Super flexibility of a 2D Cu-based porous coordination framework on gas adsorption in comparison with a 3D framework of identical composition: framework dimensionality-dependent gas adsorptivities

Selective synthetic routes to coordination polymers [Cu(bpy)(2)(OTf)(2)](n) (bpy = 4,4'-bipyridine, OTf = trifluoromethanesulfonate) with 2- and 3-dimensionalities of the frameworks were established by properly choosing each different solvent-solution system. They show a quite similar local coordination environment around the Cu(II) centers, but these assemble in a different way leading to the 2D and 3D building-up structures. Although the two kinds of porous coordination polymers (PCPs) both have flexible frameworks, the 2D shows more marked flexibility than the 3D, giving rise to different flexibility-associated gas adsorption behaviors. All adsorption isotherms for N(2), CO(2), and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms, also for CH(4) and water, in addition to these gases. The 3D structure, having hydrophilic and hydrophobic pores, shows the size-selective and quadrupole-surface electrical field interaction dependent adsorption. Remarkably, the 2D structure can accommodate greater amounts of gas molecules than that corresponding to the inherent crystallographic void volume through framework structural changes. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms. The structural diversity of the 2D PCP stems from the breathing phenomenon and expansion/shrinkage modulation.     

Cell sheet engineering: intelligent polymer patterned surfaces for tissue engineered liver

We describe a new culture system utilizing the temperature-responsive polymer grafted surface for designing of cell position and layered tissue reconstruction. Organizing of the hepatic tissue structure by controlling the culture system, that is patterned co-culture and layered cell sheet co-culture achieved by moving the cultured cells from the culture surface, resulted in regulation of the hepatocyte function. The technique for cell sheet manipulation would promote the liver tissue engineering in quality.     

Cationic β-Scission of C−H and C−C Bonds for Selective Dimerization and Subsequent Sulfur-Free RAFT Polymerization of α-Methylstyrene and Isobutylene

A series of exo-olefin compounds ((CH₃)₂C(PhY)−CH₂C(=CH₂)PhY) were prepared by selective cationic dimerization of α-methylstyrene (αMS) derivatives (CH₂=C(CH₃)PhY) with p-toluenesulfonic acid (TsOH) via β-C−H scission. They were subsequently used as reversible chain transfer agents for sulfur-free cationic RAFT polymerization of αMS via β-C−C scission in the presence of Lewis acid catalysts such as SnCl₄. In particular, exo-olefin compounds with electron-donating substituents, such as a 4-MeO group (Y) on the aromatic ring, worked as efficient cationic RAFT agents for αMS to produce poly(αMS) with controlled molecular weights and exo-olefin terminals. Other exo-olefin compounds (R−CH₂C(=CH₂)(4-MeOPh)) with various R groups were prepared by different methods to examine the effects of R groups on the cationic RAFT polymerization. A sulfur-free cationic RAFT polymerization also proceeded for isobutylene (IB) with the exo-olefin αMS dimer ((CH₃)₂C(Ph)−CH₂C(=CH₂)Ph). Furthermore, telechelic poly(IB) with exo-olefins at both terminals was obtained with a bifunctional RAFT agent containing two exo-olefins. Finally, block copolymers of αMS and methyl methacrylate (MMA) were prepared via mechanistic transformation from cationic to radical RAFT polymerization using exo-olefin terminals containing 4-MeOPh groups as common sulfur-free RAFT groups for both cationic and radical polymerizations.     

Biodegradable Polylactide and Its Nanocomposites: Opening a New Dimension for Plastics and Composites

The academic and industrial aspects of the preparation, characterization, mechanical and materials properties, crystallization behavior, melt rheology, and foam processing of pure polylactide (PLA) and PLA/layered silicate nanocomposites are described in this feature article. Recently, these materials have attracted considerable interest in polymer science research. PLA is linear aliphatic thermoplastic polyester and is made from agricultural products. Hectorite and montmorillonite are among the most commonly used smectite‐type layered silicates for the preparation of nanocomposites. Smectites are a valuable mineral class for industrial applications because of their high cation exchange capacities, surface area, surface reactivity, adsorptive properties, and, in the case of hectorite, high viscosity, and transparency in solution. In their pristine form, they are hydrophilic in nature, and this property makes them very difficult to disperse into a polymer matrix. The most common way to overcome this difficulty is to replace interlayer cations with quaternized ammonium or phosphonium cations, preferably with long alkyl chains. In general, polymer/layered silicate nanocomposites are of three different types: (1) intercalated nanocomposites, in which insertion of polymer chains into the layered silicate structure occurs in a crystallographically regular fashion, regardless of polymer to layered silicate ratio, with a repeat distance of few nanometer; (2) flocculated nanocomposites, in which intercalated and stacked silicate layers are sometimes flocculated due to the hydroxylated edge–edge interactions between the silicate layers; (3) exfoliated nanocomposites, in which individual silicate layers are uniformly distributed in the polymer matrix by average distances that totally depend on the layered silicate loading. This new family of composite materials frequently exhibits remarkable improvements in its material properties when compared with those of virgin PLA. Improved properties can include a high storage modulus both in the solid and melt states, increased flexural properties, a decrease in gas permeability, increased heat distortion temperature, an increase in the rate of biodegradability of pure PLA, and so forth.

Illustration of the biodegradability of PLA and various nanocomposites.