A novel halogen-free flame retardant containing sulfonamide, 1,3,5,7-tetrakis (phenyl-4-sulfonamide) adamantane (FRSN) was synthesized and used for improving the flame retardancy of largely used polycarbonate (PC). The flame-retardant properties of the composites with incorporation of varied amounts of FRSN were analyzed by techniques including limited oxygen index, UL 94 vertical burning, and cone calorimeter tests. The new FR system with sulfur and nitrogen elements showed effective improvements in PC’s flame retardancy: the LOI value of the modified PC increased significantly, smoke emission suppressed, and UL 94 V-0 achieved. Typically, the composite with only 0.08 wt% of FRSN added (an ultralow content) can increase the limiting oxygen index (LOI) value to 33.7% and classified as UL 94 V-0 rating. Furthermore, the mechanical properties and SEM morphology indicated that the FRSN has very good compatibility with PC matrix, which, in turn, is beneficial to the property enhancement. Finally, the analysis of sample residues after burning tests showed that a high portion of char was formed, contributing to the PC burning protection. This synthesized flame retardant provides a new way of improving PC’s flame retardancy and its mechanical property.
One of the most famous anticancer drugs, paclitaxel (PTX), has often been used in drug controlled-release studies. The polymers derived from bio-compound bile acids and degradable poly(ε-caprolactone) (PCL) form a reservoir and have been used as a drug delivery system with great advantages. Herein, we grafted poly(N,N-diethylaminoethyl methacrylate) and poly(poly(ethylene glycol) methyl ether methacrylate) into the bile acid-derived three-armed macroinitiator CA-(PCL)3, resulting in the amphiphilic block copolymers CA-(PCL-b-PDEAEMA-b-PPEGMA)3. These pH-responsive three-armed block copolymers self-assembled into micelles in aqueous solution and PTX was encapsulated into the micellar core to form PTX-loaded micelles with a drug loading of 29.92 wt %. The micelles were stable in PBS at pH 7.4 and showed a pH-triggered release behavior of PTX under acidic environments, in which 55% of PTX was released at pH 5.0 in 80 h. These cholic acid-based functionalized three-armed block polymers present good biocompatibility, showing great potential for drug controlled-release.
Considering the poor compatibility and water-resistance of sulfonate flame retardants for polycarbonate (PC), an efficient S/N-based flame retardant named 1,3,5,7-tetrakis(phenyl-4-sulfonyl-melamine)adamantane (ASN) has been developed. Fire properties studies of PC/ASN blends indicate that the addition of 0.10 wt % ASN imparts a V-0 rating and a limited oxygen index (LOI) value of 30.1% to PC specimens, and ASN can suppress the heat and toxic gas release of PC composites. Additionally, PC/ASN blends are believed to be exceptional materials for outdoor PC applications due to their superior water-resistance properties. Moreover, mechanical properties were further systematically investigated, and the correlative results indicate that the tensile strength and rigidity of specimens are improved with the addition of ASN.
Polymeric nano-carriers are considered as promising tools in biomedical applications due to multiple attractive characteristics including their low toxicity, high loading capacity, controlled drug release capabilities, and highly tunable chemical properties. Here, a series of pH-sensitive star-shaped copolymers, Ad-P[(EMA-co-MAA)-b-PPEGMA]4, was prepared via electron transfer atom radical polymerization (ARGETE ATRP) and selective hydrolysis. These star-shaped copolymers can be self-assembled into micelles (Dh = 150–160 nm) and their critical micelle concentrations (CMC) were estimated to be 3.9–5.0 mg/L. The pH-sensitiveness of the micelles was evidenced by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The maximal paclitaxel (PTX) loading efficiency (DLC) and entrapment efficiency (EE) were 18.9% and 36%, respectively. In vitro release studies revealed that about 19% of the PTX released at an acidic condition of pH 1.2 over 70 h, whereas more than 70% was released within the same time interval at pH 6.8. In vitro cytotoxicity suggested that the low cytotoxicity of the blank micelles, while the PTX-loaded micelles providing the cytotoxicity close to that of free PTX. These results indicated that this novel pH-sensitive nano-carriers have great potential applications for oral drug-controlled release.
A typical amphiphilic star polymer adamantane-[poly(lactic-co-glycolic acid)-bis(2-carboxyethyl) sulfide-poly(ethylene glycol) monomethyl ether)]4 with a specific hydrophilic/redox-sensitive/hydrophobic structure was designed and synthesized through ring opening and esterification reactions. The self-assembled nanomicelles were used as doxorubicin (DOX) delivery vehicles with suitable critical micelle concentrations (5.0 mg/L). After the drug being loaded, drug-loaded micelles showed good drug-loading efficiency (10.39%), encapsulation efficiency (58.1%), and drug release (up to 60%) under simulated biological environment conditions. In addition, the backbone structure of the biodegradable polymer was easily hydrolyzed by the action of biological enzymes. As expected, cell-based studies showed that the designed polymer micelles possessed good biocompatibility (a survival rate of 85% for NH-3T3 cells). Moreover, the drug (DOX) still maintained good anti-cancer effects after being loaded, which caused 40% of MCF-7 cells to survive. These redox-sensitive micelles showed anti-tumor therapeutic potential.
Four-arm star-shaped (denoted as ‘S’) polymer adamantane-[poly(lactic-co-glycolic acid)-b-poly(N,N’-diethylaminoethyl methacrylate) poly(ethylene glycol) monomethyl ether]4 (S-PLGA-D-P) and its linear (denoted as ‘L’) counterpart (L-PLGA-D-P) were synthesized, then their self-assembled micelles were further developed to be platforms for anticancer drug delivery. Two types of polymeric micelles exhibited strong pH-responsiveness and good drug loading capacity (21.6% for S-PLGA-D-P and 22.9% for L-PLGA-D-P). Using doxorubicin (DOX) as the model drug, their DOX-loaded micelles displayed well controlled drug release behavior (18.5–19.0% of DOX release at pH 7.4 and 77.6–78.8% of DOX release at pH 5.0 within 80 h), good cytocompatibility against NIH-3T3 cells and effective anticancer efficacy against MCF-7 cells. However, the star-shaped polymeric micelles exhibited preferable stability, which was confirmed by the lower critical micelle concentration (CMC 0.0034 mg/mL) and decrease rate of particle sizes after 7 days incubation (3.5%), compared with the linear polymeric micelle L-PLGA-D-P (CMC 0.0070 mg/mL, decrease rate of particle sizes was 9.6%). Overall, these developed polymeric micelles have promising application as drug delivery system in cancer therapy.