Nonsolvent-induced phase separation of poly(3-hydroxybutyrate) and poly(hydroxybutyrate-co-hydroxyvalerate) blend as a facile platform to fabricate versatile nanofiber gels: Aero-, hydro-, and oleogels.

We demonstrated a strategy to prepare different types of 3-D nanofibrous polymeric gels, including hydro-, aero-, and oleogels by nonsolvent-induced phase separation (NIPS). NIPS-derived gel monoliths of poly(3-hydroxybutyrate) (PHB) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) blends were converted into hydrogels and aerogels by solvent exchange and freeze-drying, respectively. The high hydrophobicity and porosity of the nanofibrous PHB/PHBV aerogels enabled them to absorb various oils and swell to 20-30 times their own weight. The pseudo-second-order model was successfully used to describe the oil absorption behavior, and the obtained absorption rate constant increased with increasing PHBV content. The oil-swollen aerogels were highly elastic, thereby indicating that NIPS-derived aerogels are an excellent template for the fabrication of oleogels. With an increase in the PHBV ratio, the gels exhibited reduced modulus and collapse strength but increased collapse strain, thereby revealing higher ductility by compression. The rapid separation and re-binding of the liquid phase entrapped in the nanofiber network resulted in the unique thixotropic properties of the hydro- and oleogels. Indomethacin, a hydrophobic model drug, was successfully incorporated into injectable self-healing oleogels containing soybean oil and aerogels. These gels exhibited excellent cytocompatibility, and a better sustained drug release was observed for the oleogels compared to the aerogels.

Injectable in Situ Forming Hydrogels of Thermosensitive Polypyrrole Nanoplatforms for Precisely Synergistic Photothermo-Chemotherapy.

The combination of photothermal therapy (PTT) with chemotherapy has great potential to maximize the synergistic effect of thermo-induced chemosensitization and improve treatment performance. To achieve high drug-loading capacity as well as precise synchronization between the controllable release of chemotherapeutics and the duration of near-infrared PTT, in this work, a facile one-step method was first developed to fabricate a novel injectable in situ forming photothermal modulated hydrogel drug delivery platform (D-PPy@PNAs), in which a PNIPAM-based temperature-sensitive acidic triblock polymer [poly(acrylic acid-b-N-isopropylamide-b-acrylic acid (PNA)] was utilized as the stabilizing agent in the polymerization of polypyrrole (PPy). The in situ forming hydrogels showed a sensitive temperature-responsive sol-gel phase-transition behavior, as well as an excellent photothermal property. The strong interaction of ionic bonds together with π-π stacking interactions resulted in high doxorubicin (DOX) loading capacity and controlled/sustained drug release behavior. In addition, D-PPy@PNAs also displayed enhanced cellular uptake and promoted intratumoral penetration of DOX upon NIR laser irradiation. The synergistic photothermal therapy-chemotherapy of D-PPy@PNA hydrogels greatly improved the antitumor efficacy in vivo. Therefore, thermosensitive polypyrrole-based D-PPy@PNA hydrogels may be powerful drug delivery nanoplatforms for precisely synergistic photothermo-chemotherapy of tumors.