Calibration of EPR signal dose response of tooth enamel to photons: experiment and Monte Carlo simulation

The experimental energy dependence of the electron paramagnetic resonance (EPR) radiation-induced signal at irradiation by photons in the energy range of 13 keV-1.25 MeV was analysed in terms of the absorbed dose in human tooth enamel. The latter was calculated using a Monte Carlo simulation of the photon and electron transport. The dependence of the calculated absorbed dose on the sample thickness was analysed. No energy dependence of the EPR signal on the absorbed dose in enamel was verified in the range of 37 keV-1.25 MeV. At 13 and 20 keV the EPR signal dose response was reduced by 8% probably due to sample powdering. Dose-depth profiles in enamel samples irradiated by 1.25 MeV photons in polymethylmethacrylate and aluminium build-up materials were calculated. It was concluded that secondary electron equilibrium conditions are better fulfilled for irradiation in aluminium, which makes this material preferable for calibration.     

Fenarimol,a Pyrimidine-Type Fungicide,Inhibits Brassinosteroid Biosynthesis

The plant steroid hormone brassinosteroids (BRs) are important signal mediators that regulate broad aspects of plant growth and development. With the discovery of brassinoazole (Brz), the first specific inhibitor of BR biosynthesis, several triazole-type BR biosynthesis inhibitors have been developed. In this article, we report that fenarimol (FM), a pyrimidine-type fungicide, exhibits potent inhibitory activity against BR biosynthesis. FM induces dwarfism and the open cotyledon phenotype of Arabidopsis seedlings in the dark. The IC₅₀ value for FM to inhibit stem elongation of Arabidopsis seedlings grown in the dark was approximately 1.8 ± 0.2 μM. FM-induced dwarfism of Arabidopsis seedlings could be restored by brassinolide (BL) but not by gibberellin (GA). Assessment of the target site of FM in BR biosynthesis by feeding BR biosynthesis intermediates indicated that FM interferes with the side chain hydroxylation of BR biosynthesis from campestanol to teasterone. Determination of the binding affinity of FM to purified recombinant CYP90D1 indicated that FM induced a typical type II binding spectrum with a K_d value of approximately 0.79 μM. Quantitative real-time PCR analysis of the expression level of the BR responsive gene in Arabidopsis seedlings indicated that FM induces the BR deficiency in Arabidopsis.     

Antioxidant activity of Magnolol, honokiol, and related phenolic compounds

The antioxidant activity of 10 Japanese and Chinese crude drugs (Kampo drugs) was determined in vitro. Extract of Magnolia cortex, which had the highest antioxidant activity, contained phenolic compounds magnolol and honokiol. However, inhibitory effects of these compounds on lipid oxidation were weaker than that of α-tocopherol as measured by thiobarbituric acid assay. The structure-activity relationship of phenolic compounds showed that antioxidant activities were in the order 4-allyl-2,6-dimethoxyphenol ≥ p,p′-biphenol > eugenol > 2-allyl-6-methylphenol > honokiol > magnolol > caffeic acid > p-ethylphenol > guaiacol. As expected, these results showed that an electron donor and/or bulky groups at the ortho- or para-position of the phenol were required for inhibition of lipid oxidation. Electron spin resonance spin trapping experiments showed that phenol compounds with an allyl substituent on their aromatic rings directly scavenged superoxide (O ₂ ⁻ ), and that only eugenol trapped hydroxyl radicals. These findings suggest that phenolic compounds that contain allyl groups may be effective antioxidants because of the scavenging ability of O ₂ ⁻ or hydroxyl radical, whereas other phenols, without an allyl moiety such as α-tocopherol, may play a role in the termination of free radical chain reactions.     

C NMR study of C-enriched single-wall carbon nanotubes synthesized by catalytic decomposition of methane

¹³C NMR spectra and spin-lattice relaxation times were measured for single-wall carbon nanotubes with 99.9 and 50.0% ¹³C enrichments and natural abundance (1.1% ¹³C) prepared by catalytic decomposition of CH₄. The ¹³C isotropic shift is about 116 ppm from tetramethylsilane, being estimated from magic-angle-spinning (MAS) spectra. The value does not depend on the degree of the ¹³C enrichment. The ¹³C MAS NMR spectra show two additional small peaks at 171 and 152 ppm, which are ascribed to carbon species at defects or edges. The line widths of the main isotropic peak in MAS spectra are about 30 ppm, the origin of which is mostly chemical shift dispersion, reflecting a distribution of diameter and helicity. The line width in the ¹³C static spectra originates from chemical shift dispersion, chemical shift anisotropy and dipole–dipole interactions between ¹³C spins as well as between ¹³C and ¹H spins at defects or edges. ¹H NMR spectra confirm the presence of H-containing species. The ¹³C spin-lattice relaxation is dominated presumably by interaction with magnetic impurities.     

Pervaporation separation of 1,1,2‐trichloroethane–water mixture through crosslinked acrylate copolymer composite membranes

The separation of a chlorinated hydrocarbon from a dilute aqueous solution through a crosslinked acrylate copolymer–porous substrate composite membrane by pervaporation was investigated. Poly(n‐butyl acrylate‐co‐acrylic acid) and poly(n‐butyl acrylate‐co‐2‐hydroxyethyl acrylate) were synthesized and composite membranes were prepared, which were made from the crosslinked polymer and a porous substrate. Pervaporation measurement was carried out for a dilute aqueous solution of 1,1,2‐trichloroethane at 25°C and under a vacuum on the permeate side (below 10 mmHg). The separation factor, overall flux, 1,1,2‐trichloroethane concentration in the membrane, and the degree of swelling decreased with increase in the acrylic acid or 2‐hydroxyethyl acrylate content of the acrylate copolymer. The influence of the crosslinking agent content on the pervaporation performance was small, and the separation factor and the overall flux showed a convex curve. The structure of the crosslinking agent had no effect on the separation. The influence of the pore size of the substrate and the thickness of the polymer layer on the separation of 1,1,2‐trichloroethane was observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 983–994, 1999     

Separation of organic solvent from dilute aqueous solutions and from organic solvent mixtures through crosslinked acrylate copolymer membranes by pervaporation

The composite membranes of acrylate polymers and porous substrate were prepared. The separation of the organic solvent–water mixtures and the organic solvent–organic solvent mixtures through these membranes by pervaporation was investigated. The acrylate copolymer membrane showed the organic solvent permselectivity for the separation of the organic solvent–water mixture, especially for the chlorinated hydrocarbon–water mixture separation. The high organic solvent permselectivity should be governed by solubility selectivity. The influence of the ester residue of acrylate on the phenol–water mixture separation was observed. The copolymerization of the macromonomers containing the polystyrene, poly(methyl methacrylate), and polydimethylsiloxane chain had a small effect on the separation of the chlorinated hydrocarbon–water mixture. High flux and low selectivity of organic solvent were observed in the case of the organic solvent mixture separation through the n-butylacrylate membrane. The difference of permeability of organic solvent was observed for the acrylate copolymer which has various structures of ester residue. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 1483–1494, 1998     

Separation of aqueous phenol through polyurethane membranes by pervaporation

The separation of a phenol-water mixture using a polyurethane membrane by a pervaporation method was investigated. Polyurethane was selected as a membrane material because its affinity for phenol was considered to be high. Polyurethane was prepared by the polyaddition of 1,6-diisocyanatohexane and polytetramethyleneglycol. The polyurethane layer was sandwiched with a porous polypropylene membrane (Celgard® 2500). Pervaporation measurement was carried out under vacuum on the permeate side, and the permeate vapor was collected with a liquid nitrogen trap. The phenol concentration in the permeate solution increased from 0 to 65 wt % with increasing feed concentration of phenol from 0 to 7 wt %. The total flux also increased up to 930 g m^-2 h^-1 with increasing phenol partial flux. In the sorption measurement at 60°C, the concentration of phenol in the membrane was 68 wt %, which was higher than that of the permeate solution. Therefore, it was considered that the phenol selectivity was based on high solubility in the polyurethane membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:469–479, 1997     

Separation of aqueous phenol through polyurethane membranes by pervaporation. III. Effect of the methylene group length in poly(alkylene glycols)

Separation of phenol from dilute aqueous solution through polyurethane membranes by pervaporation was investigated. The effect of the methylene group length in poly(alkylene glycols) on permselectivity and solubility of phenol was studied. The poly(alkylene glycols) were obtained by polycondensation of 1,6‐hexanediol, 1,8‐octanediol, and 1,10‐decanediol with a sulfuric acid catalyst. Polyethyleneglycol and polytetramethyleneglycol were commercially available. Progress of the polymerization in the poly(alkylene glycols) was confirmed by FTIR, ¹H‐NMR analysis, and SEC measurement. The polyurethanes were obtained by polyaddition reaction of 1,6‐hexamethylenediisocyanate and the poly(alkylene glycol), and were confirmed by FTIR analysis and SEC measurement. The phenol concentration in a permeate liquid increased from 25.1 to 36.2 wt %, and the phenol partial flux also increased from 49.3 to 68.9 g · m⁻² · h⁻¹ with increasing the methylene group length in the poly(alkylene glycols), whereas the water partial flux slightly decreased. As a result of sorption measurements, the change in the degree of swelling was small, and the phenol concentration in the membrane increased from 42.1 to 70.8 wt %. The increase in the methylene group length of the poly(alkylene glycols) should contribute to an increase in the hydrophobicity of the polyurethane so that the solubility of phenol to the membrane should increase. The phenol concentration in the permeate liquid and the phenol partial flux increased with an increase in the methylene group length of the poly(alkylene glycols) due to the increase in the phenol solubility for the polyurethane membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 654–664, 2000     

Carbon-coated graphite for anode of lithium ion rechargeable batteries: Graphite substrates for carbon coating

Anode performance in lithium ion rechargeable batteries (LIBs) was studied on four kinds of graphite powders, including synthetic graphite. Carbon-coated synthetic graphite gave a smaller irreversible capacity of about 20 mAh g⁻¹ and a better cyclic performance in an electrolyte solution of EC/DMC than natural graphite, though its discharge capacity of about 300 mAh g⁻¹ is a little smaller than natural graphite. Even in a PC-containing solution as EC/PC = 3/1, carbon-coated synthetic graphite had almost the same anode performance as in the solution without PC. Carbon coating of above 5 mass% on graphite particles was found to be effective to improve the anode performance at a low temperature of −5 °C, high retention in discharge capacity of about 90% being obtained. On both natural and synthetic graphite powders, carbon coating by the amount of 3–10 mass% at a temperature of 700–1000 °C was found to be optimum for the improvement of anode performance in LIBs, to have a lower irreversible capacity and higher retention in discharge capacity at −5 °C than without carbon coating.