Effect of drying on the mesoporous structure of sol-gel derived silica with PPO-PEO-PPO template block copolymer

The effects of drying method on the pore structure of mesoporous silica were studied from the viewpoint of enhancing closed porosity in mesoporous silica. The mesoporous silica was prepared via a sol-gel process using polyethyleneoxide-polypropyleneoxide-polyethyleneoxide (PEO-PPO-PEO) triblock copolymer (Pluronic P123) as the structure-directing template. The closed porosity was evaluated from the apparent mass density of the sample measured by a helium pycnometer. These mesoporous silicas were also characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen adsorption. The drying method was shown to be responsible for the finally templated mesoporous structure of the silica. More rapid drying is more preferable for enhancing the closed porosity of the mesoporous silica. The closed pores were formed by immediate immobilization of copolymer molecular assemblies in the silica matrix due to the instant removal of the solvent and solidification at higher temperatures. The drying method, mainly affecting the drying rate, is highly influential on the finally replicated mesoporous structure in silica.     

Investigation of photoluminescence in GaAs quantum well coupled with a ferromagnetic semiconductor layer of (Ga,Mn)As

We have investigated circular-polarized photoluminescence (CPL) from a novel quantum structure in which a ferromagnetic semiconductor (Ga,Mn)As is placed adjacent to the GaAs quantum well. By eliminating the contribution of the magneto-circular dichroism effect of the (Ga,Mn)As top layer from the observed CPL, we found a small but nonnegligible contribution of quantum mechanical coupling between the GaAs quantum well states and the spin-polarized states in (Ga,Mn)As.     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20-36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.     

Non-Covalent Interactions Enable the Length-Controlled Generation of Discrete Tubes Capable of Guest Exchange

Supramolecular chemistry in confined spaces constructed from macrocyclic molecules has attracted much attention because it can utilize the specific binding properties of macrocyclic cavities. Herein we report the preparation of length-controlled discrete tubular structures by homo-/co-assembly of rim-differentiated and peralkylamino-substituted pillar[5]arenes via hydrogen bonds and salt bridges. By dimerization and trimerization, the expanded tubes show a fivefold helical structure and stepwise binding, respectively. We found that the exchange speed of guest molecules in the tubes could be controlled by varying the tube length.     

In-plane mechanical behaviors of 2D repetitive frameworks with four-coordinate flexible joints and elbowed beam members

The mechanical properties of an open-framework structure constructed of joints and beam members are strongly influenced by both its geometrical configuration and joint flexibility. This paper clarifies the relationship between joint flexibility and Poisson's ratio, which is a mechanical criterion for solid deformation, and discusses two types of in-plane anisotropic structures made up of four-coordinate flexible joints and elbowed beam members. Uniaxial tensile analyses estimate the linear and nonlinear elastic properties of these frameworks by applying straightforward joint modeling with multi-rotational degrees of freedom. The numerical results show that these proposed frameworks produce a variety of deformability dependent on the joint flexibility in auxetic deformation with a negative Poisson's ratio, the folding mechanics under kinematic indeterminacy, and the transition of Poisson's ratio between the positive and negative values. The geometrical and topological aspects of the obtained mechanical behaviors are discussed.