Synthesis and application of head-to-head-type styrene dimers bearing two fluoroalkyl end-groups

Head-to-head-type styrene and substituted styrene dimers bearing two fluoroalkyl end-groups have been efficiently synthesized by a simple reaction of perfluoroalkyl iodide with styrene under radical conditions as a mixture of meso and racemic forms. The meso form obtained from the mixture by recrystallization gave a crystal suitable for X-ray diffraction study and the crystal structure was found to be based on π-stacking of benzene rings and aggregation of fluoroalkyl chains. Dynamic light scattering measurements showed that meso-styrene dimers bearing two fluoroalkyl end-groups can form the nanometer size-controlled self-assemblies through the intermolecular π-stacking of benzene rings and aggregation of end-capped fluoroalkyl groups in methanol.

α-Trifluoromethyl Chalcones as Potent Anticancer Agents for Androgen Receptor-Independent Prostate Cancer

α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins.     

Solid-Phase Radical Polymerization of Halogen-Bond-Based Crystals and Applications to Pre-Shaped Polymer Materials

Liquid vinyl monomers were converted into solid crystals via halogen bonding. They underwent solid-phase radical polymerizations through heating at 40 °C or ultraviolet photo-irradiation (365 nm). The X-ray crystallography analysis showed the high degree of monomer alignment in the crystals. The polymerizations of the solid monomer crystals yielded polymers with high molecular weights and relatively low dispersities because of the high degree of the monomer alignment in the crystal. As a unique application of this system, the crystalized monomers were assembled to pre-determined structures, followed by solid-phase polymerization, to obtain a two-layer polymer sheet and a three-dimensional house-shaped polymer material. The two-layer sheet contained a unique asymmetric pore structure and exhibited a solvent-responsive shape memory property and may find applications to asymmetric membranes and polymer actuators.     

Short Radiative Lifetime and Non-Triplet Sensitization in Near-Infrared-Luminescent Yb(III) Complex with Tripodal Schiff Base

We prepared Ln(III) (Ln=Eu, Gd, and Yb) complexes with a tripodal Schiff base, tris[2-(5-methylsalicylideneimino)ethyl]amine (H₃L) and studied their photophysical properties. Upon ligand excitation, YbL showed Yb(III)-centered luminescence in the near-infrared region. While the overall quantum yield (0.60(1)%) of YbL in acetonitrile was moderate among the reported values for Yb(III) complexes, its radiative lifetime (0.33(2) ms) was significantly shorter than those reported previously. We propose that the ligand-to-metal charge-transfer (LMCT) state mediated the sensitization in YbL. The emission and excitation spectra of EuL indicated the participation of the LMCT state in the sensitization. The radiative lifetime (0.84(7) ms) for EuL in the solid state was rather short compared to those of reported Eu(III) complexes. Our results show that the Yb(III) complex with the Schiff base ligand has two features: the short radiative lifetime and the non-triplet sensitization path.     

Photoluminescence linewidth broadening due to alloy/thickness fluctuation of CdxZn1 − xSe/ZnSe triple quantum wells

Photoluminescence (PL) linewidth broadening of Cd_xZn_{1 − x}Se/ZnSe triple quantum wells, grown on GaAs substrates by molecular beam epitaxy (MBE), has been investigated. Various quantum well (QW) samples have been prepared with different QW thickness and composition (Cd-composition). Measured and calculated PL linewidth are compared. Both composition and thickness fluctuations are considered for the calculation with the parameters such as the volume of exciton, nominal thickness and composition of QWs. Surface roughness measured by atomic force microscopy (AFM) is used to estimate the interface roughness. Results show that when Cd-composition increases additional linewidth broadening due to Zn/Cd interdiffusion is enhanced.     

磁场构型的影响及用于RIKEN的RIBF项目的新型ECR离子源

We measured the main plasma parameters(density of electron,temperature of electron and ion confinement time)and beam intensity of various heavy ions as a function of B_(min).The B_(min) strongly affects the field gradient at the resonance zone,consequently the plasma parameters and beam intensity are changed. Based on these experimental results,we started to construct new 18GHz ECRIS and make a detailed design of the 28GHz SC-ECRIS for RIKEN RI beam factory project.     

Real-space finite-difference approach for multi-body systems: path-integral renormalization group method and direct energy minimization method

The path-integral renormalization group and direct energy minimization method of practical first-principles electronic structure calculations for multi-body systems within the framework of the real-space finite-difference scheme are introduced. These two methods can handle higher dimensional systems with consideration of the correlation effect. Furthermore, they can be easily extended to the multicomponent quantum systems which contain more than two kinds of quantum particles. The key to the present methods is employing linear combinations of nonorthogonal Slater determinants (SDs) as multi-body wavefunctions. As one of the noticeable results, the same accuracy as the variational Monte Carlo method is achieved with a few SDs. This enables us to study the entire ground state consisting of electrons and nuclei without the need to use the Born-Oppenheimer approximation. Recent activities on methodological developments aiming towards practical calculations such as the implementation of auxiliary field for Coulombic interaction, the treatment of the kinetic operator in imaginary-time evolutions, the time-saving double-grid technique for bare-Coulomb atomic potentials and the optimization scheme for minimizing the total-energy functional are also introduced. As test examples, the total energy of the hydrogen molecule, the atomic configuration of the methylene and the electronic structures of two-dimensional quantum dots are calculated, and the accuracy, availability and possibility of the present methods are demonstrated.     

SiO2气凝胶中ZnS∶Mn纳米微晶的发光性质

利用溶胶 凝胶法在SiO2 气凝胶中制得了ZnS∶Mn纳米微晶 ,并对微晶的X射线衍射谱、激发 发射光谱、发光效率、时间分辨光谱进行了研究 ,讨论了发光性质变化的原因。实验表明 ,Mn2 + 在纳米微晶中的发光效率相对于体材料有明显的提高 ,弛豫时间也比在体材料中缩短了约一个数量级