Weiang Luo

Gold@Polymer Nanostructures with Tunable Permeability Shells for Selective Catalysis

National Natural Science Foundation of China [50873082, 50903067]; Scientific and Technical Project of Fujian Province of China [2009J1009, 2010H6021]

Heterogeneous silver-polyaniline nanocomposites with tunable morphology and controllable catalytic properties.

This paper introduces not only a simple hydrothermal route to silver-polyaniline (Ag-PANI) nanocomposites with controllable morphology, but also a type of catalyst possessing tunable and switchable catalytic capability. Ag-PANI Janus nanoparticles (NPs) and Ag@PANI core-shell NPs have been constructed successfully at different hydrothermal temperatures. The diameter of both Ag and PANI hemispheres of Janus NPs, as well as the PANI shell thickness of core-shell NPs, was finely tuned via adjustment of the feed ratio. We also gained a deeper insight into the functionalities of PANI components in the catalytic capability of the heterogeneous catalysts, choosing catalytic reductions of nitrobenzene (NB) and 4-nitrophenol (4-NP) as model reactions. Our results showed that the catalytic capability of the nanocomposites was dependent on the PANI morphology and hydrophobicity. The PANI shell coating on Ag NPs can concentrate the lipophilic NB, thus leading to an enhanced catalytic capability of Ag@PANI core-shell NPs. However, this enhanced catalytic capability was not observed for Ag-PANI Janus NPs when catalytically reducing NB. More importantly, the catalytic capability of the core-shell NPs in the reduction of hydrophilic 4-NP is switchable by varying the PANI shell from an undoped to a doped state.

Platinum-nanoparticle-supported core--shell polymer nanospheres with unexpected water stability and facile further modification.

Core-shell nanospheres (CSNSs) with hydrophobic cores and hydrophilic shells were fabricated via a simple mini-emulsion polymerization for the stabilization of platinum nanoparticles (Pt-NPs). The CSNSs showed extremely high loading capacity of Pt-NPs (the largest loading amount of the Pt-NPs was about 49.2 wt%). Importantly, the Pt-NPs/CSNSs nanocomposites had unexpected stability in aqueous solution. DLS results revealed that the CSNSs loaded with Pt-NPs exhibited almost no aggregation after standing for a long time . However, the Pt-NPs immobilized on the CSNSs were not straitlaced: they could transport and redistribute between CSNSs freely when the environmental temperature was higher than the melting point of the CSNS shell. Owing to their excellent stability in aqueous solution, the surface of the Pt-NPs/CSNSs nanocomposites could be further decorated easily. For example, polyaniline (PANI)-coated Pt-NPs/CSNSs, nickel (Ni)-coated Pt-NPs/CSNSs and PANI/Pt-NPs dual-layer hollow nanospheres were facilely fabricated from the Pt-NPs/CSNS nanocomposites.

Fluorescent polymeric assemblies as stimuli-responsive vehicles for drug controlled release and cell/tissue imaging

Polymer assemblies with good biocompatibility, stimuli-responsive properties and clinical imaging capability are desirable carriers for future biomedical applications. Herein, we report on the synthesis of a novel anthracenecarboxaldehyde-decorated poly(N-(4-aminophenyl) methacryl amide-oligoethyleneglycolmonomethylether methacrylate) (P(MAAPAC-MAAP-MAPEG)) copolymer, comprising fluorescent chromophore and acid-labile moiety. This copolymer can assemble into micelles in aqueous solution and shows a spherical shape with well-defined particle size and narrow particle size distribution. The pH-responsive property of the micelles has been evaluated by the change of particle size and the controlled release of guest molecules. The intrinsic fluorescence property endows the micelles with excellent cell/tissue imaging capability. Cell viability evaluation with human hepatocellular carcinoma BEL-7402 cells demonstrates that the micelles are nontoxic. The cellular uptake of the micelles indicates a time-dependent behavior. The H22-tumor bearing mice treated with the micelles clearly exhibits the tumor accumulation. These multi-functional nanocarriers may be of great interest in the application of drug delivery.

Supramolecular assembly of crosslinkable monomers for degradable and fluorescent polymer nanoparticles

Intermolecular B-N coordination has been recognized as a promising driving force for molecular self-organization. However, direct utilization of this intermolecular interaction as building bridge for the supramolecular self-assembly of chemical functionalities to form nano-sized architectures remains a daunting challenge. Here, we outline a multiple intermolecular B-N coordination based supramolecular system, where small boronate molecules can be brought together in solution to form nanoparticles with controllable sizes and morphologies. We not only demonstrate the intrinsic switchable fluorescence and the stimuli-responsive capabilities of the designed boronate molecule, but also show that the stabilized or surface functionalized nanoparticles are degradable in response to pH and D-glucose and able to retain the fluorescence features of the boronate molecule. Additionally, the degraded nanoparticles can repair themselves through the reformation of B-N coordination.

An airflow-controlled solvent evaporation route to hollow microspheres and colloidosomes

A facile and large-scale method combining airflow-controlled solvent evaporation and amphiphilic copolymer self-assembly has been developed for the generation of hollow polymer microspheres, colloidosomes or even organic–inorganic hybrid colloidosomes. By replacing traditional agitation with the controllable airflow, this surfactant free route showed promising prospect in the fabrication of microcapsules with closed pore morphology. While the hollow polymer microspheres had an adjustable pore structure, the polymer colloidosomes and the hybrid colloidosomes possessed seamless surfaces, making them suitable for the stable encapsulation of small molecules. The hybrid colloidosomes constructed from polymer and Fe3O4 nanoparticles, and the ternary hybrid colloidosomes derived from polymer, polymer nanospheres and Fe3O4 nanoparticles displayed superparamagnetic properties and were excellent contrast agents for magnetic resonance imaging. More importantly, both hybrid colloidosomes and ternary hybrid colloidosomes exhibited a significant evolution of pore morphology from a closed pore structure to an open pore structure in response to the temperature variation, which induced a controllable release of guest molecules.

A novel hybrid random copolymer poly(MAPOSS-co-NIPAM-co-OEGMA-co-2VP): Synthesis, characterization, self-assembly behaviors and multiple responsive properties

AbstractA novel organic/inorganic hybrid amphiphilic random copolymer poly(methacrylate isobutyl POSS-co-N-isopropylacrylamide-co-oligo(ethylene glycol) methyl ether methacrylate-co-2-vinylpyridine), poly(MAPOSS-co-NIPAM-co-OEGMA-co-2VP), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The self-assembly behavior of random copolymers in aqueous solution was investigated by dynamic light scattering (DLS) as well as transmission electron microscopy (TEM). The results indicate the novel random copolymer in water could self-assemble into spherical aggregates and the self-aggregate size displays a remarkable dependence on pH. The stimuli-responsive characteristics of these assembles were tested by means of UV-vis spectra, DLS and TEM. There is a critic Zn2+ concentration over which the aggregates can be coordinated into well-define spherical aggregate clusters. The critic Zn2+ concentration can be tuned finely through adjusting solution concentration or 2VP amount. Results from UV-vis and DLS reveal that the copolymer solutions exhibit a sharp and intensive lower critical solution temperature (LCST). Some factors such as the solution concentration, molecular weight, pH and copolymer generation, which could affect the cloud point, were studied systematically. The essentially predetermined LCST can be achieved by altering the content of 2VP or pH. In addition, these novel hybrid aggregates can undergo an association/disassociation cycle with the heating and cooling of solution and the degree of reversibility shows a strong concentration dependence. As a novel organic-inorganic hybrid material which can respond to multiple external stimuli including temperature, pH, metal ions with sharp stimuli-responsive behaviors, it is potentially used for biomedicine, catalysis, diagnostics, bioseparations, biosensors and for fundamental investigation.

Three-dimensional gold nanodendrimers: never conglomerating nanocatalyst

3D Au nanodendrimers constructed by radially arranged thin nano-sheets show tunable morphology and diameter. The unexpectedly large specific surface area resulting from the novel porous nanostructure makes the 3D Au nanodendrimers exhibit high catalytic activity and long service life.

Predictable particle engineering: programming the energy level, carrier generation and conductivity of core-shell particles

Core-shell structures are of particular interest in the development of advanced composite materials as they can efficiently bring different components together at nanoscale. The advantage of this structure greatly relies on the crucial design of both core and shell, thus achieving an intercomponent synergistic effect. In this report, we show that decorating semiconductor nanocrystals with a boronate polymer shell can easily achieve programmable core-shell interactions. Taking ZnO and anatase TiO2 nanocrystals as inner core examples, the effective core-shell interactions can narrow the band gap of semiconductor nanocrystals, change the HOMO and LUMO levels of boronate polymer shell, and significantly improve the carrier density of core-shell particles. The hole mobility of core-shell particles can be improved by almost 9 orders of magnitude in comparison with net boronate polymer, while the conductivity of core-shell particles is at most 30-fold of nanocrystals. The particle engineering strategy is based on two driving forces: catechol-surface binding and B-N dative bonding and having a high ability to control and predict the shell thickness. Also, this approach is applicable to various inorganic nanoparticles with different components, sizes, and shapes.

Cross-Linking Induced Self-Organization of Polymers into Degradable Assemblies

Covalently stabilized polymer assemblies are normally fabricated from the self-assembly of polymer chains followed by a cross-linking reaction. In this report, we show that a cross-linking-induced self-assembly approach, in which boronate cross-linking sites are formed by the condensation reaction between boronic and catechol groups, can organize polymer networks into uniform assemblies. Self-assembly of these boronate cross-linked polymer networks adopts two different driving forces in water and methanol solutions. Hydrophobic aggregation of polymer networks in water solution affords spherical assemblies, while B-N dative bond formed between boronate and imine functionalities in methanol solution organizes the polymer networks into bundle-like assemblies. We not only demonstrate the intrinsic stimuli-responsive degradability of these cross-linked assemblies but also show that their degradation can cause a controllable release of guest molecules. Moreover, bundle-like assemblies with rough surface and exposed boronate functionalities exhibit dramatically higher cell penetration capability than the spherical assemblies with smooth surface and embedded boronate functionalities.