Production of dihomo-γ-linolenic acid byMortierella alpina 1S-4

The mycelial dihomo-γ-linolenic acid content of an arachidonic acid-producing fungus,Mortierella alpina 1S-4, was found to increase, with an accompanying marked decrease in its arachidonic acid content, on cultivation with sesame oil. The resultant mycelia were found to be a rich source of dihomo-γ-linolenic acid. This unique phenomenon was suggested to be due to specific repression of the conversion of dihomo-γ-linolenic acid to arachidonic acid by the oil. After fractionation of the oil with acetone into oil and non-oil fractions, it was found that the effective factor(s) was present in the non-oil fraction. In a study on optimization of the culture conditions for the production of dihomo-γ-linolenic acid byM. alpina 1S-4, a medium containing glucose, yeast extract and the non-oil fraction was found to be suitable for the production. Under the optimal conditions in a 50-1 fermentor, the fungus produced 107 mg of dihomo-γ-linolenic acid/g dry mycelia (2.17 g/l of culture broth). This value accounted for 23.1% of the total fatty acids in the lipids extracted from the mycelia. The mycelia were also rich in arachidonic acid (53.5 mg/g dry mycelia, 11.2%). Other major fatty acids in the lipids were palmitic acid (24.1%), stearic acid (7.0), oleic acid (20.1), linoleic acid (6.6) and γ-linolenic acid (4.1). On leave from Suntory Ltd.     

Copolymerizations of macromonomer prepared by addition-fragmentation chain transfer polymerization of methyl acrylate trimer

Summary An oligomer of the methyl acrylate unsaturated trimer bearing 2-carbomethoxy-2-propenyl ω-end group (M _n = 1300, M _w/M _n = 1.7, and functionality > 0.7) was copolymerized as a macromonomer (0.02 mol/L) with styrene (1.0 mol/L) in benzene at 60 °C. The amounts of monomer and macromonomer in the feed simultaneously decreased with increasing time to indicate copolymer formation, and the macromonomer was found to be as reactive as styrene toward poly(styrene) radicals. The M _ns of the copolymers were 13900–22000 depending on conversion. No resonance due to the unsaturated <ω-end group bound to the poly(styrene) chain was detected by ¹H-NMR spectroscopy, indicating that no fragmentation of adduct radical of the end group to expel the poly(methyl acrylate trimer) radical. Polymerization of ethyl methacrylate (1.0 mol/L) in the presence of the macromonomer (0.02 mol/L) resulted in a mixture of the unreacted macromonomer and homopolymer of ethyl methacrylate. No end group bound to the poly(ethyl methacrylate) was detected by ¹H-NMR spectroscopy, excluding the possibility of addition fragmentation chain transfer to the macromonomer to expel an oligomer radical of the methyl acrylate trimer. Addition of the poly(methacrylate) radical to the macromonomer is extremely slow under the present conditions of copolymerization. Received: 27 March 2003/Revised version: 30 April 2003/ Accepted: 30 April 2003 Correspondence to Bunichiro Yamada     

Temperature Dependence of KIC for High-Pressure Hot-Pressed Si3N4 Without Additives

Temperature dependence of K_IC values for Si₃N₄ bodies sintered at high pressures without additives was studied from room temperature to 1400°C. Little change in K_K was found in this range.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Influence of reaction temperature on direct esterifications in a continuous recycling process between terephthalic acid and ethylene glycol

Simulations were carried out with a continuous recycle esterification model for the terephthalic acid–ethylene glycol (TPA–EG) system proposed previously. The influence of reaction temperatures, recycle ratios, and residence times on the oligomer characteristics was examined and the following results were obtained: (1) The main reactions proceed more under higher reaction temperatures, but the side reactions on diethylene glycol (DEG) proceed further than do the main reactions. (2) The higher residence time ratio of the first reactor to the total results in the proceeding of esterifications, which becomes remarkable as the temperature becomes high. (3) As the recycle ratio becomes high, the esterfications proceed, but in the very high degree of esterification, the tendency is reversed. (4) The characteristics of oligomer are almost the same at the same degree of esterification, independent of the reaction conditions. © 1994 John Wiley & Sons, Inc.     

Low-temperature selective reduction of NO with propene over alkaline-exchanged mordenites

Partially protonated alkaline mordenites showed higher activity per acid amount below 573 K than acidic zeolites for the selective reduction of NO with C₃H₆ in the presence of O₂, which can be related to a high concentration of NO₃ ^- species in the zeolite channels. This revised version was published online in July 2006 with corrections to the Cover Date.     

One-Step Synthesis of Luminescent Nanoparticles of Complex Oxide, Strontium Aluminate

An organic aqueous solution of metal acetylacetonate precursors was subjected to spray pyrolysis in order to fabricate SrAl₂O₄:Eu (SAO) nanoparticles. Non-agglomerated luminescent SAO nanoparticles, having a spherical shape with a size of 10–30 nm, were achieved in a single step, while only submicrometer-sized SAO particles were obtained from the conventional ultrasonic pyrolysis of the metal nitrates. Without any post-annealing process, the as-prepared SAO nanoparticles were observed to exhibit a strong photoluminescence, which is comparable with that of the submicrometer-sized SAO particles. A mechanism for the formation of the nanoparticles is also discussed.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Effective renaturation of reduced lysozyme by gentle removal of urea

To increase the folding yield of concentrated reduced lysozyme,we developed a renaturation method by means of dialysis fromconcentrated urea with redox agents. After lysozyme was incubatedin the reducing buffer (8 M urea solution) with oxidized glutathione,renaturation of reduced lysozyme was started by dialysis againstthe dialyzing buffer containing 8 M urea with redox agents.The urea concentration of the dialyzing bottle was graduallydiluted with dialyzing buffer without urea at a flow rate of0.1 ml/min by high pressure pump. Using this systematic dialysis,a concentration as high as 5 mg/ml of reduced lysozyme couldbe renaturated in 80% yield, while the folding yield was <5%even at a concentration of 1 mg/ml using a conventional rapiddilution method [Goldberg et al. (1991) Biochemistry, 30, 2790–2797].Therefore, it was concluded that gentle removal of urea fromdenatured proteins, dissolved in concentrated urea solution,by means of dialysis should be useful to renature denaturedproteins effectively.     

Adsorption and desorption properties of cationic polyethylene film gels to organic anions and their regeneration

An investigation was undertaken on the adsorption and desorption properties of 2‐(dimethylamino)ethyl methacrylate grafted polyethylene (PE‐g‐PDMAEMA) films to anionic dye anions with one to three sulfonic groups in response to pH and temperature changes. The amounts of dye anions adsorbed on the PE‐g‐PDMAEMA films passed through the maximum values at about pH 3 because of an increase in the protonation of dimethylamino groups caused by a decrease in the pH value. The amounts of adsorbed dye anions decreased below pH 3 because the ionic strength increased with the addition of HCl to adjust the initial pH values of the aqueous dye solutions. The amounts of adsorbed dye anions decreased with an increase in the number of sulfonic groups in the dye molecules at the same pH value because electrostatic repulsion was generated between free sulfonic groups of the dye anions adsorbed onto the PE‐g‐PDMAEMA films and free dye anions in the medium. A large number of dye anions adsorbed were desorbed from the PE‐g‐PDMAEMA film with initial pH values above 11.0. The cyclic processes of adsorption at pH 3.0 and desorption at pH 11.0 were repeated without considerable fatigue. The PE‐g‐PDMAEMA films showed practically regenerative adsorption and desorption behavior in response to the pH changes. In addition, when the dye‐anion‐adsorbed PE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed in water at higher temperatures without any chemical agents because of the deprotonation of dimethylamino groups and thermosensitive contraction of grafted PDMAEMA chains. These results indicate that PE‐g‐PDMAEMA films can be applied as regenerative ion‐exchange membranes for adsorption and desorption processes of anionic compounds in response to the pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 381–391, 2006