Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group‐containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group‐terminated polymethylphenylsilane in 15–32% yield. The isolated polymethylphenylsilane (M_n = 3350 g mol^?1, M_w/M_n = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (M_n = 4730 g mol^?1, M_w/M_n = 1.2) in 38% yield. The ratio of monomer units (? MeSiPh? to? BuSiBu? ) of the copolymer was determined to be 75:25 using ¹H NMR analysis, which was in good agreement with the calculated ratio (74:26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)‐block‐poly(dibutylsilane), was also confirmed by comparing its ¹H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group‐terminated polydibutylsilane, and polydibutylsilane‐block‐polymethylphenylsilane was also obtained using this macroinitiator. Copyright © 2011 Society of Chemical Industry     

Euphorbia tirucalli β-Amyrin Synthase: Critical Roles of Steric Sizes at Val483 and Met729 and the CH–π Interaction between Val483 and Trp534 for Catalytic Action

The functions of Val483, Trp534, and Met729 in Euphorbia tirucalli β-amyrin synthase were revealed by comparing the enzyme activities of site-directed mutants against that of the wild type. The Gly and Ala variants with a smaller bulk size at position 483 predominantly afforded monocyclic camelliol C, which suggested that the orientation of the (3S)-2,3-oxidosqualene substrate was not appropriately arranged in the reaction cavity as a result of the decreased bulk size, leading to failure of its normal folding into the chair–chair–chair–boat–boat conformation. The Ile variant, with a somewhat larger bulk, afforded β-amyrin as the dominant product. Intriguingly, various variants of Trp534 exhibited significantly decreased enzymatic activities and provided no aberrantly cyclized products, although the aromatic Phe and Tyr residues were incorporated and the steric sizes of the aliphatic residues were altered. Therefore, the Trp534 residue does not stabilize the transient cation through a cation–π interaction. Furthermore, the Trp residue, with the largest steric bulk among all natural amino acids, is essential for high enzymatic activity. Robust CH–π complexation between the Val483 and Trp534 residues is proposed herein. Altering the steric bulk at the Met729 position afforded the pentacyclic skeletons. Thus, Met729 is positioned at the E-ring formation site. More detailed insights into the functions of the Val483, Trp534, and Met729 residues are provided by homology modeling.     

Structures and electronic properties of surface/edges of nanodiamond and nanographite

The structure, electronic and magnetic properties of nanodiamond and nanographite/nanographene are investigated. Detonation nanodiamond particles that are covered with amorphous graphitic composites are hydrothermally treated to remove the graphitic surface composites and to terminate the surface carbon atoms with hydrogen. The number of localized spins of dangling bonds and the hydrogen concentration increase upon the increase in the hydrothermal treatment time up to 40 h. Above 40 h, both drop discontinuously, a surface structural reconstruction was suggested. The creation of dangling bonds and an incomplete hydrogenation of the surface carbon atoms destabilize the surface, resulting in the structural reconstruction. Nanodiamond particles are thermally converted to nanographite/nanographene. A single nanographene sheet is successfully prepared by heat-treating nanodiamond particles. The edge of graphene sheet with its edge carbon atoms being hydrogen-terminated is investigated by UHV-STM/STS. Zigzag edges are found to have non-bonding π-state of edge origin, in good agreement with theoretical prediction.     

Adsorption of amino acids by fullerenes and fullerene nanowhiskers

We have investigated the adsorption of some amino acids and an oligopeptide by fullerene (C₆₀) and fullerene nanowhiskers (FNWs). C₆₀ and FNWs hardly adsorbed amino acids. Most of the amino acids used have a hydrophobic side chain. Ala and Val, with an alkyl chain, were not adsorbed by the C₆₀ or FNWs. Trp, Phe and Pro, with a cyclic structure, were not adsorbed by them either. The aromatic group of C₆₀ did not interact with the side chain. The carboxyl or amino group, with the frame structure of an amino acid, has a positive or negative charge in solution. It is likely that the C₆₀ and FNWs would not prefer the charged carboxyl or amino group. Tri-Ala was adsorbed slightly by the C₆₀ and FNWs. The carboxyl or amino group is not close to the center of the methyl group of Tri-Ala. One of the methyl groups in Tri-Ala would interact with the aromatic structure of the C₆₀ and FNWs. We compared our results with the theoretical interaction of 20 bio-amino acids with C₆₀. The theoretical simulations showed the bonding distance between C₆₀ and an amino acid and the dissociation energy. The dissociation energy was shown to increase in the order, Val < Phe < Pro < Asp < Ala < Trp < Tyr < Arg < Leu. However, the simulation was not consistent with our experimental results. The adsorption of albumin (a protein) by C₆₀ showed the effect on the side chains of Try and Trp. The structure of albumin was changed a little by C₆₀. In our study Try and Tyr were hardly adsorbed by C₆₀ and FNWs. These amino acids did not show a different adsorption behavior compared with other amino acids. The adsorptive behavior of mono-amino acids might be different from that of polypeptides.     

Effect of CNTs on morphology and electromagnetic properties of non-firing CNTs/silica composite ceramics

Carbon composite ceramics have much attention for industry because of their excellent properties such as strong toughness, high electrical conductivity as well as low percolation threshold. Therefore, carbon nanotubes (CNTs) were used to incorporate with silica ceramics in order to improve their electromagnetic properties. The amount of CNTs in CNTs/silica composite ceramics was varied in order to investigate its effect on morphologies and electromagnetic properties of those. The composites were successfully fabricated by non-firing process. The results revealed that the obtained CNTs/silica composite ceramic have an electrical resistivity of 66.6?Ω·cm with a bending strength of 13.8?MPa. At the same time, the electromagnetic wave absorption ability achieved 70% over a wild frequency. This indicates that the CNTs in CNTs/silica composite ceramics may be potentially applied for an electromagnetic wave reflective material.     

Effect of silane modification on CNTs/silica composites fabricated by a non-firing process to enhance interfacial property and dispersibility

Carbon nanotube/ceramic composites have been in the spotlight thanks to their excellent properties. Sintering is the vital part of ceramics fabrication in terms of reliability, however sintering the carbon nanotube (CNT) based ceramic composites is a challenging task. In this study, interfacial bonding of silane functionalized CNT with silica ceramic is investigated by a non-firing sintering process. CNTs are first treated by a mixed acid with the aid of a silane 3-aminopropyl triethoxysilane (APTES), which improves the chemical bonding and dispersibility of CNT in ceramic bodies. The extent of APTES chemical functionalization and mechanical property of CNT/silica ceramic composites are characterized using Raman spectrometer, FT-IR analysis, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and three-point bending strength measurement. Results show that composites are successfully prepared without sintering with stable CNT-silica interface, superior dispersibility, and good mechanical properties.     

Manipulating the chemical affinity and kinetics of 3D silica particle network via the phase-separation technique

We developed a simple and versatile technique for a particle’s self-organizing-network based on a non-solvent induced micro-phase separation (NIPS). When a good solvent vaporizes from a particle dispersion in a ternary solution including the polymer, good solvent and non-solvent, the suspension is separated into the polymer network and non-solvent phase. If the affinity between the particles and polymer is sufficient enough, the particles are entrapped in the polymer network and particle network can be achieved. To expand this technique to particles with various physical properties, the surface of the particles was identified using the Hansen dispersibility parameter (HDP). From a comparison of the HDP of the unmodified and modified silica, an NH₂ group is suitable for entrapment of the silica by cellulose acetate as the polymer. However, with an increase in number of the silica particles, entrapment of the silica in the polymer was prevented. Control of the phase separation rate by the lowering temperature leaded to entrapment of silica particles in the polymer network. The proposed technique is effective not only for spherical oxide particles, but also for non-oxides, various shapes and structures. Depending on particle characteristics, functional films and bulk materials for thermal insulation, light diffusion, and electro conductivity can be obtained.     

Thermal conductivity analysis using three‐dimensional microstructures of gelation freezing derived cellular mullite

The relationship between thermal conductivity and unidirectional cellular mullite microstructures created with the freeze casting route is discussed using actual three‐dimensional (3D) images, in which a homogenization method was conducted with microscopic models created from 3D images, the temperature variation in macroscopic models by the finite element method (FEM), and local heat conduction in microscopic models. The simulation results were consistent with the experimental results. This image‐based modeling technique was thus confirmed to be a strong tool for the prediction of various thermal properties of porous ceramics.     

The study on change of mechanical properties of NBR due to deterioration

Rubber is an important industrial material. However, mechanical properties and deformation of the high polymer including rubber are not clear. A method of estimating the mechanical properties which can be used for the deteriorated rubber is demanded to improve the reliability of it. Improved VBO (Viscoplasticity theory based on overstress) model is a constitutive equation. We applied it for the compression stress-strain behavior of deteriorated NBR (acryloNitrile-Butadiene rubber). Furthermore, we proposed a method of estimating the mechanical properties of deteriorated NBR. In this paper, deterioration tests in water and in air were conducted. To confirm the validity of the proposed improved VBO model and estimated mechanical properties, simulations of the stress-strain curves obtained in the tests were conducted.