Rheological modifiers are essential ingredients in commercial materials that exploit facile and repeatable phase transitions. Although rheological modifiers are used to change flow behavior or quiescent stability, the complex properties of particulate gels during dilution is not well studied. We characterize a dynamically evolving colloidal gel, hydrogenated castor oil (HCO), a naturally sourced material, used in consumer products. This HCO scaffold consists of fibrous colloids, a surfactant (linear alkylbenzene sulfonate) and water. The gel undergoes critical transitions, degradation and formation, in response to an osmotic pressure gradient. Multiple particle tracking microrheology (MPT) measures the evolving material properties. In MPT, fluorescent probe particles are embedded into the sample and Brownian motion is measured. MPT data are analyzed using time-cure superposition, identifying critical transition times and critical relaxation exponents for degradation and formation where tc,deg = 102.5 min, ndeg = 0.77 ± 0.09, tc,for = 31.9 min, and nfor = 0.94 ± 0.11, respectively. During degradation and formation HCO gels evolve heterogeneously, this heterogeneity is characterized spatially and temporally. Heterogeneity of the gel is quantified by comparing variances of single particle van Hove correlation functions using an F-test with a 95% confidence interval. HCO transitions have rheological heterogeneous microenvironments that are homogeneously distributed throughout the field of view. Although HCO gels do evolve heterogeneously, this work determines that these heterogeneities do not significantly change traditional MPT measurements but the analysis techniques developed provide additional information on the unique heterogeneous scaffold microenvironments. This creates a toolbox that can be widely applied to other scaffolds during dynamic transitions.

SynopsisParticle tracking microrheology is used to study the effect of a constant applied shear during gelation of aqueous gellan gum with a monovalent salt. Shear modifies the gellan gum hydrogel microstructure and the bulk rheological properties of the system, depending on whether shear is applied during gelation or afterwards. The microstructure determines the linear elastic response of the gel, as well as the critical strain and stress above which the response becomes nonlinear. Bulk oscillatory rheology is used to study microstructured gellan gum hydrogels at different polymer and salt concentrations. The similarity between our system and concentrated microgel particle suspensions can be explained by considering the microstructured gellan system to be composed of microgel particles whose size is set by the applied shear stress magnitude during gelation. Polymer concentration and ionic strength control the individual microgel particles' elastic properties. We also find the gellan system exhibits an isoenergetic transition from the jammed to un-jammed state when sheared, similar to jammed colloidal systems ͓C. G. Robertson and X. R. Wang, a͒ Author to whom correspondence should be addressed; electronic mail: caggioni@deas.harvard.edu "Isoenergetic jamming transition in particle-filled systems," Phys. Rev. Lett. 95, 075703͑2005͔͒.

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Nanostructured capsules comprised of the anionic bile salt, sodium taurodeoxycholate (STDC), and the biocompatible cationic polymer, chitosan, were prepared to assess their potential as novel tailored release nanomaterials. For comparison, a previously studied system, sodium dodecyl sulfate (SDS), and polydiallyldimethylammonium chloride (polyDADMAC) was also investigated. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified the presence of lamellar and hexagonal phase at the surfactant-polymer interface of the respective systems. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and salt concentration, respectively, and were found to influence the liquid-crystalline nanostructure formed. The hexagonal phase persisted at high temperatures, however the lamellar phase structure was lost above ca. 45 °C. Both mesophases were found to dissociate upon addition of 4% NaCl solution. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from the lamellar phase significantly increased in response to changes in the solution conditions studied, suggesting that modulating the drug release from these bile salt-chitosan capsules is readily achieved. In contrast, release from the hexagonal phase capsules had no appreciable response to the stimuli applied. These findings provide a platform for these oppositely charged surfactant and polymer systems to function as stimuli-responsive or sustained-release drug delivery systems.

Rheological modifiers are added to formulations to tune rheology, enable function and drive phase changes requiring an understanding of material structure and properties. We characterize two colloidal rod systems during phase transitions using multiple particle tracking microrheology, which measures the Brownian motion of probes embedded in a sample. These systems include a colloid (monodisperse polyamide or polydisperse hydrogenated castor oil), surfactant (linear alkylbenzene sulfonate [LAS]), and nonabsorbing polymer (polyethylene oxide [PEO]) which drives gelation by depletion interactions. Phase transitions are characterized at all concentrations using time‐cure superposition. We determine that rheological evolution depends on LAS:colloid. The critical PEO concentration required to form a gel, cc/c*, is independent of LAS:colloid, critical relaxation exponent, n, is dependent on LAS:colloid, and both are independent of colloid polydispersity. n indicates the material structure at the phase transition. At LAS:colloid > 16, the scaffold is a tightly associated network and at LAS:colloid = 16 a loosely associated network.