrinsic viscosities corresponding to infinite ionic strength were estimated on the basis of Smidsrød's B-parameter, and the wormlike chain model then yielded q = 12 nm. Periodate oxidized alginates showed, in contrast, a pronounced decrease in persistence length with increasing degree of oxidation, reaching values below 4 nm at 44% oxidation. Periodate oxidation also resulted in some depolymerization, even in the presence of a free-radical scavenger.