Nanocomposites of chitosan and graphene oxide are prepared by simple self-assembly of both components in aqueous media. It is observed that graphene oxide is dispersed on a molecular scale in the chitosan matrix and some interactions occur between chitosan matrix and graphene oxide sheets. These are responsible for efficient load transfer between the nanofiller graphene and chitosan matrix. Compared with the pure chitosan, the tensile strength, and Young's modulus of the graphene-based materials are significantly improved by about 122 and 64%, respectively, with incorporation of 1 wt % graphene oxide. At the same time, the elongation at the break point increases remarkably. The experimental results indicate that graphene oxide sheets prefer to disperse well within the nanocomposites.

A novel giant surfactant possessing a well-defined hydrophilic head and a hydrophobic polymeric tail, polystyrene-(carboxylic acid-functionalized polyhedral oligomeric silsesquioxane) conjugate (PS-APOSS), has been designed and synthesized via living anionic polymerization, hydrosilylation, and thiol-ene "click" chemistry. PS-APOSS forms micelles in selective solvents, and the micellar morphology can be tuned from vesicles to wormlike cylinders and further to spheres by increasing the degree of ionization of the carboxylic acid. The effect of APOSS-APOSS interactions was proven to be essential in the morphological transformation of the micelles. The PS tails in these micellar cores were found to be highly stretched in comparison with those in traditional amphiphilic block copolymers, and this can be explained in terms of minimization of free energy. This novel class of giant surfactants expands the scope of macromolecular amphiphiles and provides a platform for the study of the basic physical principles of their self-assembly behavior.

A novel narrowly distributed rod-coil diblock copolymer, poly(styrene-block-(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PS-b-PMPCS), was synthesized by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated living free radical polymerization. The rodlike PMPCS block is a mesogen-jacked liquid crystalline polymer and is soluble in p-xylene at temperatures higher than 100°C. When a PS-b-PMPCS dilute solution is cooled, the copolymer chains can self-assemble into a core-shell nanostructure. The temperature-induced self-assembly was studied. We showed, for the first time, that instead of a neutron scattering, a combination of static and dynamic laser light scattering results could also lead to the core radius (R c ) and the shell thickness (∆R). Using this novel method, we found that when more chains were assembled into the nanostructure, R c remained as a constant, close to the contour length of the PMPCS block, but the shell became thicker, indicating that the attraction between the insoluble rigid rodlike PMPCS blocks led to their insertion into the core, while the repulsion between the soluble coillike PS blocks forced them to stretch in the shell.

A fullerene derivative C9 with anchoring hydroxyl groups on the long side chain is used to modify the surface of SnO2 in planar heterojunction perovskite solar cells, which exhibit high efficiency up to 21.3% with negligible hysteresis and good device stability.

Temperature-induced reversible morphological changes of polystyrene-block-poly(ethylene oxide) micelles with degrees of polymerization of 962 for the PS and 227 for the PEO blocks (PS962-b-PEO227) in N,N-dimethylformamide (DMF)/water, in which water is a selective solvent for the PEO block, were observed. For a system with 0.2 wt % copolymer concentration and 4.5 wt % water concentration in DMF/water, the micelle morphology observed in transmission electron microscopy changed from vesicles at room temperature to worm-like cylinders and then to spheres with increasing temperature. Mixed morphologies were also formed in the intermediate temperature regions. Cooling the system back to room temperature regenerated the vesicle morphology, indicating that the morphological changes were reversible. No hysteresis was observed in the morphological changes during heating and cooling. Dynamic light scattering revealed that the hydrodynamic radius of the micelles decreased with increasing temperature. Combined static and dynamic light scattering results supported the change in morphology with temperature. The critical micellization temperatures and critical morphological transition temperatures were determined by turbidity measurements and were found to be dependent on the copolymer and water concentrations in the DMF/water system. The morphological changes were only possible if the water concentration in the DMF/water system was low, or else the mobility of the PS blocks would be severely restricted. The driving force for these morphological changes was understood to be mainly a reduction in the free energy of the corona and a minor reduction in the free energy of the interface. Morphological observations at different time periods of isothermal experiments indicated that in the pathway from one equilibrium morphology to another, large compound micelles formed as an intermediate or metastable stage.

We report a novel observation of the tetragonal perforated layer structures in a series of rod-coil liquid crystalline block copolymers (BCPs), poly(styrene-block-(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PS-b-PMPCS). PMPCS forms rigid rods while PS forms the coil block. Differential scanning calorimetry (DSC), polarized light microscopy (PLM), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and transmission electron microscopy (TEM) techniques were used to investigate these rod-coil molecules, and a perforated layer structure was observed at f(PMPCS) approximately 0.37 in relatively low molecular weight (M(w)) samples and approximately 0.5 in high M(w) PS-b-PMPCS. This substantial phase boundary shift was attributed to the rod-coil nature of the BCP. The perforation obeys a tetragonal instead of hexagonal symmetry. The "onset" of perforation was also observed in real space in sample PS(272)-b-PMPCS(93) (f(PMPCS) approximately 0.52), in which few PS chains punctuate PMPCS layers. A slight increase in f(PS), by blending with PS homopolymer, led to a dramatic change in the BCP morphology, and uniform tetragonal perforations were observed at f(PMPCS) approximately 0.48.

We have found that not only block copolymers but also ionomers can self-assemble in a selective solvent to form surfactant-free nanoparticles. The self-assembly can be induced by chemical reaction, polymer-polymer complexation, and microphase inversion in addition to the temperature. A recently developed microwave method for the preparation of uniform surfactant-free polymeric nanoparticles is also reviewed. Our results have revealed that for a given dispersion, the particle surface area occupied per stabilizer (surfactant, polymer chains, and ionic groups) is close to a constant.

An iron(III) (FeCl3·6H2O) catalyst was found to be an active catalyst for initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) of methyl methacrylate (MMA), using triphenylphosphine (PPh3) as a ligand and azobis(isobutyronitrile) (AIBN) as a thermal radical initiator, and 1,4-(2-bromo-2-methylpropionato)benzene (BMPB2) as an ATRP initiator. Effects of reaction temperature, catalyst concentration and AIBN concentration on polymerization were investigated. These results showed that the catalyst was highly efficient for the ICAR ATRP of MMA. For example, even if the catalyst concentration decreased to 34 ppm, the polymerization with the molar ratio of [MMA]0/[BMPB2]0/[FeCl3·6H2O]0/[PPh3]0/[AIBN]0 = 500/1/0.03/1.5/0.1 could be carried out at 60 °C with a conversion 70.4% in 32 h. At the same time, the molecular weight of the obtained PMMA with a narrow molecular weight distribution (M w/M n = 1.37) was consistent with the theoretical one.