Charles. C. Han

Thermodynamic glass transition processes of electrospun membranes were first introduced to study their dynamic relaxation nature, which is not constantly in equilibrium. The relaxation modes of electrospun membranes are slow but measurable near and above the T_g, given the stretched chain over long distances. Based on differential scanning calorimetry (DSC) experiments and the general principle of mode-coupling theory (MCT), endothermic peak temperature and relaxation enthalpy were used to analyze the relaxation process by capturing these instantaneous “arrested” structures. The short- and long-wavelength relaxation modes could be identified with different annealing times and temperatures relative to DSC-measured T_g for electrospun membranes with different molecular weights. Results clearly showed the dynamic nature of a glass transition in polymeric materials. T_p and enthalpy loss initially increased and then directly decreased with the increase in annealing time. When T_a > T_g, regardless of the size of the molecular weight, the T_p and enthalpy loss of the PLGA fibers would directly decrease, and the curves would shift toward the melted one. Combination of electrospinningand normal DSC instrument can be used to investigating the dynamic relax process through an adequately designed kinetic scanning procedure. This result can be explained by the general principle of MCT-type dynamic theory.

Most of natural water-soluble polymers are difficult to electrospin due to their specific chain conformation in aqueous solution, which limits their applications. This study investigated the effects of polyethylene oxide (PEO) on the electrospinning of hyaluronic acid (HA) in HA/PEO aqueous solutions. The rheological properties of HA/PEO aqueous solutions showed polymer chain entanglement in HA was the essential factor affecting its electrospinnability. Wide-angle X-ray scattering and differential scanning calorimetry analyses of a PEO crystal showed different crystallization behavior of the PEO chain with different molecular weight, which indicates different interaction with HA. A schematic molecular model has been proposed to explain the effect of PEO on the chain conformation of HA along with the relationship between electrospinnability and chain entanglement. PEO with a relatively high molecular weight with limited crystal formation formed extensive chain entanglements with HA, while PEO with relatively low molecular weight weakened the interactions among HA chains. The findings of this study provide a wide perspective to better understand the electrospinning mechanisms of natural polyelectrolytes and usage in tissue engineering.

Gelation transitions in a colloidal system, where there is a strong reversible attraction between small, soft microgels and large, hard spheres, are systematically investigated. Different from widely studied depletion attraction systems that are also two-component systems, the strong attraction between small solvent and large solute particles introduces bridging attractions between large solute particles. We conclusively demonstrate that the formation of physical gels at the intermediate volume fraction of our bridging attraction system follows more closely with the percolation line that is in stark contrast to what is observed in depletion attraction systems, where the gelation transition is related with the frustrated spinodal separation, not a purely kinetic phenomenon. Our results introduce a different way to control gelation transitions in spherical colloidal systems, and imply that people need to be prudent when generalizing the physical picture of the gelation transitions obtained from systems with different origins of effective attraction as the solvent molecule may play important roles.

In this study, the attraction between large hard polystyrene (PS) spheres is studied by using three types of small microgels as bridging agents. One is a purely soft poly(N-isopropylacrylamide) (PNIPAM) microgel, the other two have a non-deformable PS hard core surrounded by a soft PNIPAM shell but are different in the core–shell ratio. The affinity for bridging the large PS spheres is provided and thus affected by the PNIPAM constituent in the microgels. The bridging effects caused by the microgels can be indirectly incorporated into their influence on the effective attraction interaction between the large hard spheres, since the size of the microgels is very small in comparison to the size of the PS hard spheres. At a given volume fraction of large PS spheres, they behave essentially as hard spheres in the absence of small microgels. By gradually adding the microgels, the large spheres are connected to each other through the bridging of small particles until the attraction strength reaches a maximum value, after which adding more small particles slowly decreases the effective attraction strength and eventually the large particles disperse individually when saturated adsorption is achieved. The aggregation and gelation behaviors triggered by these three types of small microgels are compared and discussed. A way to tune the strength and range of the short-range attractive potential via changing the softness of bridging microgels (which can be achieved either by using core–shell microgels or by changing the temperature) is proposed.

Implantation of sustained antibacterial system after abdominal surgery could effectively prevent complicated intra-abdominal infection. In this study, a simple blended electrospun membrane made of poly(d,l-lactic-co-glycolide) (PLGA)/poly(dioxanone) (PDO)/Ciprofloxacin hydrochloride (CiH) could easily result in approximately linear drug release profile and sustained antibacterial activity against both Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The addition of PDO changed the stack structure of PLGA, which in turn influenced the fiber swelling and created drug diffusion channels. It could be a good candidate for reducing postoperative infection or be associated with other implant to resist biofilm formation.

Φ _total = Φ _PSS + Φ _CS = 32% is fixed above the LCST.

Placing a physical barrier between the injured site and the adjacent tissues is a very common and highly effective approach to prevent abdominal adhesions in these days. A biodegradable trilayered barrier was fabricated to prevent formation of abdominal adhesions, in which a poly(lactide-co-glycolide)/poly(lactide)-b-poly(ethylene glycol) (PLGA/PLA-b-PEG) electrospun layer was sandwiched between layers of carboxymethyl chitosan (CMCS) sponge. The hydrophilic CMCS sponge layers with glycerin (GL) could adhere to the surface of wound easily, and present great hemostatic capability. The mechanism of the formation of adhesion related to blood clots acting with fibroblast cells was evaluated in detail. The blood clot acted as a “medium” inducing the fibroblast cells growth and proliferation, but had no special attraction on epithelial cells. CMCS sponge layer took away the blood clots during the swelling and dissolution stages. The electrospun layer promoted the growth of epithelial cells, but exhibited inhibition on the adhesion and spread of fibroblast cells, which ensured excellent effect of adhesion prevention. Evaluated by a rat model of sidewall defect-bowel abrasion, significant reductions of postoperative adhesion in its level and occurrence were observed in animals treated by the trilayered barrier.

In this study, mixed suspensions of large hard polystyrene microspheres and small soft poly(N-isopropylacrylamide) microgels are used as model systems to investigate the static and viscoelastic properties of suspensions which go through liquid to gel transitions. The microgels cause short-range attraction between microspheres through the bridging and depletion mechanism whose strength can be tuned by the microgel concentration. Rheological measurements are performed on suspensions with the volume fraction (Φ) of microspheres ranging from 0.02 to 0.15, and the transitions from liquid-like to solid-like behaviors triggered by the concentration of microgels are carefully identified. Two gel lines due to bridging attraction under unsaturated conditions are obtained. Ultra-small angle neutron scattering is used to probe the thermodynamic properties of suspensions approaching the liquid–solid transition boundaries. Baxter's sticky hard-sphere model is used to extract the effective inter-microsphere interaction introduced by the small soft microgels. It is found that the strength of attraction (characterized by a single stickiness parameter τ) on two gel lines formed by bridging is very close to the theoretical value for the spinodal line in the τ–Φ phase diagram predicted by Baxter's model. This indicates that the nature of the gel state may have the same thermodynamic origins, independent of the detailed mechanism of the short-range attraction. The relationship between the rheological criterion for the liquid–solid transition and the thermodynamic criterion for the equilibrium–nonequilibrium transition is also discussed.