Structure and dynamics in suspensions of soft core-shell colloids in the fluid regime.

We report on a detailed experimental study of the structure and short-time dynamics in fluid-regime suspensions of soft core-shell spherical particles with different molecular weights of the chains forming the soft outer shell, and therefore different degrees of particle softness, using 3D dynamic light scattering (3D-DLS). Owing to the particle softness, the liquid-crystal coexistence regime is found to be broader than that of hard-sphere (HS) suspensions. Static light scattering in the dilute regime yields form factors that can be described using a spherical core-shell model and second virial coefficients A2 > 0 indicative of purely repulsive interactions. The particle-particle interactions are longer ranged for all considered systems except those of the smaller molecular weight chain grafted particles which show a HS-like behavior. 3D-DLS experiments in the concentrated regime up to the liquid-crystal transition provide the short-time diffusion function, D(q), in a broad range of scattering wavenumbers, q, from which the structural (cage) and short-time self-diffusion coefficients D(qm) and DS = D(q ≫ qm), respectively, are deduced as functions of the effective particle volume fraction, ϕ = c/c*, where c* is the overlap concentration, calculated using the hydrodynamic particle radius, RH. The size of the nearest-neighbor cage of particles is characterized by 2π/qm, with D(q) and the static structure factor S(q) attaining at qm the smallest and largest values, respectively. Experimental data of D(qm) and DS are contrasted with analytic theoretical predictions based on a simplifying hydrodynamic radius model where the internal hydrodynamic structure of the core-shell particles is mapped on a single hydrodynamic radius parameter γ = RH/Reff, for constant direct interactions characterized by an (effective) hard-core radius Reff. The particle softness is reflected, in particular, in the corresponding shape of the static structure factor, while the mean solvent (Darcy) permeability of the particles related to γ is reflected in the dynamic properties only. For grafted particles with longer polymer chains, D(qm) and DS are indicative of larger permeability values while particles with shorter chains are practically nonpermeable. The particle softness is also evident in the effective random close packing fraction estimated from the extrapolated zero-value limit of the cage diffusion coefficient D(qm).

Physicochemical properties of electrostatically crosslinked carrageenan/chitosan hydrogels and carrageenan/chitosan/Laponite nanocomposite hydrogels.

In this work physical carrageenan/chitosan (Car/Chit) hydrogels are prepared by electrostatic complexation between the two oppositely charged polysaccharides. The hydrogels have storage moduli in the order of 5-10 kPa and swelling ratios in the order of 5000-6000 %. At conditions where both polysaccharides are highly charged (pH 5) the swelling ratios are lower than the ones at conditions of lower dissociation i.e., at pH 2 and 7 and the opposite trend is found for the storage modulus. Chit appears to act as a crosslinker for Car as increasing its concentration the swelling ratio decreases and the moduli increase. The hydrogels can incorporate the nanoclay Laponite (Lap) and form hybrid nanocomposites where the intercalation by the two biopolymers leads to exfoliation of the clay nanoplatelets in the presence of both Car and Chit. The composite hydrogels retain the mechanical properties of the Car/Chit hydrogels at the studied pH range (pH 2 to pH 7). This shows the prepared hydrogels can be potentially used as multifunctional biomaterials for drug delivery, tissue engineering and bone regeneration applications.