Tough Stretchable Physically-Cross-linked Electrospun Hydrogel Fiber Mats.

Nature uses supramolecular interactions and hierarchical structures to produce water-rich materials with combinations of properties that are challenging to obtain in synthetic systems. Here, we demonstrate hierarchical supramolecular hydrogels from electrospun, self-associated copolymers with unprecedented elongation and toughness for high porosity hydrogels. Hydrophobic association of perfluoronated comonomers provides the physical cross-links for these hydrogels based on copolymers of dimethyl acrylamide and 2-(N-ethylperfluorooctane sulfonamido)ethyl methacrylate (FOSM). Intriguingly, the hydrogel fiber mats show an enhancement in toughness in comparison to compression molded bulk hydrogels. This difference is attributed to the size distribution of the hydrophobic aggregates where narrowing the distribution in the electrospun material enhances the toughness of the hydrogel. These hydrogel fiber mats exhibit extensibility more than double that of the bulk hydrogel and a comparable modulus despite the porosity of the fiber mat leading to >25 wt % increase in water content.

Mechanically Tough, Thermally Activated Shape Memory Hydrogels.

The shape memory behavior of a series of strong, tough hybrid hydrogels prepared by covalently cross-linking quad-polymers of N,N-dimethylacrylamide (DMA), 2-(N-ethylperfluoro-octanesulfonamido) ethyl methacrylate (FOSM), hydroxyethyl acrylate, and 2-cinnamoyloxyethyl acrylate was investigated. The hybrid hydrogels, which had physical and covalent cross-links, contained ∼60-70% water, were relatively soft and elastic, and exhibited high mechanical strength, extensibility, and fracture toughness. The temporary network was derived from glassy nanodomains due to microphase separation of the FOSM species. The switching temperature for shape memory was the glass transition temperature of the nanodomains. Some creep relaxation occurred in the fixed shape due to viscoelastic effects of the nanodomain cross-links, but shape fixing efficiencies of 84-88% were achieved for the fixed shape after 24 h at 10 °C. Shape recovery to the permanent shape was achieved by reheating the hydrogel to 65 °C and was essentially quantitative.

Strain-Promoted Crosslinking of PEG-based Hydrogels via Copper-Free Cycloaddition.

The synthesis of a 4-dibenzocyclooctynol (DIBO) functionalized polyethylene glycol (PEG) and fabrication of hydrogels via strain-promoted, metal-free, azide-alkyne cycloaddition is reported. The resulting hydrogel materials provide a versatile alternative in which to encapsulate cells that are sensitive to photochemical or chemical crosslinking mechanisms.

Large-scale structures in tetrahydrofuran-water mixture with a trace amount of antioxidant butylhydroxytoluene (BHT).

Author: Because of the closed-loop phase diagram of tetrahydrofuran (THF)-water mixture, THF aqueous solution naturally exhibits concentration fluctuations near the phase boundary. Besides the fast mode induced by concentration fluctuations, the 4.5% mole fraction THF aqueous solution is also characterized by a slow mode. The existence of a trace amount of butylhydroxytoluene (BHT) antioxidant in commercial THF strongly influences the slow mode in 4.5% mole fraction THF aqueous solution. A core-shell structure with a BHT core and a shell made from THF-rich THF-D(2)O mixture was identified by the combination of dynamic laser light scattering (DLS) and small-angle neutron scattering (SANS). BHT is hydrophobic, stabilized by a THF-rich domain in THF aqueous solution and acts as a tracer to make the large-scale structure (slow mode) "visible" through SANS because of its larger contrast with the solvent. In contrast, this large-scale structure was almost not detectable by SANS when BHT was removed from the THF-D(2)O mixture. Combined UV-vis, DLS, and static light scattering (SLS) indicated that slow-moving objects do exist and that their sizes almost do not change, but their concentration decreases to a small but nonzero value at the infinite dilution limit. The origin of the elusive large-scale structure at zero BHT concentration is still not clear, but it might be associated with some hydrophobic impurities or nanobubbles. However, a polydisperse sphere model of ∼8.5% mole fraction THF-D(2)O mixture can fit the structure with a radius of ∼100 nm, which gives the temperature-dependent low-q SANS profiles of 4.5% mole fraction THF aqueous solution at zero BHT concentration.

Origin of cononsolvency, based on the structure of tetrahydrofuran-water mixture.

The origin of poly(N-isopropylacrylamide) (PNIPAM) cononsolvency in tetrahydrofuran-water (THF-water) mixture was studied from the point of view of mixed solvent structure. The dynamic equilibrium of THF-water composition fluctuation in the mixed solvent system was found to be the main variable for this cononsolvency effect. Temperature and THF content dependences of composition fluctuation were studied by a combination of small angle neutron scattering (SANS), dynamic laser light scattering, and viscometry. A lower critical solution temperature (LCST) type phase diagram for THF-water mixture was established by SANS. The composition fluctuation in THF-water system reaches the maximum at about 20 mol % THF content at constant temperature and increases with temperature as getting closer to the phase boundary. This kind of composition fluctuation induces PNIPAM cononsolvency. When the THF content is lower than 4.5 mol %, the composition fluctuation influence of the THF-water structure is quite weak and most of water structure is not disturbed. Then, at low THF content, poly(N-isopropylacrylamide-co-ethylene glycol) (PNIPAM-co-PEG) microgel can still form hydrogen bonds with water and exist in the swollen state. The basic phase transition behavior of the microgel in THF-water is relatively similar to that in pure water, except for the shift of LCST to lower temperature. With THF content increasing to 20 mol %, the influence of composition fluctuation in the THF-water mixture becomes dominant. Solvent-solvent interaction is stronger than mixed solvent-polymer interaction. So PNIPAM does not dissolve in the mixed solvent, and the microgel is in the collapsed state. Further increase in THF content abates the contribution of composition fluctuation, and the structures of mixed solvents tend to be that in pure THF. PNIPAM becomes soluble again via Van der Waals interaction between THF and polymer.