Evaluation of chain stiffness of partially oxidized polyguluronate

The chain stiffness of macromolecules is considered critical in their design and applications. This study utilizes polyguluronate derived from alginate, a typical polysaccharide widely utilized in many biomedical applications, as a model macromolecule to investigate how the chain stiffness can be tightly regulated by partial oxidation. Alginate has a backbone of inherently rigid alpha-L-guluronate (i.e., polyguluronate) and more flexible beta-D-mannuronate. The chain stiffness of the polyguluronate was specifically studied in this paper, as this component plays a critical role in the formation of alginate hydrogels with divalent cations and is the dominant factor in determining the chain stiffness of alginate. We have utilized size-exclusion chromatography, equipped with refractive index, viscosity, and light-scattering detectors, to determine the intrinsic viscosity and the weight-average molecular weight of each fraction of samples. The chain stiffness of partially oxidized polyguluronate was then evaluated from the exponent of the Mark-Houwink equation and the persistence length. We have found that partial oxidation can be used to tightly regulate the steric hindrance and stiffness of the polyguluronate backbone. This approach to control the chain stiffness of inherently rigid polysaccharides by partial oxidation may find many applications in biomedical utilization of these materials.