Effect of dehydration and urea on stability of homosulfamine in solid states

In the presence of urea in solid states, the stability of unpulverized homosulfamine hydrate (phase I; UHH) is significantly decreased whereas that of unpulverized homosulfamine anhydrate (UHA) is not. The stability of UHH is decreased slightly more by pulverization (PHH). The major objective of this study was to investigate the effects of urea, dehydration, and pulverization on the stability of homosulfamine in solid states. Binary mixtures of UHH and urea, PHH and urea, and UHA and urea in a ratio of 1:1 (wt/wt) were prepared as physical mixtures and were analyzed by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), and Fourier transform infrared (FTIR) spectroscopy to study their appearance and structural changes before and after storage. PXRD analysis revealed that physical mixtures comprising UHH and urea and PHH and urea have the same diffraction pattern as that of the mixture of UHA and urea after preparation. The dehydration rate of the crystal water of UHH was accelerated by the presence of urea in addition to pulverization. Moreover, the PXRD patterns of the physical mixtures of UHH/urea and PHH/urea were significantly altered during storage, whereas that of UHA/urea was not, which was consistent with the SEM and FTIR results. The particle shape and appearance of UHH varied significantly as a result of pulverization. The stability of homosulfamine was influenced not only by the presence of urea and dehydration but also by the surface state and particle size of the crystalline form.     

Purification and properties of rabbit muscle proteasome, and its effect on myofibrillar structure

This paper describes the purification and properties of a multicatalytic proteinase complex, proteasome, from rabbit skeletal muscle, and its effect on myofibrillar structure. The purified proteasome gave a single band on polyacrylamide gel electrophoresis under non-denaturing conditions and gave eight bands under denaturing conditions, indicating that this enzyme comprises multiple hetero-subunits with low molecular mass. The purified proteasome was not activated by ATP and ubiquitin, and was markedly inhibited by Z-Leu-Leu-Leu-H (aldehyde). These data indicate that the purified proteasome is not 26S, but 20S. The proteasome degraded synthetic peptides maximally at pH 8.0. Relative to pH 8.0, activities were gradually decreased with the lowering of pH, but the degree of decrease was substrate-dependent, and the activity at pH 5.0 still retained about 30˜60% of the activity at pH 8.0, indicating the possibility that the proteasome is active in the muscle during conditioning. When the proteasome was heated at 60 °C for 20 min and treated in the presence of 0.005% SDS, the activity increased over 1.5 and 4.5 times, respectively. SDS remarkably increased the V_max value of the enzyme at pH 8.0. The proteasome was also activated by high hydrostatic pressure up to 100˜150 M Pa and gradually decreased at 200 MPa or higher. Electron microscopic observation revealed that obvious gaps between filamentous structure, the complete loss of M-line and partial loss of Z-line structure were caused by proteasome.     

Synthesis of C2H4 by partial oxidation of CH4 over LiCl/NiO

Alkali halide added transition metal oxides produced ethylene selectively in oxidative coupling of methane. The role of alkali halides has been investigated for LiCl-added NiO (LiCl/NiO). In the absence of LiCl the reaction over NiO produced only carbon oxides (CO₂ + CO). However, addition of LiCl drastically improved the yield of C₂ compounds (C₂H₆ + C₂H₄). One of the roles of LiCl is to inhibit the catalytic activity of the host NiO for deep oxidation of CH₄. The reaction catalyzed by the LiCl/NiO proceeds stepwise from CH₄ to C₂H₄ through C₂H₆ (2CH₄ → C₂H₆ → C₂H₄). The study on the oxidation of C₂H₆ over the LiCl/NiO showed that the oxidative dehydrogenation of C₂H₆ to C₂H₄ occurs very selectively, which is the main reason why partial oxidation of CH₄ over LiCl/NiO gives C₂H₄ quite selectively. The other role of LiCl is to prevent the host oxide (NiO) from being reduced by CH₄. The catalyst model under working conditions was suggested to be the NiO covered with molten LiCl. XPS studies suggested that the catalytically active species on the LiCl/NiO is a surface compound oxide which has higher valent nickel cations (Ni^(2+δ)+ or Ni³⁺). The catalyst was deactivated at the temperatures>973 K due to vaporization of LiCl and consumption of chlorine during reaction. The kinetic and CH₄---CD₄ exchange studies suggested that the rate-determining step of the reaction is the abstraction of H from the vibrationally excited methane by the molecular oxygen adsorbed on the surface compound oxide.     

A tetrameric dialdehyde formed in the reaction of butyral dehyde and benzylamine: A possible intermediary component for protein cross-linking induced by lipid oxidation

We investigated the reaction of butyraldehyde and benzylamine and analyzed the products to identify the components that produce protein cross-linking in the reaction of butyraldehyde and proteins. When the mixtures of butyraldehyde and benzylamine were incubated at pH 7 and 37°C for 48 hr, many reaction products other than 2-ethyl-2-hexenal and Schiff bases of butyraldehyde and 2-ethyl-2-hexenal were produced. Fluorescent substance(s) were formed only in the presence of dissolved oxygen in the reaction mixture. Three new nonflourescent products—d,e andf—were isolated, and their structures are suggested to be 2,9-dibenzyl-4,6,8-triethyl-7-propyl-2,9-diazabicyclo[3,3,1] nona-3-ene (d), 1-phenyl-2-benzyl- 4,5,7-triethyl-6-propyl-1H,2H,3H,5H,6H,7H,8H-pyrido[1,2-clpyrimidine (e) and 1-phenyl-2-benzyl-4,5,7-triethyl-6-propyl-1H,2H,4aH,5H,6H,7H,8H-pyrido[1,2-c]pyrimidine (f). Formation of these compounds suggested that the protein, cross-linking with butyraldehyde is caused by the tretrameric dialdehyde formed by repeated aldol condensation and Michael reaction of butyraldehyde.     

Fabrication and electrical properties of SrTiO3/diamond junctions

Strontium titanate (STO) films were directly deposited on Ib (100) single crystal diamond by r.f. magnetron sputtering. The as-deposited STO film was in amorphous state. On the other hand, the crystalline STO film was obtained under the optimized condition of a deposition temperature of 250 °C and a post-annealing temperature of 650 °C. STO/diamond junctions were fabricated on boron-doped homoepitaxial layers grown on p⁺-type single crystal diamond substrates. Electrical properties of the STO/diamond junction were investigated by changing the surface terminations of diamond with hydrogen or oxygen and the crystallinity of the STO film. It was found that the amorphous STO acted like a semi-insulator on H-diamond surface and that the amorphous STO/O-diamond junction behaved like a Schottky diode. The crystalline STO/O-diamond showed a complex rectifying behavior. The crystalline STO film possessed a higher dielectric constant as compared to that of the amorphous one.     

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.     

Macro- and nanotribological properties of organosilane monolayers prepared by a chemical vapor adsorption method on silicon substrates

Organosilane monolayers are novel ultrathin films used to control the physicochemical properties, such as friction and wear, of solid surfaces. In this study, the authors prepared alkylsilane and fluoroalkylsilane monolayers with a series of chain lengths by a chemical vapor adsorption method. The monolayers tribological properties were investigated by lateral force microscope (LFM) and friction tester. LFM nanoscale measurements of tribological properties showed that alkylsilane monolayer gave lower lateral force than the Si substrate surface. The lateral force decreased as the length of the alkyl chain increased. On the macroscale, friction test revealed that the organosilane monolayers gave lower dynamic friction coefficients than the Si substrate surface in air at room temperature. The longer the alkyl chain, the greater the wear resistance of the organosilane monolayers. Friction experiments using tetradecane as a lubricant showed better tribological properties than were obtained in air. Furthermore, microscopically line-patterned two-component organosilane monolayers were prepared and their macroscopic friction behavior was investigated. Even though the height difference between the two-components was less than 1 nm, friction force anisotropy between the parallel and perpendicular directions against the line pattern was observed.     

Chemistry and melting characteristics of fireside deposits taken from boiler tubes in waste incinerators

Twenty-three tube deposits taken from seven heat-recovery boilers of municipal solid waste incinerators were examined by chemical analyses and X-ray diffraction. These deposits were measured by Differential Scanning Calorimeter (DSC) in N₂ to investigate their melting characteristics. Sixteen deposits were used to evaluate their corrosiveness to carbon steel by high-temperature corrosion test conducted at 400 °C for 20 h in 1500 ppm HCl – 300 ppm SO₂ – 7.5%O₂ – 7.5%CO₂ – 20%H₂O – N₂. Total heat of endothermic reactions of the deposits taking place between 200 and 400 °C can be related to the corrosion rate of carbon steel at 400 °C. Corrosion initiated at temperatures when the deposits started to melt, became severe when fused salt constituents increased, and alleviated when the majority of the deposits became fused. The corrosion can be interpreted as fused salt corrosion caused by chloride and sulfate salts.