Crosslinked polymer from N-vinylcarbazole and formalin

A crosslinked polymer has been synthesized from the reaction of N-vinylcarbazole and formalin in toluene in the presence of dry HCl gas. The copolycondensate is insoluble in all common solvents for poly-N-vinylcarbazole, and exhibits higher thermal stability than the unmodified poly-N-vinylcarbazole. However, this polymer is less thermally stable than the corresponding furfural modified poly-N-vinylcarbazole. A mechanism for the overall reaction has been suggested and the factors affecting the synthesis have been discussed.     

Voltammetric study of electrocatalysis for dioxygen reduction by trinuclear rutheniumammine complex confined in a polymer membrane

Electrocatalytic O₂ reduction was studied using a modified electrode coated with a Nafion membrane (Nf) dispersing a trinuclear ruthenium ammine complex ([(NH₃)₅Ru^IIIORu^IV(NH₃)₄ORu^III(NH₃)₅]Cl₆, Ru-red). When measuring cyclic voltammogram under O₂ atmosphere (at 0.5 mV s⁻¹), catalytic currents due to O₂ reduction were found to develop below −0.2 V (vs. Ag/AgCl). Since Ru-red undergoes irreversible decomposition into the mononuclear complexes via the reduced state (Ru^III-Ru^III-Ru^III) (∼−0.1 V), it is suggested that the electrocatalysis originates from the decomposed species (initial active species: Ru^II(NH₃)₅(OH₂) and Ru^II(NH₃)₄(OH₂)₂) rather than from the Ru-red. Although the present electrocatalyst was also applied to H₂O₂ reduction system, the catalytic activity was found to be poor from the voltammetric behavior. It appeared that the kinetics of the electrocatalysis is much faster in the O₂ reduction than in the H₂O₂ one. A selective and direct catalysis for O₂ reduction into H₂O was suggested from a ring-disk voltammogram to take place by an aggregate of the mononuclear ruthenium complexes in the polymer matrix. In addition, it was found that electrocatalytic O₂ reduction involves a slow kinetic process, so that factors affecting the overall kinetics were discussed in terms of the catalysis mechanism.     

Production of Carbon Nanotube by Ethylene Decomposition over Silica-Coated Metal Catalysts

Formation of carbon nanofibers (CNFs) and carbon nanotubes (CNTs) through the decomposition of ethylene at 973 K was achieved using various metal catalysts covered with silica layers. CNFs of various diameters were formed by ethylene decomposition over a Co metal catalyst supported on the outer surface of the silica. In contrast, silica-coated Co catalysts formed CNTs with uniform diameters by ethylene decomposition. Silica-coated Ni/SiO₂ and Pt/carbon black also formed CNTs with uniform diameters, while CNFs and CNTs with various diameters were formed over Ni/SiO₂ and Pt/carbon black without a silica coating. These results indicate that silica layers that envelop metal particles prevent sintering of the metal particles during ethylene decomposition. This results in the preferential formation of CNTs with a uniform diameter.     

Anisotropic in vitro vessel model using poly(vinyl alcohol) hydro gel and mesh material

In the present study, the authors fabricated straight multilayer hybrid tubular in vitro vessel models (inner diameter D_in = 10 mm; thickness T = 4 mm) composed of poly(vinyl alcohol) hydrogel (PVA‐H) and anisotropic mesh materials. The authors performed tensile, stress‐relaxation and cyclic‐tensile tests using axial and circumferential test pieces as well as pressure‐diameter (P‐D) tests using tubular test piece. In the tensile and stress‐relaxation tests, the anisotropic and nonlinear mechanical properties and hysteresis characteristic of the in vitro models were confirmed. The in vitro models also showed behavior qualitatively similar to that of native arteries in cycle‐tensile and P‐D tests. These results demonstrate that the mechanical properties of native vessels can be duplicated in an in vitro model by controlling the components of the mesh material, the orientation of elastic fibers in the mesh material, and the concentration and thickness of PVA‐H layers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Deposition and structural analyses of molybdenum-disulfide (MoS2)–amorphous hydrogenated carbon (a-C:H) composite coatings

In this study we developed composite coatings consisting of amorphous hydrogenated carbon (a-C:H) and molybdenum-disulfide (MoS₂), and clarified their microstructure. In addition, we interpreted the tribological properties of the composite coatings in the viewpoint of a deposition-induced microstructural modification. The coatings were produced by the hybrid deposition technique of RF-generated methane and argon plasma and DC magnetron co-sputtering of MoS₂ target. The deposition parameter investigated in this study was methane flow rate. Structural analyses were performed using a transmission electron microscope (TEM) and an atomic force microscope (AFM). Friction tests were conducted using a ball-on-disk type tribometer. From an electron micrograph, it was confirmed that nano-clusters were embedded into an amorphous carbon host matrix. Surface roughness of the composite coating was ～ 0.25 nm in R_a compared to 5.0 nm in R_a of sputtered MoS₂. The concentration measurements were performed, and the results show that the sulfur and molybdenum concentration ratio, [S]/[Mo], is ～ 0.9, which indicates that the amount of sulfur was reduced due to the discharged plasma. In friction tests, composite coatings showed high friction in a vacuum condition. It was considered that lubricant MoS₂ lamellar structures showing super-low friction in a vacuum condition during friction could not be formed between ball and coating during friction because of the lack of sulfur in embedded clusters.     

Light-Wavelength-Based Quantitative Control of Dihydrofolate Reductase Activity by Using a Photochromic Isostere of an Inhibitor

Photopharmacology has attracted research attention as a new tool for achieving optical control of biomolecules, following the methods of caged compounds and optogenetics. We have developed an efficient photopharmacological inhibitor—azoMTX—for Escherichia coli dihydrofolate reductase (eDHFR) by replacing some atoms of the original ligand, methotrexate, to achieve photoisomerization properties. This fine molecular design enabled quick structural conversion between the active “bent” Z isomer of azoMTX and the inactive “extended” E isomer, and this property afforded quantitative control over the enzyme activity, depending on the wavelength of irradiating light applied. Real-time photoreversible control over enzyme activity was also achieved.     

Preparation and electrooptical properties of liquid crystal dispersed film by electron-beam irradiation

Polymer films consisting of nematic liquid crystal (LC) droplets and polymer networks were prepared by using a low-energy electron beam to irradiate a homogeneous mixture of nematic LC and bifunctional methacrylate monomer. Influences of such polymerization conditions as polymerization temperature, monomer concentration, and radiation energy on electrooptical properties of the compound films were examined. The polymer yield, affecting to a large extent the film properties, depended on the monomer concentration and the radiation energy. Compound films, which have a switching function from the scattering state to transparency by applying approximately 20–30 V between the two sides of the film, were obtained. In addition, it was found that a compound film with excellent electrooptical properties was prepared by changing impure LC in the droplets into pure LC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1675–1681, 1997     

Fabrication of Transparent, Sintered Sc2O3 Ceramics

We report here the fabrication of transparent Sc₂O₃ ceramics via vacuum sintering. The starting Sc₂O₃ powders are pyrolyzed from a basic sulfate precursor (Sc(OH)_2.6(SO₄)_0.2·H₂O) precipitated from scandium sulfate solution with hexamethylenetetramine as the precipitant. Thermal decomposition behavior of the precursor is studied via differential thermal analysis/thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffractometry, and elemental analysis. Sinterability of the Sc₂O₃ powders is studied via dilatometry. Microstructure evolution of the ceramic during sintering is investigated via field emission scanning electron microscopy. The best calcination temperature for the precursor is 1100°C, at which the resultant Sc₂O₃ powder is ultrafine (∼85 nm), well dispersed, and almost free from residual sulfur contamination. With this reactive powder, transparent Sc₂O₃ ceramics having an average grain size of ∼9 μm and showing a visible wavelength transmittance of ∼60–62% (∼76% of that of Sc₂O₃ single crystal) have been fabricated via vacuum sintering at a relatively low temperature of 1700°C for 4 h.     

Properties of novel diallyl phthalate resin modified with sulfur‐containing allyl ester compounds

Sulfur‐containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur‐containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur‐containing allyl ester compound, the T‐peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (?S?S?) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (T_g) and the thermal decomposition temperature (T_d) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of T_g is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry     

Production of thin graphite sheets for a high electrical conductivity film by the mechanical delamination of ternary graphite intercalation compounds

Herein we propose a production scheme for conductive films composed of thin graphite sheets with high crystallinity and polymeric resin. The crystalline graphite sheets were successfully produced from natural graphite powder by solution-phase synthesis of graphite intercalation compounds (GICs), following a wet planetary-ball milling under mild conditions. The shear forces in the milling pot lead to a peeling of graphite flakes. Taking into consideration the interlayer bonding force, the delamination should be preferentially done from the expanded GICs interlayer rather than intrinsic graphite one. Some composite films derived from the phenolic resin and flaky graphite sheets displayed much higher electrical conductivities compared to the film from the feed graphite particles. We also demonstrate the stage structure of synthetic GICs affected the film conductivity. The composite films made from exfoliated products of ground (around stage IV) GICs exhibited high electrical conductivity with a small amount of the graphite sheets.