Silica-supported cobalt catalysts for the selective reduction of nitrogen monoxide with propene

Catalytic behavior of silica-supported transition metals for NO reduction with propene in the presence of oxygen was investigated. While both silica and cobalt oxides did not show any activity for the selective NO reduction, impregnated CoO/SiO₂ prepared from cobalt acetate showed good activity although the preparation conditions had significant effect on the activity. It was suggested that highly dispersed surface Co²⁺ ions on silica are responsible for the catalytic activity.     

A new concept for determining triglyceride composition of fats and oils by liquid chromatography

The matrix concept was used to characterize the chromatographic rules in the elution of molecular species of triglyceride. To prove the hypothesis experimentally, cacao butter, palm oil, linseed oil, olive oil, rapeseed oil and triglyceride of “Ogonori” (Gracilaria verrucosa) were examined. A matrix model was suggested to help determine the individual molecular species of naturally occurring triglycerides.     

Synthesis and electrode performance of layered nickel dioxide containing alkaline ions

Several polymorphs of layered nickel dioxide were prepared by using the chemical insertion of alkaline ions into Li_0.10NiO₂. We used aqueous AOH (A = Li, Na, K) solutions as reducing agents. Sodium and potassium insertion resulted in hydrated layered compounds that can be classified as γ-NiOOH with high crystallinity, while lithium insertion occurred without hydration. We discuss the coordination environment around the A⁺ ions for these inserted compounds. The thermal behavior, analyzed using high temperature (HT) X-ray diffraction (XRD) and thermogravimetric (TG) measurements, indicated that heating the hydrate at 150 °C yielded its dehydrate. The electrode performance of the nickelate was studied in lithium cells. We discuss the effect of interlayer water on cell rechargeability and the similarity between these nickelate and hydrated manganese dioxide (birnessite).     

Effect of EFA deficiency on lipid transport from liver

Studies are reported of the effect of an essential fatty acid (EFA) deficiency on synthesis of triglycerides (TG) and phospholipids (PL) and secretion of these compounds by livers of male Sprague-Dawley rats. Animals were fed a semipurified diet containing corn oil or hydrogenated coconut oil (HCO) as the sole source of fat or no fat from weaning to 20 weeks of age. Liver function of the animals in each group was compared by an isolated liver perfusion technique with perfusates containing erythrocytes and linoleate, and in vivo experiments via tail vein injection of palmitate-³H. Perfusion experiments showed that an EFA deficiency reduced the ability of the liver to secrete TG and PL. Accumulation of TG in the liver and its diminished secretion into the blood of EFA deficient animals were demonstrated by in vivo experiments with palmitate-³H. The rate of conversion of linoleate to arachidonate and synthesis of PL was greater in livers of EFA deficient rats than in the control, corn oil fed animals. The results suggest a relationship of EFA metabolism to lipid transport. One of five papers to be published from the Symposium “Lipid Transport” presented at the AOCS Meeting, New Orleans, April 1970.     

Enzymatic modification of canola/palm oil mixtures: Effects on the fluidity of the mixture

The bioreactor system to interesterify edible oils and fats at an ultra-micro aqueous phase of 100 ppm and less was investigated. The adsorption of lecithin, together with lipase onto a carrier, was effective for conducting the interesterifying reaction efficiently for oils and fats in micro aqueous phase. To improve the handling properties of palm oil at rather low temperature, palm oil was blended with canola or soybean oil, and then these blended oils were modified by enzymatic selective interesterification in a solvent-free, ultra-micro aqueous bioreactor system with an immobilized lipase that had 1,3-positional specificity. The effects of enzymatic interesterification were confirmed by triglyceride determination, by solid fat content profiles and by cloud point profiles, which were also compared to products of chemical interesterification. The improvement in the fluidity of blended oils with canola oil by the enzymatic reaction was bigger than with soybean oil, and chemical interesterification had no effects on the fluidity of blended oils.     

Synthesis of γ-Ga2O3–Al2O3 Solid Solutions by the Glycothermal Method

The reaction of mixtures of aluminum isopropoxide and gallium acetylacetonate in 1,4-butanediol or 1,5-pentanediol at high temperatures (glycothermal reaction) directly gave the γ-Ga₂O₃–Al₂O₃ solid solutions, which had high catalytic activities for selective reduction of NO using methane as the reducing agent. However, the reaction with a higher Al/(Ga+Al) charged ratio yielded the glycol derivative of boehmite as a by-product and the catalytic activity of the solid solution decreased. Therefore, synthesis of the solid solution using various glycols was examined and it was found that solid solutions with high Al contents without contamination of the glycol derivative of boehmite were obtained by using 1,6-hexanediol as a reaction medium. The solid solution exhibited a higher NO conversion than that synthesized in other glycols.     

Oxide ion conduction in the sintered oxides of MoO3-doped Bi2O3

In order to examine the conduction behaviour in the sintered oxides of MoO₃-doped Bi₂O₃, the electrical conductivity in air and the EMF of oxygen gas concentration cell were measured with respect to the phase relation determined by X-ray diffraction.The tetragonal single phase oxide containing 22 mol% MoO₃ was found to be a high oxide ion conductor, the conductivity of which was comparable to those of stabilized zirconias. The partial electronic conduction in this phase was negligibly small at relatively high oxygen pressure. The oxide ion conduction was considered to be attributable to an appreciable amount of oxygen vacancies present in the crystal. In the monoclinic compound 3Bi₂O₃·2MoO₃, the oxide ion conduction was also observed. Although the conductivity of this phase was somewhat lower than that of the tetragonal phase, the activation energy for conduction (53·5 kJ mol^–1) was much lower than the values for usual oxide ion conductors.     

Shear-rate dependence of first normal stress difference of poly(isoprene-b-styrene) in solution near the order-disorder transition temperature

Viscoelastic properties of poly(isoprene-b-styrene) in dioctylphthalate under steady shear flow were measured near the order—disorder transition temperature. In ordered states, first normal stress difference N₁ is proportional to shear rate at low region, but becomes proportional to at the high region, similar to the N₁ behaviour of polymer blends undergoing shear-induced homogenization. Because the existence of microdomains was confirmed at the high region by the flow birefringence method, it is concluded that the above N₁ behaviour is not caused by shear-induced homogenization, but is probably caused by the shear-induced alignment of the microdomain structure.     

Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

Selective detection of acetylene gas extracted from isolation oil by an electrochemical sensor using a gold electrode

The selective detection of acetylene in gases extracted from isolation oils has been studied to develop an electrochemical sensor for the diagnostic monitoring of the condition of in-service electrical instruments. Effects of coexisting gases (CH₄, C₂H₆, C₂H₄, H₂ and CO) on the oxidation current of C₂H₂ were tested using gas-permeable gold-coated and platinum-black electrodes as the sensor. The gold-coated electrode showed good behaviour for the selective current detection of acetylene under potentiostatic conditions (−0.1 V/Pt-black reference electrode) in 10m H₂SO₄ electrolyte solution.