One of the breakthroughs in biomaterials and regenerative medicine in the latest decade is the finding that matrix stiffness affords a crucial physical cue of stem cell differentiation. This statement was recently challenged by another understanding that protein tethering on material surfaces instead of matrix stiffness was the essential cue to regulate stem cells. Herein, we employed nonfouling poly(ethylene glycol) (PEG) hydrogels as the matrix to prevent nonspecific protein adsorption, and meanwhile covalently bound cell-adhesive arginine-glycine-aspartate (RGD) peptides onto the hydrogel surfaces in the form of well-defined nanoarrays to control specific cell adhesion. This approach enables the decoupling of the effects of matrix stiffness and surface chemistry. Mesenchymal stem cells (MSCs) were cultured on four substrates (two compressive moduli of the PEG hydrogels multiplied by two RGD nanospacings) and incubated in the mixed osteogenic and adipogenic medium. The results illustrate unambiguously that matrix stiffness is a potent regulator of stem cell differentiation. Moreover, we reveal that RGD nanospacing affects spreading area and differentiation of rat MSCs, regardless of the hydrogel stiffness. Therefore, both matrix stiffness and nanoscale spatial organization of cell-adhesive ligands direct stem cell fate.

Stem cells are capable of sensing and responding to the mechanical properties of extracellular matrixes (ECMs). It is well-known that, while osteogenesis is promoted on the stiff matrixes, adipogenesis is enhanced on the soft ones. Herein, we report an "abnormal" tendency of matrix-stiffness-directed stem cell differentiation. Well-defined nanoarrays of cell-adhesive arginine-glycine-aspartate (RGD) peptides were modified onto the surfaces of persistently nonfouling poly(ethylene glycol) (PEG) hydrogels to achieve controlled specific cell adhesion and simultaneously eliminate nonspecific protein adsorption. Mesenchymal stem cells were cultivated on the RGD-nanopatterned PEG hydrogels with the same RGD nanospacing but different hydrogel stiffnesses and incubated in the induction medium to examine the effect of matrix stiffness on osteogenic and adipogenic differentiation extents. When stem cells were kept at a low density during the induction period, the differentiation tendency was consistent with the previous reports in the literature; however, both lineage commitments were favored on the stiff matrices at a high cell density. We interpreted such a complicated stiffness effect at a high cell density in two-dimensional culture as the interplay of matrix stiffness and cell-cell contact. As a result, this study strengthens the essence of the stiffness effect and highlights the combinatory effects of ECM cues and cell cues on stem cell differentiation.

The current study examined the foaming behavior of poly(vinylpyrrolidone) (PVP)-silica composite nanoparticles. Individually, the two components, PVP and silica nanoparticles, exhibited very little potential to partition at the air-water interface, and as such, stable foams could not be generated. In contrast, combining the two components to form silica-PVP core-shell nanocomposites led to good "foamability" and long-term foam stability. Addition of an electrolyte (NaSO) was shown to have a marked effect on the foam stability. By varying the concentration of electrolyte between 0 and 0.55 M, three regions of foam stability were observed: rapid foam collapse at low electrolyte concentrations, delayed foam collapse at intermediate concentrations, and long-term stability (∼10 days) at the highest electrolyte concentration. The observed transitions in foam stability were better understood by studying the microstructure and physical and mechanical properties of the particle-laden interface. For rapidly collapsing foams the nanocomposite particles were weakly retained at the air-water interface. The interfaces in this case were characterized as being "liquid-like" and the foams collapsed within 100 min. At an intermediate electrolyte concentration (0.1 M), delayed foam collapse over ∼16 h was observed. The particle-laden interface was shown to be pseudo-solid-like as measured under shear and compression. The increased interfacial rigidity was attributed to adhesion between interpenetrating polymer layers. For the most stable foam (prepared in 0.55 M NaSO), the ratio of the viscoelastic moduli, G'/G″, was found to be equal to ∼3, confirming a strongly elastic interfacial layer. Using optical microscopy, enhanced foam stability was assessed and attributed to a change in the mechanism of foam collapse. Bubble-bubble coalescence was found to be significantly retarded by the aggregation of nanocomposite particles, with the long-term destabilization being recognized to result from bubble coarsening. For rapidly destabilizing foams, the contribution from bubble-bubble coalescence was shown to be more significant.

The yielding behaviour of silica nanoparticles partitioned at an air-aqueous interface is reported. Linear viscoelasticity of the particle-laden interface can be retrieved via a timedependent and electrolyte-dependent superposition, and the applicability of the 'soft glassy rheology' (SGR) model is confirmed. With increasing electrolyte concentration a non-ergodic state is achieved with particle dynamics arrested firstly from attraction induced bonding bridges and then from the cage effect of particle jamming, manifesting in a two-step yielding process under large amplitude oscillation strain (LAOS). The Lissajous curves disclose a shear-induced in-cage particle re-displacement within oscillation cycles between the two yielding steps, exhibiting a 'strain softening' transitioning to 'strain stiffening' as the interparticle attraction increases. By varying and the particle spreading concentration, , a variety of phase transitions from fluid-to gel-and glass-like can be unified to construct a state diagram mapping the yielding behaviors from one-step to two-step before finally exhibiting one-step yielding at high and .

Particle-stabilized emulsions and foams are widely encountered, as such there remains a concerted effort to better understand the relationship between the particle network structure surrounding droplets and bubbles, and the rheology of the particle-stabilized interface. Poly(vinylpyrrolidone)-coated silica nanoparticles were used to stabilize foams. The shear rheology of planar particle-laden interfaces were measured using an interfacial shear rheometer and the rheological properties measured as a function of the sub-phase electrolyte concentration and surface pressure. All particle-laden interfaces exhibited a liquid-like to solid-like transition with increasing surface pressure. The surface pressure-dependent interfacial rheology was then correlated to the formed micron-scale structures of the particle-laden interfaces which were imaged using a Brewster angle microscope. With the baseline knowledge established, foams were prepared using the same composite particles and the particle network structure imaged using cryo-SEM. An attempt has been made to correlate the two structures observed at a planar interface and that surrounding a bubble to elucidate the likely rheology of the bubble stabilizing particle network. Independent of the sub-phase electrolyte concentration, the resulting rheology of the bubble stabilizing particle network was strongly elastic and appeared to be in a compression state at the region of the L-S phase transition.