Oxidation of methane to formaldehyde over Fe/SiO2 and Sn---W mixed oxides

In an attempt to develop new catalysts for the formation of formaldehyde from methane, the promotion effect of Fe on SiO₂ and that of Sn on WO₃ have been studied. The formation of formaldehyde on silica can be appreciably enhanced by the impregnation of Fe, as far as iron loadings are kept below 0.1 atom.% (Fe/Si × 100). In the case of Sn---W---Ox catalysts, both the addition of Sn to WO₃, and that of W on SnO₂ were effective to the selective formaldehyde formation. Absorption spectra (UV-Vis) and ESR measurements revealed that tetrahedrally coordinated Fe³⁺ in the silica network plays an important role in the formation of formaldehyde. A thin surface layer consisting of W and Sn oxides can account for the selective formaldehyde formation on the Sn---W---Ox catalysts.     

Thermodynamic Regularities in Perovskite and K2NiF4 Compounds

It has been found that the enthalpy of formation of perovskite compounds, Δ_fH° (ABO₃, B = transition metais), from binary oxides can be well characterized in terms the tolerance factor, t≡(r_A+ r_o)√2 (r_B+ r_o), where r_A and r_B are the radii of A-site ions with 12-coordination and B-site ions with 6-coordination, respectively, and Δ_fH°=−168 + 270(1 − t) kJ·mol⁻¹ for A^IB^VO₃, Δ_fH°=−125 + 1000(1 − t) kJ·mol⁻¹ for A^IIB^IVO₃, and Δ_fH°=− 90 + 720(1 − t) kJ·mol⁻¹ for A^IIIB^IIIO₃. Although the thermodynamic data of K₂NiF₄ compounds are not extensive, a similar regularity can be found when use is made of the radii of A-site ions with 9-coordination for the K₂NiF₄ compounds. These correlations will be quite useful in predicting.     

Protective effect of phytic acid hydrolysis products on iron-induced lipid peroxidation of liposomal membranes

Beneficial effects of dietary phytic acid (myo-inositol hexaphosphate; IP₆) have often been explained by its strong iron ion-chelating ability, which possibly suppresses iron ion-induced oxidative damage in the gastrointestinal tract. Because phytic acid is hydrolyzed during digestion, this work aimed to know whether its hydrolysis products (IP_2′ IP_3′, IP_4′ and IP₅) could still prevent iron ion-induced lipid peroxidation. Studies using liposomal membranes demonstrated that hydrolysis products containing three or more phosphate groups are able to inhibit iron ion-induced lipid peroxidation although their effectiveness decreased with dephosphorylation. Similarly, they also prevented iron ion-induced decomposition of phosphatidylcholine hydroperoxide. These results demonstrate that intermediate products of phytic acid hydrolysis still possess iron ion-chelating ability, and thus they can probably prevent iron ion-induced lipid peroxidation in biological systems.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

Factors associated with serum magnesium and vascular stiffness in maintenance hemodialysis patients

Introduction : We evaluated the associated factors of serum magnesium in patients on maintenance hemodialysis (MHD). Furthermore, we evaluated the relationship between low serum magnesium and arteriosclerosis in these patients. Methods : In 129 patients on MHD, we evaluated the blood levels of magnesium, brachial‐ankle pulse wave velocity (ba‐PWV), ankle‐brachial index (ABI), and intima‐media thickness of the common carotid artery (IMT). Findings : In MHD patients, the serum level of magnesium was significantly correlated with age, calcium, TNF‐α, albumin, and ba‐PWV but not with ABI or IMT. In the multiple regression analysis, albumin (P = 0.0001, β = 0.31) and calcium (P = 0.029, β = 0.18) were selected as significant predictors of the magnesium level in MHD patients. Furthermore, the serum level of magnesium, as well as systolic blood pressure (P = 0.0001, β = 0.32) and age (P = 0.005, β = 0.25), were selected as significant (P = 0.012, β = ?0.22) predictors of ba‐PWV in MHD patients. Discussion : In MHD patients, the serum magnesium level was associated with the serum levels of calcium and albumin. Furthermore, a low serum magnesium level in MHD patients was associated with the index of vascular stiffness.     

Colorimetric microdetermination of sulphites in foods by use of the modified rankine apparatus. IV.

Summary Detection and determination of traces of sulphites in foods was attempted by use of the modified Rankine apparatus and pararosaniline colorimetry. Replacement of alkaline titration reported previously by pararosaniline colorimetry lowered the absolute detection limit from 30 g (titration method) to 2 g. In view of clean analysis, in the color developing system, 0.1 N-sodium hydroxide was used in place of mercuric chloride solution commonly used as an absorbant of sulphites. In order to prevent oxidative decomposition of sulphites during operation, nitrogen gas was used as carrier instead of air. Dimedone and sodium azide were used for the elimination of aldehydes and nitrites, respecitvely, in the sample, which will disturb the color development of sulphites with pararosaniline-formaldehyde reagents. With this improved method, it was possible to determine the residual sulphites in frozen peeled shrimps, sugared beans and other foods with low sulphite contents accurately.

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Colorimetrische Mikrobestimmung von Sulfiten in Lebensmitteln bei Anwendung der modifizierten IV. Rankine Apparatur

Zusammenfassung Geringe Sulfitmengen in Lebensmitteln (geschälte Garnelen, gezuckerte Bohnen) können colorimetrisch bestimmt werden. Die neuentwickelte Methode beruht auf einer Kombination von colorimetrischer Bestimmung mittels p-Rosanilin und der Bestimmungsmethode nach Rankine. Auf diese Weise lassen sich Gehalte von 2 g noch genau bestimmen. Bei der Farbentwicklung wurde das giftige Quecksilbertetrachlorid durch 0.1 n-NaOH ersetzt, anstelle von Luft Stickstoff als Trägergas verwendet und somit eine Oxydation des Sulfits während der Bestimmung vermieden. Da Nitrit und Aldehyde die Farbentwicklung stören, wurde ihr Einfluß durch Dimedon und Natriumazid ausgeschaltet.

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Studies on the Analyses of Sulphites in Foods (IV)     

High Temperature Schottky Barrier on n-Type SrTiO3 and Its Sensitivity to Ambient Gases

Metal or oxide electrodes (Pt, Au, Ag, (La, Sr)CoO₃) were deposited on single crystals of 0.02 mol% Nb doped SrTiO₃ by pulsed laser deposition. Current-voltage and capacitance-voltage responses were measured using three-terminal electrode configuration. Under high oxygen partial pressures, clear rectification behaviors were observed. Diffusion model well explained the current vs. voltage relationship with ideality factors close to unity. The barrier height varied reversibly with oxygen partial pressure, and was almost independent of the electrode materials, which suggested that the Fermi level at the interface was pinned by the surface states. The origin of the surface states was discussed in terms of oxygen adsorption or oxidative formation of metal vacancies around the surface. Chemical interaction between the surface and oxygen and resulting cation rearrangement was concluded to play an important role from the long stabilization time on oxygen partial pressure change. The water vapor pressure dependence of the barrier height was also explained by competitive adsorption of oxygen and water.