Synthesis of functional π-conjugated polymers from aromatic acetylenes

Because of their unique structures and properties, π-conjugated polymers have attracted the attention of scientists and engineers. The authors have studied the synthesis of two kinds of π-conjugated poly(aromatic acetylene)s, i.e. poly(arylacetylene)s and poly(aryleneethynylene)s with the aim of obtaining new polymers having novel functions or higher performances. This review mainly concerns the authors' results, as follows: first, we describe the synthesis and properties of achiral poly(arylacetylene)s, containing trimethylsilyl groups, oligodimethylsiloxanyl groups, dendritic groups, and glavinoxyl groups, for application as oxygen permselective membrane materials. Their self-membrane-forming abilities and high oxygen permeabilities are presented. Second, the synthesis by asymmetric-induced polymerization of chiral poly(arylacetylene)s having both a main-chain chirality and chiral pendant groups and their application as optical resolution membranes are described. Third, two new synthetic methods for preparing chiral helical poly(phenylacetylene)s without the coexistence of any other chiral moieties are presented. One is helix-sense-selective addition polymerization and the other is in situ removal of chiral pendant groups from membranes of poly(arylacetylene)s that also contain a main-chain chirality. The chiral helical poly(arylacetylene)s were tested as optical resolution membranes. The chiral and achiral poly(arylacetylene)s were synthesized by addition polymerization using metathesis catalysts or rhodium complexes. Finally, the synthesis of regiospecific poly(aryleneethynylene)s bearing stable radicals by the polycondensation of bromoethynylanthracene derivatives using a Pd(0) complex is described. The magnetization and the static magnetic susceptibility of the polyradicals are explained.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

Application of polymerizable surfactant in the preparation of polystyrene/nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> composite

Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano-Fe₃O₄ particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe₃O₄ particles into styrene monomer, and the polystyrene/nano-Fe₃O₄ composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano-Fe₃O₄ particles were studied by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experimental results show that the nano-Fe₃O₄ particles modified by monooctadecyl maleate with the size of about 7–10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) indicate that the thermal stability of polystyrene/nano-Fe₃O₄ composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials.     

Elastoplastic Finite Element Analysis and Strength Evaluation of Adhesive Butt Joints of Similar and Dissimilar Hollow Shafts Subjected to External Bending Moments

Stress distributions and deformation of adhesive butt joints are analyzed by an elastoplastic finite element method when the joints of similar and dissimilar shafts are subjected to external bending moments. The effects of the ratio of Young's modulus for the adherends to that for an adhesive and the effects of the adhesive thickness on the interface stress distribution are investigated. Joint strength is predicted by using the elastoplastic interface stress distributions. It is found that the singular stress at the edge of the interfaces increases with an increase of the ratio of Young's modulus. Measurement of strains in joints and experiments on joint strength were conducted. The numerical results are in fairly good agreement with the experimental results. It is observed that the joint strength for dissimilar shafts are smaller than those for similar shafts. A fracture of dissimilar adhesive up-bonded shafts occurred from the interface of the adherend with smaller Young's modulus. It is seen that joint strength increases as the adhesive thickness increases.     

Microstructure development of steel during severe plastic deformation

The microstructure development during plastic deformation was reviewed for iron and steel which were subjected to cold rolling or mechanical milling (MM) treatment, and the change in strengthening mechanism caused by the severe plastic deformation (SPD) was also discussed in terms of ultra grain refinement behavior. The microstructure of cold-rolled iron is characterized by a typical dislocation cell structure, where the strength can be explained by dislocation strengthening. It was confirmed that the increase in dislocation density by cold working is limited at 10¹⁶m⁻², which means the maximum hardness obtained by dislocation strengthening is HV3.7 GPa. However, the iron is abnormally work-hardened over the maximum dislocation strengthening by SPD of MM because of the ultra grain refinement caused by the SPD. In addition, impurity of carbon plays an important role in such grain refinement: the carbon addition leads to the formation of nano-crystallized structure in iron.     

Difference between mechanical alloying and mechanical disordering in the amorphization reaction of Al50Ta50 in a rod mill

Amorphous Al₅₀Ta₆₀ alloy powders have been synthesized by mechanical alloying (MA) from elemental powders of aluminium and tantalum, and mechanical disordering (MD) from crystalline intermetallic compound powders of AlTa respectively using the rod milling technique. The mechanically alloyed and the mechanically disordered alloy powders were characterized by X-ray diffraction, scanning electron microscopy, electron probe microanalysis, transmission electron microscopy, differential thermal analysis, differential scanning calorimetry and chemical analysis. The results have shown that the crystal-to amorphous transformation in the MD process occurs through one stage, while the crystallineto-amorphous formation in the MA process occurs through three stages. At the early and intermediate stages of the MA time, heating the alloy powders to 700 K leads to the formation of an amorphous phase by a solid-state amorphizing reaction. At the final stage of the MA time, the amorphous phase is crystallized through a single sharp exothermic peak. Contrary to this, amorphous alloy powders produced by MD are crystallized through two broad exothermic peaks.     

Shape optimization for a link mechanism

This paper presents a numerical solution for shape optimization problems for link mechanisms, such as a piston-crank mechanism. The dynamic behavior of a link mechanism is described by a differential-algebraic equation (DAE) system consisting of motion equations for each single body and constraints of linkages and rigid motions. In a shape optimization problem, the objective function to maximize is constructed from the external work done by a given external force, which agrees with the kinetic energy of the link mechanism, for an assigned time interval, and the total volume of all the links forms the constraint function. The Fréchet derivatives of these cost functions with respect to the domain variation, which we call the shape derivatives of these cost functions, are evaluated theoretically. A scheme to solve the shape optimization problem is presented using the H ¹ gradient method (the traction method) proposed by the authors as a reshaping algorithm, since it retains the smoothness of the boundary. A numerical example shows that reasonable shapes for each link such that mobility of the link mechanism is improved are obtained by this approach.     

Superconductivity in the tetragonal phase of La1.9Bi0.1CuO4+δ annealed under high oxygen pressure

We have investigated the relation between the crystal structure and superconductivity in La_1.9Bi_0.1CuO₄₊ , in which the phase separation observed in La₂CuO₄₊ is suppressed. A phase diagram in theT– plane is given for La_1.9Bi_0.1CuO₄₊ with excess oxygen. For very small values, the crystal structure is orthorhombic, and an orthorhombic-tetragonal phase transition occurs markedly at 0.03 in the measured temperature range between 13 and 293 K. Superconductivity is observed in the range of 0.04<<0.11. This is clear evidence thathigh-T _c superconductivity also appears in the tetragonal phase.     

Chemical modification of group IV graphene analogs

Mono-elemental two-dimensional (2D) crystals (graphene, silicene, germanene, stanene, and so on), termed 2D-Xenes, have been brought to the forefront of scientific research. The stability and electronic properties of 2D-Xenes are main challenges in developing practical devices. Therefore, in this review, we focus on 2D free-standing group-IV graphene analogs (graphene quantum dots, silicane, and germanane) and the functionalization of these sheets with organic moieties, which could be handled under ambient conditions. We highlight the present results and future opportunities, functions and applications, and novel device concepts.