Modern interpretation on the high-stretching of natural rubber attained by the classic ‘racking’ method

To investigate the mechanism of high elongation of natural rubber attained by the ‘racking method’, a strip of smoked-sheet was elongated up to 150 times in length, by stretching rapidly at room temperature and forcing to shrink at 75-80 °C repeatedly. On X-ray diffraction, a typical fibre pattern with an amorphous ring appeared already at ×10 (stretch ratio=10). The degree of crystallinity increased to the level of 17-18% at ×20 and turned to decrease after ×60, but the degree of crystallite orientation reached at a high level already at ×10 and did not change significantly and the half-height width of reflection profiles stayed almost at a constant level, while the Young's modulus increased up to ca. 300 MPa at ×100 and then fell rather discontinuously. It was assumed that some fractions of chain segments between entanglements were gradually broken in each step of stretching operation, rather than disentangled and slipped.     

Star-shaped poly(lactic acid) with carboxylic acid terminal groups via poly-condensation

A series of star-shaped poly(lactic acid)s with carboxylic acid terminal groups have been synthesized by direct poly-condensation of lactic acid in the presence of a poly-carboxylic acid core molecule with triphenylphosphonium trifluoromethanesulfonate (TPP-T) catalyst.These star-polymers had thermal properties not very much different from those of star-shaped poly(lactic acid) with hydroxyl terminal groups and linear poly(lactic acid), irrespective of the structure of the core molecule and number of polymer arms. Solubility and degradability of these star-polymers were, however, greatly enhanced compared to those of star-polymers with hydroxyl terminal groups and increased depending on the number of polymer arms. From the star-shaped polymers, a variety of ammonium salts and the corresponding carboxyamides were successfully prepared.     

Syntheses of Spinon Thermal Conductivity Materials in Sr–Cu–O System by Glass‐Ceramics Technique

We have synthesized spinon thermal conductivity materials in Sr–Cu–O system by glass‐ceramics technique. The materials are promising for active control of thermal energy in microelectronic devices because of high and anisotropic thermal conduction, its controllability, and electric insulation. Nevertheless, research on these materials has been limited to that concerning theoretical perspectives and investigation of physical properties using large single crystals. In this study, we adopt glass‐ceramics technique to synthesize these materials: We prepared melt‐quenched multicomponent oxides including SrO and CuO, and checked its glass‐forming ability and crystallization behaviors by heating. As a result, we have found that SrCuO₂ and Sr₁₄Cu₂₄O₄₁, known as the spinon thermal conductivity materials, are synthesized using SrO–CuO–?Li₂O–?Al₂O₃?–Ga₂O₃ system. This synthesis process for the system will provide practical application of the spinon thermal conductivity materials.     

Ursodeoxycholic Acid Suppresses Lipogenesis in Mouse Liver: Possible Role of the Decrease in β-Muricholic Acid,a Farnesoid X Receptor Antagonist

The farnesoid X receptor (FXR) is a major nuclear receptor of bile acids; its activation suppresses sterol regulatory element-binding protein 1c (SREBP1c)-mediated lipogenesis and decreases the lipid contents in the liver. There are many reports showing that the administration of ursodeoxycholic acid (UDCA) suppresses lipogenesis and reduces the lipid contents in the liver of experimental animals. Since UDCA is not recognized as an FXR agonist, these effects of UDCA cannot be readily explained by its direct activation of FXR. We observed that the dietary administration of UDCA in mice decreased the expression levels of SREBP1c and its target lipogenic genes. Alpha- and β-muricholic acids (MCA) and cholic acid (CA) were the major bile acids in the mouse liver but their contents decreased upon UDCA administration. The hepatic contents of chenodeoxycholic acid and deoxycholic acid (DCA) were relatively low but were not changed by UDCA. UDCA did not show FXR agonistic or antagonistic potency in in vitro FXR transactivation assay. Taking these together, we deduced that the above-mentioned change in hepatic bile acid composition induced upon UDCA administration might cause the relative increase in the FXR activity in the liver, mainly by the reduction in the content of β-MCA, a farnesoid X receptor antagonist, which suggests a mechanism by which UDCA suppresses lipogenesis and decreases the lipid contents in the mouse liver.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Formation of carbon nanotubes through ethylene decomposition over supported Pt catalysts and silica-coated Pt catalysts

Ethylene decomposition was performed over supported Pt catalysts to fabricate composites of Pt metal nanoparticles and carbon nanotubes (CNTs). All supported Pt catalysts (Pt/carbon black, Pt/CNT, Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂) showed catalytic activity for ethylene decomposition at 973 K to form CNTs. Pt metal particles were found at tips of CNTs. These results indicate that Pt metal particles have catalytic activity for growth of CNTs through hydrocarbon decomposition. A broad range (5-50 nm) of CNT diameters were formed from the use of supported Pt metal catalysts although Pt metal particles in the catalysts before ethylene decomposition were relatively uniform in size (2-5 nm). These results imply that Pt metal particles in the catalysts aggregated during ethylene decomposition at 973 K. Aggregation of Pt metal particles in catalysts during ethylene decomposition could be suppressed by covering catalysts with silica layers that were a few nanometers thick. Silica-coated Pt catalysts showed high activity for ethylene decomposition to form CNTs with uniform diameters (8-10 nm) despite the uniform coverage of Pt metal particles with silica layers.     

Cross-coupling reaction of alkyl halides with grignard reagents catalyzed by Ni, Pd, or Cu complexes with pi-carbon ligand(s)

Transition metal-catalyzed cross-coupling reactions of organic halides and pseudo-halides containing a C-X bond (X = I, Br, Cl, OTf, OTs, etc.) with organometallic reagents are among the most important transformations for carbon-carbon bond formation between a variety of sp, sp(2), and sp(3)-hybridized carbon atoms. In particular, researchers have widely employed Ni- and Pd-catalyzed cross-coupling to synthesize complex organic structures from readily available components. The catalytic cycle of this process comprises oxidative addition, transmetalation, and reductive elimination steps. In these reactions, various organometallic reagents could bear a variety of R groups (alkyl, vinyl, aryl, or allyl), but the coupling partner has been primarily limited to sp and sp(2) carbon compounds: alkynes, alkenes, and arenes. With alkyl coupling partners, these reactions typically run into two problems within the catalytic cycle. First, oxidative addition of alkyl halides to a metal catalyst is generally less efficient than that of aryl or alkenyl compounds. Second, the alkylmetal intermediates formed tend to undergo intramolecular beta-hydrogen elimination. In this Account, we describe our efforts to overcome these problems for Ni and Pd chemistry. We have developed new catalytic systems that do not involve M(0) species but proceed via an anionic complex as the key intermediate. For example, we developed a unique cross-coupling reaction of alkyl halides with organomagnesium or organozinc reagents catalyzed by using a 1,3-butadiene as the additive. This reaction follows a new catalytic pathway: the Ni or Pd catalyst reacts first with R-MgX to form an anionic complex, which then reacts with alkyl halides. Bis-dienes were also effective additives for the Ni-catalyzed cross-coupling reaction of organozinc reagents with alkyl halides. This catalytic system tolerates a wide variety of functional groups, including nitriles, ketones, amides, and esters. In addition, we have extended the utility of Cu-catalyzed cross-coupling reactions. With 1-phenylpropyne as an additive, Cu-catalyzed reactions of alkyl chlorides, fluorides, and mesylates with Grignard reagents proceed efficiently. These new catalytic reactions use pi-carbon ligands such as pi-allyl units or alkynes instead of heteroatom ligands such as phosphines or amines. Overall, these reactions provide new methodology for introducing alkyl moieties into organic molecules.     

热处理温度对莫来石-铝矾土浇注料性能的影响

以莫来石、铝矾土为主要原料,铝酸钙水泥为结合系统,研究了不同热处理温度对莫来石—铝矾土浇注料性能的影响。结果表明,随着热处理温度的提高,莫来石—铝矾土浇注料的体积密度减小;线变化率随着热处理温度的提高呈现收缩先增大后减小,最终出现膨胀的变化规律。莫来石—铝矾土浇注料的抗折强度随着热处理温度的提高先减小后增大;耐压强度随着热处理温度的提高先增大后减小。莫来石—铝矾土浇注料的热膨胀系数在450℃时出现最小值2.65×10-6℃-1。