Selective and Controlled Release Responsive Nanoparticles with Adsorption-Pairing Synergy for Anthocyanin Extraction.

Anthocyanins with different structures have different anti-inflammatory and anti-cancer properties. Precise structural use can improve the chemopreventive effects of anthocyanins and enhance treatment outcomes because the anthocyanin structure influences its functional sites and activities. However, owing to the available variety of anthocyanins and their complex structures, the low matching of intermolecular forces between existing adsorbents and anthocyanins limits the targeted separation of anthocyanin monomers. Short-range and efficient selective binding, which is difficult to achieve, is the current focus in the extraction field. We here developed self-assembled Fe3O4-based nano adsorbers with different surface modifications based on adsorption-pairing synergy. The electrostatic force, coordination bond, hydrogen bond, and π-π* bond together induced selective adsorption between Fe3O4 nanoparticles and anthocyanin molecules. An acid-release solution disrupted the polarity balance in the aforementioned association system, thereby promoting the controlled release of anthocyanins. Among the candidates, the effects of morphology, particle size, surface charge, and functional group on adsorption performance were analyzed. The polyacrylamide-modified magnetic Fe3O4 nanoparticles were found to be favorable for selectively extracting anthocyanin, with an adsorption capacity of 19.74 ± 0.07 mg g-1. The release percentage of cyanidin-3-O-glucoside reached up to 98.6% ± 1.4%. This study offers a scientific basis for developing feasible nanotechniques to extract anthocyanins and plant active substances.

Biofunctionalized chondrogenic shape-memory ternary scaffolds for efficient cell-free cartilage regeneration.

Cartilage defect repair remains a great clinical challenge due to the limited self-regeneration capacity of cartilage tissue. Surgical treatment of injured cartilage is rather difficult due to the narrow space in the articular cavity and irregular defect area. Herein, we designed and fabricated chondrogenic and physiological-temperature-triggered shape-memory ternary scaffolds for cell-free cartilage repair, where the poly (glycerol sebacate) (PGS) networks ensured elasticity and shape recovery, crystallized poly (1,3-propylene sebacate) (PPS) acted as switchable phase, and immobilized bioactive kartogenin (KGN) endowed the scaffolds with chondrogenic capacity. The resultant scaffolds exhibited shape-memory properties with shape-memory fixed ratio of 98% and recovered ratio of 97% at 37°C for PPS/PGS/KGN-100, indicating a good potential for minimally invasive implantation. The scaffolds gradually degraded in Dulbecco's phosphate-buffered saline and released KGN up to 12 weeks in vitro. In addition, the scaffolds promoted chondrogenic differentiation while inhibiting osteogenic differentiation of bone marrow-derived mesenchymal stem cells in a concentration-dependent manner and cartilage regeneration in full-thickness defects of rat femoropatellar groove for 12 weeks. Consequently, the PPS/PGS/KGN-100 scaffolds stimulated the formation of an overlying layer of neocartilage mimicking the characteristic architecture of native articular cartilage even in the absence of exogenous growth factors and seeded cells. This study provides much inspiration for future research on cartilage tissue engineering. STATEMENT OF SIGNIFICANCE: There are two crucial challenges for cartilage defect repair: the lack of self-regeneration capacity of cartilage tissue and difficult scaffold implantation via traditional open surgery due to space-limited joints. Herein, bioactive body-temperature-responsive shape memory scaffolds are designed to simultaneously address the challenges. The scaffolds can be readily implanted by minimally invasive approach and recover by body-temperature of patient. The integration of kartogenin endows scaffolds the bioactivity, leading to the first example of bulk shape-memory scaffolds for cell-free cartilage repair. These characteristics make the scaffolds advantageous for clinical translation. Moreover, our developed material is easy to be functionalized due to the presence of extensive free hydroxyl groups and provides a versatile platform to design diverse functional shape memory biomaterials.

Fabrication of In Situ Nanofiber-Reinforced Molecular Composites by Nonequilibrium Self-Assembly.

Although the concept of molecular composites (MCs) is very promising, there are major obstacles arising from the immiscibility of the rigid-rod with the random-coil polymers. Here, we developed a novel method for fabricating an in situ reinforced MC system with nonequilibrium self-assembled nanofibrous structures based on bisphenol A epoxy resin, 4,4'-diaminodiphenylsulfone, bismaleimide, and a polyphenylene ether (PPO) oligomer. A variety of spectroscopic and morphological techniques were used to probe the structural evolution from the emergence of nanofibrils, to growth and aggregation of nanofibers, and then to the formation of in situ reinforced MC with strong interfacial interactions. The in situ nanofibers within the polymer matrix could be formed by the polymerization force extruding the PPO phase through the interspaces within the simultaneous interpenetrating network polymers during the cure process of the thermosetting resin system. Compared to the control sample, the in situ nanofiber-reinforced MC exhibited better thermal properties and flame retardancy. In particular, the obtained MC showed a significant improvement in glass transition temperature and mechanical properties, which were mainly attributed to the restriction of high thermal stability of PPO on the segmental motion of polymer chains, the toughening and reinforcement behaviors of PPO nanofibers on the matrix, and the chemical interaction at the PPO/matrix interface.