Transition in the Glassy Dynamics of Melts of Acid-Hydrolyzed Phytoglycogen Nanoparticles.

The deformability, responsiveness, and tunability of soft nanoparticles (NPs) offer unique opportunities to learn about their complex properties and the interactions between particles. In the present study, we provide new insights into the physical properties of phytoglycogen (PG) NPs, which are soft, compact particles with a dendritic architecture that are produced in the kernels of sweet corn. In particular, we study PG NPs modified using acid hydrolysis, which not only reduces their diameter but also alters their stiffness, internal structure, and the interactions between particles in aqueous dispersions. We used steady shear rheology to determine the dependence of the relative zero-shear viscosity ηr of aqueous dispersions of acid-hydrolyzed PG NPs on the effective volume fraction ϕeff, which indicated a reduction in stiffness of the particles relative to that of native PG NPs. We quantified this difference by analyzing the nature of the colloidal glasses formed at high ϕeff. We measured a smaller value of the fragility index m for acid-hydrolyzed PG NP glasses than that for native PG NP glasses, indicating that acid-hydrolyzed PG NPs form stronger glasses and are therefore softer than native PG NPs. Unlike the native PG NPs, we observed a distinctive change in the character of the glass transition of the acid-hydrolyzed PG NPs as ϕeff was increased above ϕeff∼1: a crossover in the dependence of ηr on ϕeff from Vogel-Fulcher-Tammann behavior to a more gradual, Arrhenius-like behavior. By expressing the steady shear and oscillatory rheology data in terms of generalized Péclet numbers, we obtained collapse of the data onto master curves. We interpret this result in terms of the acid-hydrolyzed PG NPs predominantly interpenetrating neighboring particles at large ϕeff, for which fluctuations of the outer chains enhance the mobility of the particles and make α-relaxation times τα experimentally accessible.

Structure, Hydration, and Interactions of Native and Hydrophobically Modified Phytoglycogen Nanoparticles.

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.

Unusual polysaccharide rheology of aqueous dispersions of soft phytoglycogen nanoparticles.

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.