Synthesis of metal nitrides and carbide powders by a spark discharge method in liquid media

Metal nitrides and carbides powders were synthesized by the spark discharge method in liquid ammonia at 100 °C and 11 kV of the spark discharge voltage and in n-heptane at 25 °C and 7.5 kV using the pellets of aluminum, titanium, iron and chromium as the starting material. The main products were AlN, TiN_0.51, -Fe, -Cr₂N in liquid ammonia, and Al₄C₃, TiC, -Fe, Fe₂C and Cr₇C₃ in n-heptane. The agglomerated particle size decreased with increasing melting point of the metal used as the starting material.     

Enhancement of superconductivity in Pb-Bi-Sn and Pb-Bi-In alloy filaments produced by glass-coated melt spinning

The enhancement ofT _c in Pb-Bi-Sn and Pb-Bi-In system alloy filaments produced by glass-coated melt spinning was investigated as a means of producing a new type of superconducting filament with highT _c. Long filaments of Pb-Bi-Sn alloy withT _c higher than 10 K and Pb-Bi-In alloy withT _c higher than 9 K were obtained from the molten state at a temperature of 1500 K with a winding speed of 2.63 m sec^–1. For example, a Pb₄₅Bi₃₅Sn₂₀ filament withT _c of 10.1 K was 15 m in diameter and polycrystalline with a grain size of 100 nm. The structure of the filament was a mixture of , tin and bismuth phases and a metastable phase of mixed structure of bismuth and supersaturated solid solution of tin in -phase was detected. TheT _c of the filament decreased on heat treatment. A metastable phase of mixed structure of bismuth and -phase was also detected for a Pb₄₅Bi₄₅In₁₀ filament withT _c of 9.3 K. As the metastable phase for the Pb-Bi-In filament was more unstable than that for the Pb-Bi-Sn filament, theT _c of the filament was drastically decreased by heat treatment. The metastable phase was considered to play an important role in the enhancement ofT _c for Pb-Bi-Sn and Pb-Bi-In alloy filaments.     

Selective oxidation of Fe-30Ni alloy in a low-temperature range (433–473 K)

Fe-30Ni alloy specimens were oxidized for 10–240 min at 433–473 K in pure oxygen at a pressure of 1.33×10⁴ Pa. The thickness of oxide films was measured by a multiple-angle-of-incidence ellipsometer. The kinetics of film growth were found to obey a parabolic rate law. The depth-profiling of oxidized surfaces, performed with simultaneous use of Auger electron spectroscopy (AES) and argon-ion sputter-etching technique, reveals that iron component is selectively oxidized and an iron-depeletion zone is formed in the underlying alloy. The thickness of the iron depletion zone increases with increasing oxidation time or oxidation temperature. During surface oxidation of the alloy, the transport rate of iron component in the film is almost equal to the interdiffusion rate in the underlying alloy, indicating the establishment of a steady state. The values of the interdiffusion coefficient, , of the underlying alloy estimated from the depth-composition profiles are more than 10 orders of magnitude as large as the values extrapolated from the lattice diffusion data of the corresponding alloy obtained at high temperature. The enormously large values of may be explained in terms of the vacancy (monovacancy or divacancy)-enhanced lattice diffusion mechanism.     

Current Understanding of the Structure,Stability and Dynamic Properties of Amyloid Fibrils

Amyloid fibrils are supramolecular protein assemblies represented by a cross-β structure and fibrous morphology, whose structural architecture has been previously investigated. While amyloid fibrils are basically a main-chain-dominated structure consisting of a backbone of hydrogen bonds, side-chain interactions also play an important role in determining their detailed structures and physicochemical properties. In amyloid fibrils comprising short peptide segments, a steric zipper where a pair of β-sheets with side chains interdigitate tightly is found as a fundamental motif. In amyloid fibrils comprising longer polypeptides, each polypeptide chain folds into a planar structure composed of several β-strands linked by turns or loops, and the steric zippers are formed locally to stabilize the structure. Multiple segments capable of forming steric zippers are contained within a single protein molecule in many cases, and polymorphism appears as a result of the diverse regions and counterparts of the steric zippers. Furthermore, the β-solenoid structure, where the polypeptide chain folds in a solenoid shape with side chains packed inside, is recognized as another important amyloid motif. While side-chain interactions are primarily achieved by non-polar residues in disease-related amyloid fibrils, the participation of hydrophilic and charged residues is prominent in functional amyloids, which often leads to spatiotemporally controlled fibrillation, high reversibility, and the formation of labile amyloids with kinked backbone topology. Achieving precise control of the side-chain interactions within amyloid structures will open up a new horizon for designing useful amyloid-based nanomaterials.     

Identification of Tumor Suppressive Genes Regulated by miR-31-5p and miR-31-3p in Head and Neck Squamous Cell Carcinoma

We identified the microRNA (miRNA) expression signature of head and neck squamous cell carcinoma (HNSCC) tissues by RNA sequencing, in which 168 miRNAs were significantly upregulated, including both strands of the miR-31 duplex (miR-31-5p and miR-31-3p). The aims of this study were to identify networks of tumor suppressor genes regulated by miR-31-5p and miR-31-3p in HNSCC cells. Our functional assays showed that inhibition of miR-31-5p and miR-31-3p attenuated cancer cell malignant phenotypes (cell proliferation, migration, and invasion), suggesting that they had oncogenic potential in HNSCC cells. Our in silico analysis revealed 146 genes regulated by miR-31 in HNSCC cells. Among these targets, the low expression of seven genes (miR-31-5p targets: CACNB2 and IL34; miR-31-3p targets: CGNL1, CNTN3, GAS7, HOPX, and PBX1) was closely associated with poor prognosis in HNSCC. According to multivariate Cox regression analyses, the expression levels of five of those genes (CACNB2: p = 0.0189; IL34: p = 0.0425; CGNL1: p = 0.0014; CNTN3: p = 0.0304; and GAS7: p = 0.0412) were independent prognostic factors in patients with HNSCC. Our miRNA signature and miRNA-based approach will provide new insights into the molecular pathogenesis of HNSCC.     

A distribution kinetics model for chromatography of block-like molecules

We develop the theory for chromatographic separation of isomers such as polycyclic aromatic hydrocarbons, polychlorinated biphenyls, dioxins, steroids, and carotenoids based on shape-selective mechanisms for either exclusion or adsorption. Block-like solute transport and retention on oriented stationary phases are modeled by a dispersed-flow chromatographic equation combined with simultaneous exclusion partitioning and shaped-based adsorption. Molecules to be separated are considered distributed continuously with respect to the shape and sorption parameters. The population balance equations of distribution kinetics provide the governing differential equations that are solved for the temporal moments of the concentration in a chromatographic column. By including dispersive mass transport effects, the model allows estimation of peak variance and HETP and is thus an improvement over theories that focus solely on retention time. The model predictions are compared with experimental data from the literature for gas chromatography.     

Surface active N-acylglutamate: I. Preparation of long chain N-acylglutamic acid

Long chain N-acylglutamic acid was prepared in a high yield by a reaction of glutamic acid with fatty acid chloride in a mixed solvent of water and a water miscible organic solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran,t-butyl alcohol or cyclohexanone. In this reaction the composition of the mixed solvent influenced the yield of N-acylated glutamic acid and the best yield was obtained when the reaction was carried out in the mixed solvent comprising 30–60% v/v of the organic solvent. Long chain N-acylaspartic acid was also obtained in a high yield by the same method. As the other method to obtain N-lauroyl-D L-glutamic acid, it was examined that N-acyl-α-aminoglutarodinitrile which was obtained by a reaction of α-aminoglutarodinitrile with fatty acid chloride was hydrolyzed with an aqueous alkaline solution. The salts of long chain N-acylglutamic acid are known as the surface active agents that react mildly on the human skin.     

A Practical Model for the Interactions Between Hydrating Portland Cements and Poly-β-Naphthalene Sulfonate Condensate Superplasticizers

The performance of poly-β-naphthalene sulfonate condensate superplasticizer (BNS) as a dispersant for cement in concrete is affected severely by slight differences in the characteristics of the cement. In order to be able to predict these effects, a model for estimating the fluidity of cement paste containing BNS is proposed. This model is based on an assumption that the fluidity of cement paste is proportional to the BNS adsorption amount per surface area of hydrated cement (Ad/Hy). BNS is known to show two types of sorption on hydrated cement: one is the bulk absorption into initial hydrates and the other one is the superficial adsorption onto hydrates. Only the superficially adsorbed BNS is expected to work as a dispersant. By assuming a competitive Langmuir-type adsorption on hydrates between BNS and SO₄²⁻, a simple method to estimate Ad/Hy is developed, with the concentrations of BNS and SO₄²⁻ as the only two independent parameters. The resulting estimates of Ad/Hy show a good correlation with paste flow and its change with elapsed time for a broad range of cements. The SO₄²⁻ concentration in the aqueous phase of the cement paste just after the beginning of the mixing is known to affect the performance of BNS as a dispersant. By using the proposed model to discriminate between the superficial adsorption and bulk absorption of BNS, this phenomenon is explained quantitatively.     

Preparation and properties of graft and block copolymers of poly(p-phenylene terephthalamide) with polybutadiene

Graft copolymers of polybutadiene (PBD) onto poly(p-phenylene terephthalamide) (PPTA) were prepared by the nucleophilic substitution of N-metalated PPTA with telechelic PBD having bromide end groups. Block copolymers were synthesized by the condensation reaction of telechelic PBD having acid chloride end groups with amino-group-terminated PPTA. The structure of these copolymers was identified by IR spectra. Graft and block copolymers contained PBD segments up to 85 wt % and 45 wt %, respectively. Thermomechanical analyses (TMA) proved the existence of distinctive primary absorption peak corresponding with T_g of PBD for both graft and block copolymers. The T_g's of both types of the copolymers were further ascertained by the DSC curves. TMA curves suggested that the microphase separation occurred between PPTA and PBD. The incorporation of PPTA segments into PBD increased the decomposition temperature compared with the blend polymer composed of PPTA and PBD with the same composition.     

Fabrication of Nonadditive Mica Ceramics by Hot Isostatic Processing

Powder compacts of synthetic mica (fluorphlogopite) encapsulated in a boro–silicate glass tube were isostatically hot–pressed in a Roy–Tuttle–type pressure vessel. Synthetic mica was sintered to a density of 2.60 g/cm³ (91.2% of theoretical density) without additives under 98 MPa of water at 800°C for 45 min.