Preparation of multiple oxide BaTiO3 fibres by the sol-gel method

Multiple oxide BaTiO₃ gel fibres were prepared by the sol-gel method from Ba(OC₂H₅)₂-Ti(O-isoC₃H₇)₄-H₂O-C₂H₅OH-CH₃COOH and Ba(CH₃COO)₂-Ti(O-isoC₃H₇)₄-H₂O-CH₃COOH solutions. Relatively long gel fibres of 10cm length were obtained from both solutions in the limited composition region. The latter solution in particular showed a spinnability even when it contained no water. Therefore, the occurrence of spinnability of the solution was considered to be due to the formation of linear polymers composed of bridging acetate groups such as TiO-C(CH₃)-O-Ti rather than metalloxane bonding as Ti-O-Ti. Addition of water to the solutions seems to break the bridging acetate bonds and replace some of them by bridging oxygen bonds. The as-drawn gel fibres which were X-ray amorphous crystallized into BaTiO₃ ceramic fibres of 5mm average length upon heating above 600 ° C. However, the gel fibres drawn from the sols without water became powdery on heating because of the lack of Ti-O-Ti metalloxane bonds. The crystallization behaviour of the BaTiO₃ gel fibres is discussed based on the infrared spectroscopy, X-ray diffraction analysis and thermogravimetric-differential thermal analysis.     

Structural changes of glass-ceramics of the Cu2O-Al2O3-SiO2 system on heating in air

The behaviour of copper ions in low thermal expansion glass-ceramics prepared from Cu₂O · Al₂O₃ ·_nSiO₂ glasses, or in-spodumene type Cu₂O · Ae₂O₃ ·nSiO₂ crystals included in the glass-ceramics on heating in air was investigated. On hewing at 300 to 500° C, the copper ions behaved as in the corresponding glasses. Cuprous ions in the glass-ceramics or-spondumene type crystals were oxidized into the cupric state, and at the same time an equal amount of cuprous ions to those oxidized were expelled out of the specimen for the requirement of electrical charge neutrality and then reacted with oxygen to form CuO on the surface. The oxidation of cuprous ions and the decrease of the copper content of the-spondumene type crystals brought about a considerable decrease in the lattice spooings.     

The Attenuated Secretion of Hyaluronan by UVA-Exposed Human Fibroblasts Is Associated with Up- and Downregulation of HYBID and HAS2 Expression via Activated and Inactivated Signaling of the p38/ATF2 and JAK2/STAT3 Cascades

Little is known about the effects on hyaluronan (HA) metabolism of UVA radiation. This study demonstrates that the secretion of HA by human dermal fibroblasts (HDFs) is downregulated by UVA, accompanied by the down- and upregulation of mRNA and protein levels of the HA-synthesizing enzyme (HAS2) and the HA-degrading protein, HYaluronan Binding protein Involved in HA Depolymerization(HYBID), respectively. Signaling analysis revealed that the exposure distinctly elicits activation of the p38/MSK1/CREB/c-Fos/AP-1 axis, the JNK/c-Jun axis, and the p38/ATF-2 axis, but downregulates the phosphorylation of NF-kB and JAK/STAT3. A signal inhibition study demonstrated that the inhibition of p38 significantly abrogates the UVA-accentuated mRNA level of HYBID. Furthermore, the inhibition of STAT3 significantly downregulates the level of HAS2 mRNA in non-UVA exposed HDFs. Analysis using siRNAs demonstrated that transfection of ATF-2 siRNA but not c-Fos siRNA abrogates the increased protein level of HYBID in UVA-exposed HDFs. An inhibitor of protein tyrosine phosphatase but not of protein serine/threonine phosphatase restored the diminished phosphorylation level of STAT3 at Tyr 705, accompanied by a significant abolishing effect on the decreased mRNA expression level of HAS2. Silencing with a protein tyrosine phosphatase PTP-Meg2 siRNA revealed that it abrogates the decreased phosphorylation of STAT3 at Tyr 705 in UVA-exposed HDFs. These findings suggest that the UVA-induced decrease in HA secretion by HDFs is attributable to the down- and upregulation of HAS2 and HYBID expression, respectively, changes that are mainly ascribed to the inactivated signaling of the STAT3 axis due to the activated tyrosine protein phosphatase PTP-Meg2 and the activated signaling of the p38/ATF2 axis, respectively.     

An absolute requirement of fructose 1,6-bisphosphate for the Lactobacillus caseiL-lactate dehydrogenase activity induced by a single amino acid substitution

Lactobacillus casei allosteric L-lactate dehydrogenase (L-LDH)absolutely requires fructose 1,6-bisphosphate [Fru(1,6)P2] forits catalytic activity under neutral conditions, but exhibitsmarked catalytic activity in the absence of Fru(1,6)P₂ underacidic conditions through the homotropic activation effect ofsubstrate pyruvate. In this enzyme, a single amino acid replacement,i.e. that of His205 conserved in the Fru(1,6)P₂-binding siteof certain allosteric L-LDHs of lactic acid bacteria with Thr,did not induce a marked loss of the activation effect of Fru(1,6)P₂or divalent metal ions, which are potent activators that improvethe activation function of Fru(1,6)P₂ under neutral conditions.However, this replacement induced a great loss of the Fru(1,6)P₂-independentactivation effect of pyruvate or pyruvate analogs under acidicconditions, consequently indicating an absolute Fru(1,6)P₂ requirementfor the enzyme activity. The replacement also induced a significantreduction in the pH-dependent sensitivity of the enzyme to Fru(1,6)P₂,through a slight decrease and increase of the Fru(1,6)P₂ sensitivityunder acidic and neutral conditions, respectively, indicatingthat His205 is also largely involved in the pH-dependent sensitivityof L.casei L-LDH to Fru(1,6)P₂. The role of His205 in the allostericregulation of the enzyme is discussed on the basis of the knowncrystal structures of L-LDHs.     

Recognition of substrates by membrane potential of immobilized glucose oxidase membranes

The shifts in membrane potential, caused by the injection of glucose into a permeation cell, were measured using immobilized (entrapped) glucose oxidase membranes. No, pH change in the permeation cell was observed upon injection of glucose, but the shift in membrane potential was definitely detected. The shift in membrane potential was observed under nitrogen bubbling (in the absence of oxygen) using initially used enzyme membranes. It was, therefore, suggested that the shifts in membrane potential were not caused by an enzyme-substrate reaction, but by binding of the substrate to the enzyme, which indues a conformational change in the enzyme and leads to a change in charge density in the enzyme membrane. This mechanism is also supported by the fact that the shifts in membrane potential were observed upon injection of not only D-glucose but also L-glucose as reported in our previous study [J. Chem. Soc. Faraday Trans., 87 , 695 (1991)]. © 1994 John Wiley & Sons, Inc.     

Retardation of volatile aldehyde formation in the exhaust of frying oil by heating under low oxygen atmospheres

Volatile aldehydes were generated in the exhaust of high-oleic safflower oil during heating at 180°C by spraying water into atmospheres with four levels of oxygen concentrations (2, 4, 10, and 20%). These aldehydes were quantitatively analyzed by HPLC after the conversion to 2,4-dinitrophenyl hydrazones. Ten alkanals (C₂ through C₁₀), eight 2-alkenals (C₃ through C₁₀) and three 2,4-alkadienals (C₇, C₉, and C₁₀) were found. These aldehyde levels were found to be positively correlated with both the heating time and the atmospheric oxygen concentration. The total amounts of aldehydes were the lowest in the oil heated in an atmosphere with 2% O₂, and corresponded to 1/10 of those in the atmosphere with 20% O₂. Acrolein was not found in oils heated in the atmosphere with 2% oxygen. These results suggest that frying in atmospheres with low oxygen levels can effectively decrease the generation of volatile aldehydes in the exhaust.     

Liquefaction of wood in the presence of phenol using phosphoric acid as a catalyst and the flow properties of the liquefied wood

The liquefaction of wood in the presence of phenol using phosphoric acid as a catalyst and the flow properties of the obtained liquefied wood were investigated. It was found that phosphoric acid is a satisfactory catalyst for liquefying wood. The amount of phenol that reacts with the liquefied wood components (i.e., combined phenol) increases with an increase in liquefaction temperature, liquefaction time, catalyst content, or liquid ratio. By removing the free phenol, the resulting liquefied woods become novolaclike resins. The measurements of the flow properties of these liquefied woods reveal that the melts of liquefied woods behave as pseudoplastics and their flows obey the Ostwald de Waele power law equation. The amount of combined phenol within the liquefied wood and the presence of filler in the liquefied wood have great influence on their flow properties. The flowing temperature, activation energy, and zero shear viscosity of the liquefied woods show tendencies to increase with an increase in combined phenol. © 1994 John Wiley & Sons, Inc.     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosillcate Glasses in Copper-Containing Molten Salt: I, Monovalent Copper Salt, CuCl

Cu⁺⇌ R⁺ (R = Li, Na, and K) ion exchange experiments were conducted for 20R₂O·10Al₂O₃·70SiO₂ glasses in molten CuCl at 550°C in air and nitrogen atmospheres. The depth profiles of the copper incorporated into glasses were determined with an electron microprobe X-ray analyzer. The total amount of diffusing copper, M _t, strongly depended on the type of alkali ion in the glass and the ion-exchange atmosphere; i.e., M _t increased with increasing cationic size in the order Li < Na < K and M _t was greater in air than in nitrogen. The Cu ⇌ R⁺ ion exchange kinetics are discussed in detail.     

Relative reactivity of hydrogen donor solvent in coal liquefaction

Hydrogen transfer from donor solvent to coal must involve reactions such as hydrogen donation to free radicals and hydrogenation of aromatic structures. The relative reactivities of five typical hydrogen donor solvents, more reactive than tetralin, were determined using a competing elimination reaction in the liquefaction of a bituminous coal at 400 °C and a brown coal at 350 °C. 9,10-Dihydroanthracene, 9,10-dihydrophenanthrene and 1,2,3,4-tetrahydroquinoline exhibited outstanding hydrogen donating ability. Further, the relative reactivities of five mild hydrogen donor solvents such as acenaphthene and indan were determined by a similar elimination reaction using a bituminous coal at 450 °C.     

Nitridation of the Sol–Gel-Derived Titanium Oxide Films by Heating in Ammonia Gas

Dip-coated sol–gel-derived TiO₂ films on an alumina substrate were converted to nonstoichiometric titanium nitride (TiN _x ( x ≦ 1)) films by heating at approxmately 1000°C in NH₃ gas. TiO₂ films made from TiO₂ sols prepared from Ti(O– i -C₃H₇)₄ and stabilized by diethanolamine were more easily nitrided than those from sols containing HCl as a deflocculant reagent. This appears to be a result of the more porous structure of the former films.