Nonreleasing AgNP Colloids Composite Hydrogel with Potent Hemostatic, Photodynamic Bactericidal and Wound Healing-Promoting Properties.

Reactive oxygen species (ROS) produced by noble metallic nanoparticles under visible light is an effective way to combat drug-resistant bacteria colonized on the wound. However, the photocatalytic efficiency of noble metallic nanoparticles is limited by its self-aggregation in water media. Moreover, the fast release of noble metallic ions from nanoparticles might engender cellular toxicity and hazardous environmental issues. Herein, we chose AgNPs, the most common plasmonic noble metallic nanoparticles, as an example, modifying the surface of AgNPs with oleic acid and n-butylamine and imbedded them into calcium alginate (CA) hydrogel that holds tissue adhesion, rapid hemostatic, sunlight-sensitive antibacterial and anti-inflammatory abilities, and thus effectively promotes the healing of wounds. Unlike conventional AgNP-based materials, the constrain of colloids and hydrogel networks hinders the leach of Ag+. Nonetheless, the CA/Ag hydrogels exhibit on-demand photodynamic antibacterial efficacy due to the generation of ROS under visible light. In addition, the CA/Ag hydrogel can effectively stop the hemorrhage in a mouse liver bleeding model due to their skin-adaptive flexibility and tissue adhesiveness. The potent sunlight-responsive antibacterial activity of the CA/Ag hydrogel can effectively kill multidrug-resistant bacteria both in vitro (>99.999%) and in vivo (>99.9%), while the diminished Ag+ release guarantees its biocompatibility. The CA/Ag hydrogel significantly promotes the wound healing process by the downregulation of proinflammatory cytokines (TNF-α and IL-6) in a rodent full-thickness cutaneous wound model. Overall, the proposed multifunctional CA/Ag nanocomposite hydrogel has excellent prospects as an advanced wound dressing.

Synthesis of DOPO-Based Phosphorus-Nitrogen Containing Hyperbranched Flame Retardant and Its Effective Application for Poly(ethylene terephthalate) via Synergistic Effect.

To obtain industrialized poly(ethylene terephthalate) (PET) composites with highly efficient flame retardancy, a phosphorus-nitrogen (P-N) containing hyperbranched flame retardant additive was synthesized by 9,10-dihydro-9-oxa-10-phospho-phenanthrene-butyric acid (DDP) and tris(2-hydroxyethyl) isocyanurate (THEIC) through high temperature esterification known as hyperbranched DDP-THEIC (hbDT). The chemical structure of the synthesized hbDT was determined by FTIR, 1H NMR, 13C NMR, and GPC, etc. Subsequently, hbDT/PET composites were prepared by co-blending, and the effects of hbDT on the thermal stability, flame retardancy, combustion performance, and thermal degradation behavior of PET were explored to deeply analyze its flame retardant mechanism. The test results showed that hbDT was successfully synthesized, and that hbDT maintained thermal stability well with the required processing conditions of PET as retardant additives. The flame retardant efficiency of PET was clearly improved by the addition of hbDT via the synergistic flame-retardant effect of P and N elements. When the mass fraction of flame retardant was 5%, the LOI of the hbDT/PET composite increased to 30.2%, and the vertical combustion grade reached UL-94 V-0. Compared with pure PET, great decreased total heat release (decreased by 16.3%) and peak heat release rate (decreased by 54.9%) were exhibited. Finally, the flame retardant mechanism of hbDT/PET was supposed, and it was confirmed that retardant effect happened in both the gas phase and condensed phase. This study is expected to provide a new idea for the development of low toxic, environment-friendly and highly efficient flame retardant additive for polyesters in an industry scale.

Aqueous Self-Assembly of Hydrophobic Molecules Influenced by the Molecular Geometry.

Water, in addition to acting as a solvent, plays a constructional role in aqueous self-assembly. The hydrophobic molecule of POSS-PDI-POSS (POSS = polyhedral oligomeric silsesquioxanes, PDI = perylene diimide) has a shape anisotropy in which POSS is a ball-like bulky group and PDI is a flat aromatic group. The self-assembly of this molecule in water created assemblies with inner spaces due to the steric effect, which suppressed aromatic interactions of PDI and trapped water for the colloidal stability. By replacing POSS with dodecyl (C12), C12-PDI-C12 aggregated with extended aromatic interaction of PDI and less inner water. The resulting aggregates tended to agglomerate and precipitate. This discovery extended the scope of aqueous self-assembly by using the building blocks without amphiphilicity and created knowledge for biophysics.

Host-guest chemistry of giant molecular shape amphiphiles based on POSS-PDI conjugates.

Giant shape amphiphiles (GSA) are giant molecules made with nano-building blocks that have distinct shapes. The incompatible packing behaviors of the nano-building blocks of GSA could create cavities within certain conformers of the GSA, but the host-guest chemistry of GSA has not been explored yet. In this study, POSS-PDI-POSS (PPP), which is made by connecting two nano-cubes, isobutyl-polyhedral oligomeric silsesquioxanes (POSS), to a conjugated π-conjugated core, perylene diimide (PDI), is demonstrated as a novel acyclic synthetic host. In its bent conformer, PPP shows a cavity next to its PDI core. Via forming host-guest complexes with π-conjugated guests such as pyrene and perylene, PPP is found to transform from the bent-conformer into the extended-conformer, creating the steric features to accommodate guest molecules. Subsequent thermal annealing of the host-guest complexes removes the π-conjugated guests and restores the bent conformation and photophysical properties of PPP, which verifies that PPP, as a novel acyclic host, is capable of dynamic host-guest assembly. Moreover, the results prove that cavities at the molecular level can be created by connecting nano-building blocks with distinct shapes. This finding may inspire developments in the host-guest chemistry of GSA and nanomaterial innovation.

Novel block glycopolymers prepared as delivery nanocarriers for controlled release of bortezomib.

To explore block glycopolymers as novel polymeric delivery nanocarriers for anticancer drug bortezomib (BTZ), three types of block glycopolymers, poly(ethylene glycol)-block-poly(gluconamido ethyl methacrylate) (PEG113-b-PGAMA20), poly(ethylene glycol)-block-poly(styrene)-block-poly(gluconamido ethyl methacrylate) (PEG113-b-PS50-b-PGAMA20), and poly(ethylene glycol)-block-poly(2-(diethyl amino) ethyl methacrylate)-block-poly(gluconamido ethyl methacrylate) (PEG113-b-PDEA50-b-PGAMA20), were synthesized via atom transfer radical polymerization (ATRP) using a PEG-based ATRP macroinitiator. Three glycopolymers possess the capacity to load BTZ via pH-induced dynamic covalent bonding and/or hydrophobic interaction with their specific self-assembly behaviors, and PEG113-b-PS50-b-PGAMA20 carrier maintains the sustain release behavior of BTZ due to the stable micellar structure; PEG113-b-PDEA50-b-PGAMA20 carrier realizes the abrupt release at pH 5.5 by collapse of micellar structure, while PEG113-b-PGAMA20 carrier exhibits the fastest release at studied solution pHs. This study would provide a light to develop novel block glycopolymer carrier for the delivery of anticancer drug bearing boronic acid groups. Graphical abstractᅟᅟ.

A monodisperse anionic silver nanoparticles colloid: Its selective adsorption and excellent plasmon-induced photodegradation of Methylene Blue.

To address the pollution problem of organic dyes, monodispersed anionic silver nanoparticles (AgNPs) with an average size of 6 nm were prepared in water media via chemical reduction method from oleic acid and n-butyl amine. The aqueous solution of the resultant AgNPs was utilized as a photocatalyst to investigate the adsorption and photodegradation behaviors of organic dyes under different light irradiation. The morphology and surface characteristics of the synthesized AgNPs were probed using TEM, XRD, FTIR and zeta potential analysis. The adsorption and degradation process of organic dyes on the AgNPs were characterized in details by UV-Vis spectrophotometer. The results showed that the AgNPs exhibited a characteristic charge- and size-selective adsorption of dyes owing to the profoundly negative charged surface, which enables the AgNPs to possess high selective degradation of Methylene Blue. More still, due to the surface plasmon resonance (SPR) effect of AgNPs, the obtained AgNPs presented a higher photocatalytic activity to Methylene Blue under UV light, visible light, and solar light compared with commercial photocatalysts. The 5 cyclic reactions revealed its high stability and reusability. In a nutshell, the proposed mechanism systematically combined the selective adsorption and the SPR effect to explain the detailed photocatalytic process of the obtained AgNPs.

The morphologies and fluorescence quantum yields of perylene diimide dye-doped PS and PHVB microspheres.

Aggregation and continuous π-stacking have been the major obstacles hindering the fluorescence (FL) quantum yield (Φ F) of perylene diimide (PDI) derivatives in the condensed phase. To prepare polymer microspheres with nearly unity Φ F, in this work a POSS functionalized PDI derivative, POSS-PDI-POSS (PPP), was applied as the red fluorophore of poly(3-hydroxylbutyrate-co-3-hydroxyvalerate) (PHBV) and polystyrene (PS) microspheres. The electrosprayed PPP/PHBV and PPP/PS microspheres have unique hollow structures. Moreover, they show bright red FL under a fluorescence microscope. A photophysical study of the microspheres indicates a significant role of the polymer matrix in disrupting the aggregation state and the Φ F of the embedded PPP fluorophore. Both the PPP/PHBV and the PPP/PS microspheres show higher Φ F than most PDI materials in the condensed phase. The PPP/PHBV microspheres show Φ F of 28%, whereas the PPP/PS microspheres give nearly unity Φ F.