Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Photocatalytic partial oxidation of methylpyridine isomers on TiO2 particles under an anaerobic condition

Photocatalytic oxidation of methylpyridine isomers (2-methylpyridine, 3-methylpyridine, and 4-methylpyridine) was investigated in a mixed solution of acetonitrile and water or acetonitrile using various kinds of TiO₂ powders as photocatalysts. The main products from methylpyridine isomers were pyridinecarboxaldehyde isomers (2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde, and 4-pyridinecarboxaldehyde). Rutile large TiO₂ particles showed the highest level of activity for oxidation of 2-methylpyridine probably because band bending was necessary for the oxidation of 2-methylpyridine. On the other hand, a fine particle having an anatase or rutile phase showed a higher level of activity than large TiO₂ particles for oxidation of 3-methylpyridine. A rutile fine particle showed the highest level of activity for the reaction. It was found that pure rutile or pure anatase particles were inactive for oxidation of 4-mathylpyridine. If the particles are not extremely small, pure rutile and pure anatase powders show fairly high levels of activity, and those containing both anatase and rutile phases show the highest level of activity. The activity of pure rutile particles was also enhanced by physically mixing them with a small amount of small anatase particles, which were inactive for this reaction. These results can be explained by the synergism between rutile and anatase particles. All of these reactions effectively proceeded even under anaerobic conditions. Photocatalytic reduction of methylpyridine isomers concomitantly proceeded on TiO₂ particles under the conditions used. These results suggest that the activities of TiO₂ photocatalysts for oxidation of methylpyridine isomers are dominated by the oxidation potential of alkylpiridine and band bending of TiO₂ particles.     

Effects of isocyanuric acid on the monochlorodimedone chlorinating rates with free chlorine and ammonia chloramine in water

Changes in monochlorodimedone (MCD) chlorinating rates with free chlorine (mixture of HOCl and OCl-) and ammonia monochloramine (NH2Cl) in water at pH 7 by the addition of isocyanuric acid (H3Cy) were determined at room temperature. Decreases in MCD absorbance at 290nm in equimolar (0.04mM) reactions of MCD and free available chlorine solutions containing H3Cy (0.01-1.60 mM) were recorded in a stopped-flow spectrophotometer. The rates indicate second-order reactions. Since the rate with free chlorine was high (> 7.6 x 10(6) M(-1) s(-1)), the amounts of free chlorine in the solutions could be distinguished from that of chlorinated cyanurates. The chlorinating rates with chlorinated cyanurates decreased with an increase in H3Cy concentrations. Plotting the rates against the molar ratio of chlorine to H3Cy showed a linear correlation and the rates with chlorinated cyanurates (H2ClCy) was estimated at 0.5 x 10(5) M(-1) s(-1). In contrast, the rates with the NH2Cl solution containing H3Cy increased with an increase in H3Cy concentrations, increasing from 1.2 x 10 to 2.7 x 10 M(-1) s(-1) by the addition of 1.55 mM H3Cy. The DPD color development rates (OD512/t1/2/M) with free available chlorine (0.015mM) declined from 1.3 x 10(5) to 0.9 x 10(5)M(-1) by the addition of 0.61 mM H3Cy.     

Experimental visualization of lithium diffusion in LixFePO4

Chemical energy storage using batteries will become increasingly important for future environmentally friendly ('green') societies. The lithium-ion battery is the most advanced energy storage system, but its application has been limited to portable electronics devices owing to cost and safety issues. State-of-the-art LiFePO4 technology as a new cathode material with surprisingly high charge-discharge rate capability has opened the door for large-scale application of lithium-ion batteries such as in plug-in hybrid vehicles. The scientific community has raised the important question of why a facile redox reaction is possible in the insulating material. Geometric information on lithium diffusion is essential to understand the facile electrode reaction of LixFePO4 (0相似文献   

Two-dimensional “transXend” detector for third-generation energy-resolved computed tomography

The “transXend” detector measures X-rays as electric currents and provides the energy distribution of the measured X-rays after analysis. Capabilities of material distinction, effective atomic number measurement, and low-dose exposure computed tomography (CT) with high K-edge contrast agent from the use of the transXend detector in energy-resolved CT have been demonstrated via the first-generation CT measurements. For application of the principle of the transXend detector to the third-generation CT for human subjects in future work, a method for fabrication of a two-dimensional transXend detector is proposed and demonstrated using a commercial two-dimensional detector and two kinds of strip absorbers. The energy-resolved CT is performed by placing a proposed absorber system in front of a two-dimensional detector, which is used for conventional current measurement CT.     

Vacuum ultraviolet photoionization mass spectra and cross-sections for volatile organic compounds at 10.5 eV

Vacuum ultraviolet single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) has been applied to the detection of volatile organic compounds (VOCs), including aromatic, chlorinated, and oxygenated compounds. Photoionization mass spectra of 23 VOCs were measured using SPI-TOFMS at 10.5 eV (118 nm). The limits of detection of VOCs using SPI-TOFMS at 10.5 eV were estimated to be a few ppbv. The mass spectra of 20 VOCs exhibit only the parent ion and its isotopes' signals. The ionization processes of the VOCs were discussed on the basis of the reaction enthalpies predicted by the quantum chemical calculations. Absolute photoionization cross-sections for 23 VOCs, including 12 newly measured VOCs, at 10.5 eV were determined in comparison to the reported absolute photoionization cross-section of NO.     

Investigation of pathways of advanced glycation end-products accumulation in macrophages

Advanced glycation end-products (AGE) play a role in the pathogenesis of several diseases, including diabetic complications and atherosclerosis. In atherosclerotic lesions of human aortas, AGE are localized in the extracellular matrix and intracellularly in foam cells. Two interpretations are possible for AGE accumulation inside macrophages, one is endocytic uptake of extracellular AGE-proteins by scavenger receptors; the other is intracellular AGE formation inside the macrophages. In the present study, we determined the pathways involved in AGE accumulation inside macrophages. RAW 264.7 cells, a murine macrophage cell line, incubated with BSA and 1600 mM glucose for 40 weeks, recognized heavily modified AGE- BSA. In contrast, the cells showed no ligand activity for mildly modified AGE-BSA, prepared by incubating BSA with 50 mM glucose for 24 weeks. Nepsilon-(carboxymethyl)lysine (CML)-modified proteins of about 65 kDa were detected in human monocyte-derived macrophages incubated for 7 days with 30 mM glucose and phorbol myristate acetate. Furthermore, CML was generated when glycated protein was incubated with hypochloric acid. Taken together, our results indicate that AGE detected inside foam cells in atherosclerotic lesions are generated intracellularly rather than representing endocytic uptake of extracellular AGE-proteins by scavenger receptors.     

Verb generation in Japanese--A multicenter PET activation study

Cerebral blood flow (CBF) during silent verb generation was measured at four Japanese PET centers. To minimize the variance of the measurement, speakers of a single language (Japanese) served as subjects and experimental conditions at the four PET centers were controlled as much as possible. Two types of activation patterns were observed: activations in the left dorsolateral prefrontal cortices and the medial frontal cortex (at the two centers with a 2D PET scanner) and additional activation in the left posterior temporal cortex (at the two centers with a 3D scanner). This suggests either a difference in the sensitivity of the two types of PET scanners (viz., a 3D scanner is generally more sensitive than a 2D scanner) and/or subject bias due to the small number of subjects at the individual centers. The pooled activation pattern was fundamentally similar to activation patterns obtained in the previous studies for verb generation in English and other European languages, suggesting that regions for verb generation are independent of particular languages. Regions relevant to verb generation are discussed.     

Synthesis and properties of poly(phenylacetylene)s having dialkylamino groups

Summary Poly(phenylacetylene)s bearing dialkylamino groups were prepared by the polymerization of p-(N,N-dialkylamino)phenylacetylenes with [Rh(nbd)Cl]₂, and their electrochemical behavior was examined. Rh-catalyzed polymerization of p-(N,N-diethylamino)phenylacetylene (DEAPA) and p-(N,N-di-n-butylamino)phenylacetylene (DBAPA) in toluene in the presence of triethylamine gave good yields of the polymers (86 and 90%, respectively). Poly(DEAPA) was soluble in chloroform and dichloromethane, and poly(DBAPA) dissolved in various solvents such as toluene, THF, dichloromethane and chloroform. Poly(DEAPA) and poly(DBAPA) showed onset temperatures at 248 and 190°C, respectively, and absorptions around 300–400 nm. Electrochemical doping of the polymer films resulted in the shift of the absorptions to a region around 680 nm, which accompanied a color change of the polymer films from green ocher to deep blue. Received: 26 October 1998/Revised version: 6 November 1998/Accepted: 12 November 1998     

Synthesis and polymerization of a self-condensable macromonomer

Summary A novel self-condensable macromonomer that has a polymerizable group at one terminal and an initiator at the other was synthesized by the combination of the conventional macromonomer technique and the SmI₂-induced transformation. Namely, living poly(tetrahydrofuran) [poly(THF)] carrying α-methacryloyl group was prepared by using methacryloyl chloride and silver trifluoromethanesulfonate. The living chain end was capped with sodium 2-bromoisobutyrate, and the sequential reduction of the terminal C-Br bond with SmI₂ gave a terminating samarium enolate. The resulting samarium enolate copolymerized the α-methacryloyl group with methyl methacrylate, giving a hyperbranched block copolymer whose dendritic part consists of two kinds of polymer segments. Received: 4 January 1999/Accepted: 2 February 1999