Structure and Dynamics of Water in Polysaccharide (Alginate) Solutions and Gels Explained by the Core-Shell Model.

In both biological and engineered systems, polysaccharides offer a means of establishing structural stiffness without altering the availability of water. Notable examples include the extracellular matrix of prokaryotes and eukaryotes, artificial skin grafts, drug delivery materials, and gels for water harvesting. Proper design and modeling of these systems require detailed understanding of the behavior of water confined in pores narrower than about 1 nm. We use molecular dynamics simulations to investigate the properties of water in solutions and gels of the polysaccharide alginate as a function of the water content and polymer cross-linking. We find that a detailed understanding of the nanoscale dynamics of water in alginate solutions and gels requires consideration of the discrete nature of water. However, we also find that the trends in tortuosity, permeability, dielectric constant, and shear viscosity can be adequately represented using the "core-shell" conceptual model that considers the confined fluid as a continuum.