Effect of Surface Functionality on the Rheological and Self-Assembly Properties of Chitin and Chitosan Nanocrystals and Use in Biopolymer Films.

Chitin nanocrystals (ChNCs) are unique to all other bio-derived nanomaterials in one aspect: the inherent presence of a nitrogen moiety. By tuning the chemical functionality of this nanomaterial, and thus its charge and hydrogen bonding capacity, one can heavily impact its macroscopic properties such as its rheological and self-assembly characteristics. In this study, two types of ChNCs are made using acid hydrolysis (AH-ChNCs) and oxidative (OX-ChNCs) pathways, unto which deacetylation using a solvent-free procedure is utilized to create chitosan nanocrystals (ChsNCs) of varying degree of deacetylation (DDA). These nanocrystals were then studied for their rheological behavior and liquid crystalline ordering. It was found that with both deacetylation and carboxylation of ChNCs, viscosity continually increased with increasing concentrations from 2 to 8 wt %, contrary to AH-ChNC dispersions in the same range. Interestingly, increasing the amine content of ChNCs was not proportional to the storage modulus, where a peak saturation of amines provided the most stiffness. Conversely, while the introduction of carboxylation increased the elastic modulus of OX-ChNCs by an order of magnitude from that of AH-ChNCs, it was decreased by increasing DDA. Deacetylation and carboxylation both inhibited the formation of a chiral nematic phase. Finally, these series of nanocrystals were incorporated into biodegradable pectin-alginate films as a physical reinforcement, which showed increased tensile strength and Young's modulus values for the films incorporated with ChsNCs. Overall, this study is the first to investigate how surface functionalization of chitin-derived nanocrystals can affect their rheological and liquid crystalline properties and how it augments pectin/alginate films as a physical reinforcement nanofiller.

A Janus Au-Polymersome Heterostructure with Near-Field Enhancement Effect for Implant-Associated Infection Phototherapy.

Polymer-inorganic hybrid Janus nanoparticles (PI-JNPs) have attracted extensive attention due to their special structures and functions. However, achieving the synergistic enhancement of photochemical activity between polymer and inorganic moieties in PI-JNPs remains challenging. Herein, the construction of a novel Janus Au-porphyrin polymersome (J-AuPPS) heterostructure by a facile one-step photocatalytic synthesis is reported. The near-field enhancement (NFE) effect between porphyrin polymersome (PPS) and Au nanoparticles in J-AuPPS is achieved to enhance its near-infrared (NIR) light absorption and electric/thermal field intensity at their interface, which improves the energy transfer and energetic charge-carrier generation. Therefore, J-AuPPS shows a higher NIR-activated photothermal conversion efficiency (48.4%) and generates more singlet oxygen compared with non-Janus core-particle Au-PPS nanostructure (28.4%). As a result, J-AuPPS exhibits excellent dual-mode (photothermal/photodynamic) antibacterial and anti-biofilm performance, thereby significantly enhancing the in vivo therapeutic effect in an implant-associated-infection rat model. This work is believed to motivate the rational design of advanced hybrid JNPs with desirable NFE effect and further extend their biological applications.