The preparation of thermoresponsive drug carriers with a self-destruction property is presented. These drug carriers were fabricated by incorporation of drug molecules and thermoresponsive copolymer, poly(N-isopropylacrylamide-co-acrylamide), into silica nanoparticles in a one-pot preparation process. The enhanced drug release was primarily attributed to faster molecule diffusion resulting from the particle decomposition triggered by phase transformation of the copolymer upon the temperature change. The decomposition of the drug carriers into small fragments should benefit their fast excretion from the body. In addition, the resulting drug-loaded nanoparticles showed faster drug release in an acidic environment (pH 5) than in a neutral one. The controlled drug release of methylene blue and doxorubicin hydrochloride and the self-decomposition of the drug carriers were successfully characterized by using TEM, UV/Vis spectroscopy, and confocal microscopy. Together with the nontoxicity and excellent biocompatibility of the copolymer/SiO₂ composite, the features of controlled drug release and simultaneous carrier self-destruction provided a promising opportunity for designing various novel drug-delivery systems.

A recyclable solid-state photoinitiator based on the surface modified niobium hydroxide is prepared and successfully introduces into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed by gel permeation chromatography analysis that well-defined polymers with controlled molecular weight and narrow polydispersity index can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to external stimulus and when light is removed from the system polymerization stops almost immediately. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. At last, the mechanism for the light initiated polymerization is proposed to illuminate how the initiation and chain propagation proceed. This facile, green and visible light initiation methodology could attract more and more applications in polymer science with the depletion of fossil energy.

A recyclable solid-state photoinitiator based on the surface modified niobium hydroxide was prepared and successfully introduced into reversible addition–fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed that well-defined polymers with controlled molecular weight and narrow polydispersity index (PDI) can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to light initiation. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2715–2724

In this article, the preparation of fluorescent nanohybrids with core–shell structure and metal-enhanced fluorescence (MEF) effect was presented. The fluorescent core–shell nanohybrids were prepared using silver nanoparticles (AgNPs) as cores and fluorophore tethered thermoresponsive copolymers with tunable lower critical solution temperature (LCST) from 15 to 90 °C as shells. These thermoresponsive copolymers were synthesized by the random copolymerization of oligo(ethylene oxide) acrylate and di(ethylene oxide) ethyl ether acrylate using reversible addition–fragmentation chain transfer polymerization and grafted on to AgNPs surface via Ag–S coordination interaction. By thermal manipulation of polymer spacer between AgNPs and fluorophores, the tunable MEF was achieved. It was also revealed that the fluorescent nanohybrids would exhibit maximal MEF when the polymerization degree was tuned to 350. The manipulation of the solution temperatures below and above LCST resulted in switchable MEF behavior. In addition, the phase transition process of the thermoresponsive copolymer was also studied by MEF effect using this fluorescent core–shell nanohybrid design. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 87–95

Graphene–polymer composites of positive-charged poly(dimethyl aminoethyl acrylate), negative-charged poly(acrylic acid), and neutral polystyrene were prepared by “graft from” methodology using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene functional RAFT agent (PFRA) modified graphene precursor. Fluorescence spectroscopy and attenuated total reflection infrared (ATR-IR) evidenced that the PFRA was attached on the graphene basal planes by π–π stacking interactions, which is strong enough to anti-dissociation in the polymerization mixture up to 80°C. Atomic force microscopy (AFM) revealed that the thickness of a graphene–polymer sheet was about 4.0 nm. Graphene composites of different polymers with the same polymerization degree exhibited similar conductivity; however, when the polymer chain was designed as random copolymer the conductivity was significantly decreased. It was also observed that the longer the grafted polymer chains the lower the conductivity. ATR-IR spectroscopy and thermogravimetric analysis were also performed to characterize the as-prepared composites. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

In this article, poly[poly(ethyleneglycol) acrylate] (polyPEG-A) with mercaptothiazoline ester terminal group was synthesized directly by reversible addition fragmentation chain transfer (RAFT) polymerization using a mercaptothiazoline ester functional RAFT agent. The functional polyPEG-A was then conjugated to glucose oxidase (GOx) via surface-tethered amino groups through covalent amide coupling. Sorensenformaltitration assay revealed that GOx retained ∼14 free amino groups available for covalent modification. The conjugation reaction turned out to be efficient and mild. Colorimetric method was applied to evaluate the enzymatic activity of native GOx and its derivatives by introducing another enzyme, horseradish peroxidase. The modified GOx with polymeric chains exhibited reduced enzymatic activity toward the catalytical oxidation of glucose, but with significantly increased thermal stability and elongated lifetime. When GOx was modified with polyPEG-A [molecular weight (MW), 45,000; polydispersity index, 1.12] the enzymatic activity was decreased to 37 U/mg, only 29% left. However, when incubated at 25 °C the modified GOx still retained 9.6% of its original bioactivity after 60 days, whereas the native GOx only lived for 29 days. The more polymer chains or the longer polymer chain attached, the more reduction of the enzymatic activity resulted, however, the longer the lifetime of the enzyme obtained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012