Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Influence of reaction temperature on direct esterifications in a continuous recycling process between terephthalic acid and ethylene glycol

Simulations were carried out with a continuous recycle esterification model for the terephthalic acid–ethylene glycol (TPA–EG) system proposed previously. The influence of reaction temperatures, recycle ratios, and residence times on the oligomer characteristics was examined and the following results were obtained: (1) The main reactions proceed more under higher reaction temperatures, but the side reactions on diethylene glycol (DEG) proceed further than do the main reactions. (2) The higher residence time ratio of the first reactor to the total results in the proceeding of esterifications, which becomes remarkable as the temperature becomes high. (3) As the recycle ratio becomes high, the esterfications proceed, but in the very high degree of esterification, the tendency is reversed. (4) The characteristics of oligomer are almost the same at the same degree of esterification, independent of the reaction conditions. © 1994 John Wiley & Sons, Inc.     

Resistance to sulfur poisoning of hot gas cleaning catalysts for the removal of tar from the pyrolysis of cedar wood

In the partial oxidation of tar derived from the pyrolysis of cedar wood, the effect of H₂S addition was investigated over non-catalyst, steam reforming Ni catalyst, and Rh/CeO₂/SiO₂ using a fluidized bed reactor. In the non-catalytic gasification, the product distribution was not influenced by the presence of H₂S. Steam reforming Ni catalyst was effective for the tar removal without H₂S addition, however, the addition of H₂S deactivated drastically. In contrast, Rh/CeO₂/SiO₂ exhibited higher and more stable activity than the Ni catalyst even under the presence of high concentration of H₂S (280 ppm). On the Ni catalyst, the adsorption of sulfur was observed by XPS and Ni species was oxidized during the partial oxidation of tar. In the case of Rh/CeO₂/SiO₂, the adsorption of sulfur was below the detection limit of XPS. This can be related to the self-cleaning of catalyst surface during the circulation in the fluidized bed reactor for the partial oxidation of tar derived from cedar pyrolysis.     

Low-temperature selective reduction of NO with propene over alkaline-exchanged mordenites

Partially protonated alkaline mordenites showed higher activity per acid amount below 573 K than acidic zeolites for the selective reduction of NO with C₃H₆ in the presence of O₂, which can be related to a high concentration of NO₃ ^- species in the zeolite channels. This revised version was published online in July 2006 with corrections to the Cover Date.     

Microstructure and Thermal Shock Resistance of Molten Glass-Coated Carbon Materials Fabricated by Interfacial Control

Carbon substrates were coated completely with a molten silicate glass, where the wettability of carbon to glass was improved by infiltration and pyrolysis of perhydropolysilazane. Microstructures of the carbon–glass interface were dependent on P n ₂ during coating. Coating at lower P n ₂ induced the formation of cristobalite at the carbon–glass interface. When the coating was performed at higher P n ₂, the glass and carbon were strongly adhered, without the formation of cristobalite. Coating at higher P n ₂ improved the thermal shock resistance of the glass layer, because crack initiation was not induced by the phase transformation of cristobalite during the cooling process. In the case of coating at higher P n ₂, an oxynitride glass layer was formed at the glass subsurface by dissolution of N₂. A porous glass subsurface layer with uniform spherical micro-pores could be produced by soaking near the glass transition temperature in a steam environment. The porous layer with fine and homogeneous microstructure acts as a thermal shock absorbing layer, so that glass-coated carbon with a porous glass layer has excellent thermal shock resistance in addition to steam oxidation resistance.     

Production of finely ground natural graphite particles with high electrical conductivity by controlling the grinding atmosphere

Natural graphite particles with high crystallinity sieved to obtain a particle size range of under 63 μm were ground with a ball mill, under various well-controlled grinding atmospheres such as N₂, O₂, He, H₂, and vacuum. The ratio, X_dif50/X_st50, i.e. between the 50 wt.% Stokes diameter and the 50 wt.% laser diffraction diameter, of the ground particles, was used as an index of the flakiness of the particles. The specific resistance of films composed of the ground graphite particles was systematically measured. The rate of reduction in the size of the particles by grinding was slow under an O₂-rich atmosphere such as 100% O₂ and dry air. On the other hand, it was relatively fast in vacuum, or under an N₂ or He atmosphere, and a gas mixture of 99% N₂ and 1% O₂. The rate of size reduction by grinding under a H₂ atmosphere was intermediate. In our experimental conditions, the flakiness of the ground particles increased with the decrease in the particles’ sizes. The electrical conductivity of the ground particles, however, tended to decrease with the decrease in their sizes. Under the condition that the Stokes diameter of the ground particles remains constant, the electrical conductivity of films made from the ground particles increases with the increase in the flakiness of the particles. It was finally determined from our systematic grinding experiments that small flaky particles, which had a size, X_st of ∼1 μm, with a high electrical conductivity can be produced by grinding in a gas mixture of 99% N₂ and 1% O₂. In this case, the flaky shape of the ground particles was visually confirmed by scanning electron microscopy.     

One-Step Synthesis of Luminescent Nanoparticles of Complex Oxide, Strontium Aluminate

An organic aqueous solution of metal acetylacetonate precursors was subjected to spray pyrolysis in order to fabricate SrAl₂O₄:Eu (SAO) nanoparticles. Non-agglomerated luminescent SAO nanoparticles, having a spherical shape with a size of 10–30 nm, were achieved in a single step, while only submicrometer-sized SAO particles were obtained from the conventional ultrasonic pyrolysis of the metal nitrates. Without any post-annealing process, the as-prepared SAO nanoparticles were observed to exhibit a strong photoluminescence, which is comparable with that of the submicrometer-sized SAO particles. A mechanism for the formation of the nanoparticles is also discussed.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Formation of Bromate Ion Through a Radical Pathway in a Continuous Flow Reactor

The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ～ 3.8 mgL), pH (6.5 ～ 8.5), and t-butanol concentration (0 ～ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k _HO,Br^? of 1.7 × 10⁹ (M^?1s^?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor.     

Plasma developable photoresist containing electronic excitation energy quenching system

A dry developable negative working resist composition comprised of poly(methyl isopropenyl ketone) (PMIPK) and 4-methyl-2,6-di(4′-azido-benzylidene) cyclohexanone-1 was examined. The main photochemical product formed in the resist pattern was found to be a secondary amine which crosslinks PMIPK. Post-annealing forms a hydrogen-bonded product which shows a powerful electronic excitation energy quenching effect. The quencher is more powerful than the aromatic compound arising from the azide by post-annealing only. The residual resist thickness of the negative pattern is about 80 percent of the initial thickness of the coating in spite of all the azide compound remaining in the resist coating. The obtained dry developed resist pattern has a high dry etch resistance. Etchings of Si and SiO₂ were performed by plasma and reactive ion etching, respectively.