Synthesis of anatase TiO_2 with exposed {001} and {101} facets and photocatalytic activity

Anatase titanium(Ⅳ) oxide(TiO_2) particles with exposed {001} and {101} facets were prepared by hydrothermal treatment of amorphous TiO_2 with H_2O_2-NH_3 solution. Crystal phase, shape, and size of TiO_2 particles are found to be greatly dependent on the ratio of H_2O_2-NH_3 solution. The prepared TiO_2 particles with specific exposed crystal faces show higher photocatalytic activity for acetaldehyde decomposition than commercial spherical TiO_2 particles. This result implies that recombination is prevented by spatial separation of redox sites in the particles because of selective migration of electrons and positive holes to specific exposed crystal faces and/or different reactivity of electrons and positive holes on the specific exposed crystal face.     

High-melt-strength polypropylene with electron beam irradiation in the presence of polyfunctional monomers

High-melt-strength polypropylene (PP) was achieved with irradiation by an electron beam generated from an accelerator in the presence of polyfunctional monomers (PFM). Among 16 PFMs, the relatively shorter molecular chain bifunctional monomers such as 1,4-butanediol diacrylate (BDDA) and 1,6-hexanediol diacrylate (HDDA) were the most effective for enhancing the melt strength of PP. The concentration and dose of the HDDA to obtain the high melt strength PP in irradiation under nitrogen gas atmosphere were 1.5 mmol/100 g PP and 1 kGy, respectively. DSC measurement and dynamic mechanical analysis showed that the thermal behavior of the high-melt-strength PP was different from that of the original PP. Crystallinity and crystallization temperature during cooling after heating were lower and higher in high melt strength PP than original PP, respectively. Elongational viscosity at 180°C of the high-melt-strength PP showed a remarkable increase at a certain elongational time with constant strain rate, demonstrating the typical property of high-melt-strength samples. This implies that a few higher molecular chains of PP, formed by intermolecular combination of its chain by HDDA in irradiation, give higher melt strength to induce entanglement of molecular chains. © 1996 John Wiley & Sons, Inc.     

Some experiments on the micro-indentation of digital audio tape

The durability of digital audio tape is a function of the elastic and plastic properties of the magnetic layer and substrate. In this work a micro-indentation method has been used to estimate these properties. The loading part of the compliance curve (load against indentor penetration) is analysed to obtain magnetic layer hardness. The unloading part is used to determine the reduced elastic modulus. Indentations at various depths have been recorded and an extrapolation technique used to predict layer properties. Rate dependence of the magnetic layer has been studied through constant loading rate tests. Results are presented isochronally, to indicate any viscous elastic–plastic non-linearities.     

Effect of Storage Conditions on 2–Acetyl-1–pyrroline Content in Aromatic Rice Variety, Khao Dawk Mali 105

ABSTRACT: The effect of package and temperature on 2–acetyl-1–pyrroline content in milled aromatic rice during storage was investigated. 2 -Acetyl-1 -pyrroline content was decreased faster at higher storage temperature. However, fat acidity of rice was increased during storage and inversely correlated with 2–acetyl-1–pyrroline content at an early stage of storage. The difference in 2–acetyl-1 -pyrroline recovery from the samples, which were extracted with ethanol at 40 °C and 75 °C, revealed that the starch bound and free forms of 2–acetyl-1–pyrroline may occur in aromatic rice. These results suggested that the biosynthesis of 2–acetyl-1 -pyrroline before starch structure formation in rice kernel could play a key role in the aroma quality of aromatic rice.     

Relationship between local structure and stability in hen egg white lysozyme mutant with alanine substituted for glycine

We prepared five mutant lysozymes in which glycines whose dihedralangles are located in the region of the left-handed helix, Gly49,Gly67, Gly71, Gly102 and Gly117, were mutated to an alanineresidue. From analyses of their thermal stabilities using differentialscanning calorimetry, most of them were more destabilized thanthe native lysozyme, except for the G102A mutant, which hasa stability similar to that of the native lysozyme at pH 2.7.As for the destabilized mutant lysozymes, their X-ray crystallographicanalyses showed that their global structures did not changebut that the local structures changed slightly. By examiningthe dihedral angles at the mutation sites based on X-ray crystallographicresults, it was found that the dihedral angles at these mutationsites tended to adopt favorable values in a Ramachandran plotand that the extent and direction of their shifts from the originalvalue had similar tendencies. Therefore, the change in dihedralangles may be the cause of the slight local structural changesaround the mutation site. On the other hand, regarding the mutationof G102A, the global structure was almost identical with thatof the native structure but the local structure was drasticallychanged. Therefore, it was suggested that the drastic localconformational change might be effective in releasing the unfavorableinteraction of the native state at the mutation site.     

Occurrence and sources of perfluorinated surfactants in rivers in Japan

We analyzed perfluorinated surfactants (PFSs) in 20 river samples and 5 wastewater secondary effluent samples in Japan to reveal their occurrence and sources. Nine PFS species were determined: perfluorooctanesulfonate (PFOS), perfluorooctane sulfonamide (FOSA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), perfluorododecanoate (PFDDA), and perfluorotridecanoate (PFTDA). PFSs were detected in all rivers, revealing nationwide contamination of rivers. In particular, 11 out of 20 river samples exceeded New Jersey guidance for PFOA in drinking water (40 ng/L). PFOS, PFHpA, PFOA, and PFNA were major species in Japan. Concentrations of PFOS, PFHpA, and PFNA in rivers were strongly correlated with population density, suggesting that the chemicals were derived from urban activities. PFOA showed a significant but weak correlation. We used crotamiton, a marker of sewage effluent, for further source analysis. Concentrations of PFOS, PFHpA, and PFNAwere strongly correlated with those of crotamiton, and plots of secondary effluents fell near the regression lines of rivers, indicating that the PFOS, PFHpA, and PFNA in rivers were derived from sewage effluent. On the other hand, PFOA was found at remarkably high levels (54-192 ng/L) in seven river samples containing low levels of crotamiton, suggesting that it was derived from nonsewage point sources, as well as sewage effluent. The total fluxes of sewage-derived PFOS, PFHpA, PFOA, and PFNA from Japan were estimated to be 3.6, 2.6, 5.6, and 2.6 t/year, respectively. This is the first report to identify PFOA in several rivers, derived from nonsewage point sources, by using a marker of sewage effluent.     

Contrasting effects of water-soluble and water-insoluble dietary fibers on bile acid conjugation and taurine metabolism in the rat

The effect of the type of dietary fiber on the bile acid and taurine metabolism was examined in rats. Diets containing 10% of various water-soluble fibers (citrus pectin, konjak mannan, guar gum) as compared to a fiber-free diet increased biliary excretion of total bile acids. In contrast, water-insoluble dietary fibers (cellulose, corn bran, chitin; 10% in the diets) as well as cholestyramine (5% in the diet) considerably, decreased bile acid excretion. Water-soluble dietary fibermediated increases in bile acid excretion were totally attributable to increases in glycine-conjugates. Thus, these fibers greatly increased by the bile acid glycine-to-taurine ratio (G/T). Excretio of glycine conjugates decreased more than that of taurine conjugates in rats fed various water-insoluble dietary fibers. As a results, G/T in rats fed water-insoluble fibers was significantly lowered as compared to G/T in animals fed a fiber-free diet. Cholestyramine did not affect the G/T ratio of bile acids. Fecal bile acid excretion and the activities of hepatic cholesterol 7α-hydroxylase (EC 1.14.13.17) in rats fed various water-soluble dietary fibers approximately doubled as compared to the respective values for rats fed a fiber-free diet. Whereas cholestyramine greatly increased these parameters, water-insoluble fibers did not significantly affect them. Various water-soluble fibers decreased hepatic concentration and urinary excretion of taurine as well as the activity of hepatic cysteine dioxygenase (EC 1.13.11.20). In contrast, water-insoluble fibers considerably increased hepatic taurine concentrations and enzyme activities. The parameters for taurine metabolism were unaffected by cholestyramine. It was suggested that the types of dietary fiber affected hepatic taurine synthesis and thus modified bile acid glycine/taurine ratios.     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.     

Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

Measurement of liquid water content in cathode gas diffusion electrode of polymer electrolyte fuel cell

Water management in cathode gas diffusion electrode (GDE) of polymer electrolyte fuel cell (PEFC) is essential for high performance operation, because liquid water condensed in porous gas diffusion layer (GDL) and catalyst layer (CL) blocks oxygen transport to active reaction sites. In this study, the average liquid water content inside the cathode GDE of a low-temperature PEFC is experimentally and quantitatively estimated by the weight measurement, and the relationship between the water accumulation rate in the cathode GDE and the cell voltage is investigated. The liquid water behavior at the cathode is also visualized using an optical diagnostic, and the effects of operating conditions and GDL structures on the water transport in the cathode GDE are discussed. It is found that the liquid water content in the cathode GDE increases remarkably after starting the fuel cell operation due to the water production at the CL. At a high current density, the cell voltage drops suddenly after starting the operation in spite of a low water content in the cathode GDE. When the GDL thickness is increased, much water accumulates near the cathode CL and the fuel cell shuts down immediately after the operation. In the final section of this paper, the structure of cathode GDL that has several grooves for water removal is proposed to prevent water flooding and improve fuel cell performance. This groove structure is effective to promote the removal of the liquid water accumulated near the active catalyst sites.