The physical properties of confined water can differ dramatically from those of bulk water. Hydration water associated with polysaccharides provides a particularly interesting example of confined water, because differences in polysaccharide structure provide different spatially confined environments for water sorption. We have used attenuated total reflection infrared (ATR-IR) spectroscopy to investigate the structure of hydration water in films of three different polysaccharides under controlled relative humidity (RH) conditions. We compare the results obtained for films of highly branched, dendrimer-like phytoglycogen nanoparticles to those obtained for two unbranched polysaccharides, hyaluronic acid (HA), and chitosan. We find similarities between the water structuring in the two linear polysaccharides and significant differences for phytoglycogen. In particular, the results suggest that the high degree of branching in phytoglycogen leads to a much more well-ordered water structure (low density, high connectivity network water), indicating the strong influence of chain architecture on the structuring of water. These measurements provide unique insight into the relationship between the structure and hydration of polysaccharides, which is important for understanding and exploiting these sustainable nanomaterials in a wide range of applications.
Phytoglycogen is a highly branched polymer of glucose produced as soft, compact nanoparticles by sweet corn. Properties such as softness, porosity, and mechanical integrity, combined with nontoxicity and biodegradability, make phytoglycogen nanoparticles ideal for applications involving the human body, ranging from skin moisturizing and rejuvenation agents in personal care formulations to functional therapeutics in biomedicine. To further broaden the range of applications, phytoglycogen nanoparticles can be chemically modified with hydrophobic species such as octenyl succinic anhydride (OSA). Here, we present a self-consistent model of the particle structure, water content, and degree of chemical modification of the particles, as well as the emergence of well-defined interparticle spacings in concentrated dispersions, based on small-angle neutron scattering (SANS) measurements of aqueous dispersions of native phytoglycogen nanoparticles and particles that were hydrophobically modified using octenyl succinic anhydride (OSA) in both its protiated (pOSA) and deuterated (dOSA) forms. Measurements on native particles with reduced polydispersity have allowed us to refine the particle morphology, which is well described by a hairy particle (core-chain) geometry with short chains decorating the surface of the particles. The isotopic variants of OSA-modified particles enhanced the scattering contrast for neutrons, revealing lightly modified hairy chains for small degrees of substitution (DS) of OSA, and a raspberry particle geometry for the largest DS value, where the OSA-modified hairy chains collapse to form small seeds on the surface of the particles. This refined model of native and OSA-modified phytoglycogen nanoparticles establishes a quantitative basis for the development of new applications of this promising sustainable nanotechnology.
Phytoglycogen is a natural polysaccharide produced in the form of dense, 35 nm diameter nanoparticles by some varieties of plants such as sweet corn. The highly-branched, dendrimeric structure of phytoglycogen leads to interesting and useful properties such as softness and deformability of the particles, and a strong interaction with water. These properties make the particles ideal for use as unique additives in personal care, nutrition and biomedical formulations. In the present study, we describe rheology measurements of aqueous dispersions of phytoglycogen nanoparticles. The viscosity of the dispersions remained Newtonian up to large concentrations (∼20% w/w). For higher concentrations, the zero-shear viscosity increased dramatically, reaching values that exceeded that of the water solvent by six orders of magnitude at a concentration of 30% w/w and were well described by the Vogel-Fulcher-Tammann relation of glassy dynamics. The very large values of the zero-shear viscosity are coupled with significant deformation of the soft nanoparticles. We quantified the softness of the particles by performing osmotic pressure measurements on concentrated dispersions, obtaining a value of 15 kPa for the compressional modulus. For the most concentrated samples, we observed flow at stresses less than the apparent yield stress value determined by fitting the high strain rate data to the Herschel-Bulkley model. This behavior, similar to that of star polymer glasses, suggests the possibility of a hairy colloid particle geometry. Remarkably, phytoglycogen nanoparticles dispersed in water provide a very simple experimental realization of glass-forming dispersions of soft colloidal particles that can be used to validate theoretical models in detail.
Phytoglycogen is a highly branched polymer of glucose that forms dendrimeric nanoparticles. This special structure leads to a strong interaction with water that produces exceptional properties such as high water retention, low viscosity, and high stability of aqueous dispersions. We have used ellipsometry at controlled relative humidity (RH) to measure the equilibrium swelling of ultrathin films of phytoglycogen, which directly probes the interstitial forces acting within the films. Comparison of the swelling behavior of films of highly branched phytoglycogen to that of other glucose-based polysaccharides shows that the chain architecture plays an important role in determining both the strong, short-range repulsion of the chains at low RH and the repulsive hydration forces at high RH. In particular, the length scale λ that characterizes the exponentially decaying hydration forces provides a quantitative, RH-independent measure of film swelling that differs significantly for different glucose-based polysaccharides. By combining ellipsometry with infrared spectroscopy, we have determined the relationship between water structuring and inter-chain separation in the highly branched phytoglycogen nanoparticles, with maintenance of a high degree of water structure as the film swells significantly at high RH. These insights into the structure-hydration relationship for phytoglycogen are essential to the development of new products and technologies based on this sustainable nanomaterial.
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