Phytoglycogen is a naturally occurring polysaccharide nanoparticle made up of extensively branched glucose monomers. It has a number of unusual and advantageous properties, such as high water retention, low viscosity, and high stability in water, which make this biomaterial a promising candidate for a wide variety of applications. In this study, we have characterized the structure and hydration of aqueous dispersions of phytoglycogen nanoparticles using neutron scattering. Small angle neutron scattering results suggest that the phytoglycogen nanoparticles behave similar to hard sphere colloids and are hydrated by a large number of water molecules (each nanoparticle contains between 250% and 285% of its mass in water). This suggests that phytoglycogen is an ideal sample in which to study the dynamics of hydration water. To this end, we used quasielastic neutron scattering (QENS) to provide an independent and consistent measure of the hydration number, and to estimate the retardation factor (or degree of water slow-down) for hydration water translational motions. These data demonstrate a length-scale dependence in the measured retardation factors that clarifies the origin of discrepancies between retardation factor values reported for hydration water using different experimental techniques. The present approach can be generalized to other systems containing nanoconfined water.

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Phytoglycogen is a naturally occurring glucose polymer that is produced by sweet corn in the form of compact nanoparticles with a dendritic or tree-like architecture. The soft and porous nature of the nanoparticles, combined with their biodegradability and lack of toxicity, makes them ideal for a broad range of applications in personal care, nutrition, and biomedicine. To fully exploit these applications, it is necessary to understand the complex properties of the soft, hydrated nanoparticles in detail. In the present study, we have used atomic force microscopy (AFM) force spectroscopy to collect high-resolution force−distance maps of a large number of individual phytoglycogen nanoparticles, providing unique insights into the morphology and mechanical stiffness of the nanoparticles at the single-particle level. Our measurements performed in water on nanoparticles covalently bonded to gold surfaces revealed an inner branched structure and high deformability of the nanoparticles at modest values of the applied force. These measurements also allowed us to determine the spatial distribution of Young's modulus values within individual nanoparticles. Drying of the nanoparticles resulted in a dramatic increase in Young's modulus, quantifying the effect of hydration on their mechanical stiffness. We obtained excellent agreement between AFM and osmotic pressure measurements of the mechanical properties of hydrated phytoglycogen nanoparticles; the ratio of the average Young's modulus measured using AFM to the bulk modulus measured using osmotic pressure was in close agreement with that expected for a material with Poisson's ratio ν = 0. The soft, deformable nature of phytoglycogen nanoparticles revealed by our measurements provides new insights at the single-nanoparticle level and suggests their suitability for biomedical applications such as transdermal and targeted drug delivery.

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Phytoglycogen (PG) is a polysaccharide produced in the kernels of sweet corn as soft, highly branched, compact nanoparticles. Its tree-like or dendritic architecture, combined with a high-safety profile, makes PG nanoparticles attractive for use in biological applications, many of which rely on the association or binding of small biomolecules. We have developed a methodology to functionalize surface plasmon resonance (SPR) sensor surfaces with PG nanoparticles, and we demonstrate the utility of the PG-functionalized SPR sensor by measuring the binding affinity of the tetrameric concanavalin A (ConA) protein to both native PG nanoparticles and smaller, softer acid-hydrolyzed PG nanoparticles. We measure comparable values of the equilibrium association constant K for native and acid-hydrolyzed PG, with a slightly smaller value for the acid-hydrolyzed particles that we attribute to unfavorable lateral interactions between the tetrameric subunits of ConA due to the increase in surface curvature of the smaller acid-hydrolyzed PG particles. We also use infrared reflection-absorption spectroscopy (IRRAS) to show that ConA maintains a large fraction of its native conformation, and thus its bioactivity, upon binding to PG, representing an important step toward the realization of PG as a novel bioactive delivery vehicle.