The
correlation of aggregation-induced emission (AIE) to the nanostructure
of polymer assemblies was investigated. A series of AIE-active PDMA-b-P(BzMA-TPE) [PDMA: poly(
N
,
N
-dimethylaminoethyl methacrylate);
P(BzMA-TPE): poly[benzyl methacrylate-co-1-ethenyl-4-(1,2,2-triphenylethenyl)benzene]]
assemblies with controlled nanostructures were prepared via polymerization-induced
self-assembly of BzMA and TPE, an AIEgen, in the presence of PDMA
macro-chain-transfer agents. We found that the fluorescence intensity
and fluorescent quantum yield increase in the order of vesicles >
wormlike micelles > spherical micelles. For spherical micelles
and
vesicles, the AIE effect strengthens with increase in micellar size
and wall thickness, respectively. As the AIE effect indicates the
packing compactness of the AIEgens, the discovered structure-correlated
emission can be attributed to the stress variation of polymer chains
in the aggregates. AIE is therefore potentially useful as a probe
for the investigation and understanding of nanostructure and evolution
process of polymer self-assemblies.
A series
of azo-containing copolymeric assemblies based on poly(
N
,
N
-dimethylaminoethyl
methacrylate)-b-poly[(benzyl methacrylate)-co-(4-phenylazophenyl methacrylate)] [PDMA-b-P(BzMA-co-AzoMA)] were prepared by reversible
addition–fragmentation chain transfer polymerization-induced
self-assembly at high solid contents. Depending on the chain length
of P(BzMA-co-AzoMA), spheres, worms, and vesicles
were readily prepared. These azo-containing wormlike micelles underwent
reversible worm-to-vesicle transformation upon alternative UV/vis
light irradiation. By investigating the morphology evolution, a series
of intermediates were observed, including coalesced worms as well
as “octopus”-like and “jellyfish”-like
structures. The morphology transformation was rationalized by the
volume change of the P(BzMA-co-AzoMA) block caused
by the trans–cis isomerization of the azobenzene
groups. It is the first demonstration of light-stimulated reversible
worm-to-vesicle transition and would benefit for the understanding
of morphology evolution of polymer assemblies under external stimuli.
A CO 2 -responsive well-defined magneto-polymeric drug delivery system has been developed.An dosing release of doxorubicin (DOX) in vitro in a time-controllable manner can be easily executed under alternative CO 2 /N 2 treatment by these smart nanocarriers.CO2-resonsive well-defined core-shell-corona structure magnetic Fe3O4@SiO2-poly(N,Ndimethylaminoethyl methacrylate) (PDMAEMA) nanocarriers have been developed as efficient drug delivery system. The hybrid magnetic nanoparticles (MNPs) demonstrated a sandwich structure and high super-paramagnetic, biocompatibility properties as well as gas-responsive behavior. We found that the hydrodynamic radius (Rh) of the magnetic hybrid nanoparticles could be adjusted by alternate CO2/N2 treatment driving a switchable volume transition from contraction to expansion because of the CO2 responsiveness of PDMAEMA. The CO2-triggered protonation of the polymer shell gives rise to obvious zeta potential change of the nanoparticles. Importantly, the CO2 induced reversible "on-off" transformation makes it possible to perform an dosing release of doxorubicin (DOX) in vitro in a time-controllable manner which is of great significance in controlled drug release. In the presence of CO2, the drug release rate is significantly accelerated; while low drug release could be achieved by removal of CO2 using N2. Moreover, in vitro cytotoxicity represented that the CO2-responsive magnetic nanocarries have good biocompatibility and could be safely used in living systems.
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