A far-infrared spectroscopic study of low temperature soft phonon mode in Tris-Sarcosine Calcium Chloride(TSCC)

Temperature dependences of the soft phonon frequency and the damping constant in Tris-Sarcosine Calcium Chloride (TSCC) single crystal have been investigated between 5K and 100K by using a Fourier-transform far-infrared spectrometer. It has been observed that the soft phonon frequency decreases gradually and the damping constant increases as the transition temperature is approached from below The damping constant varies from 7cm^-1 a 90K to less than 0.5cm^-1 at 5K. It has been found that the damping constant is approximately proportional to temperature below about 60K.     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Improvement in Thermoelectric Characteristics of n-type Iron Disilicide by Local Composition Modification

High thermoelectric figure of merit semiconducting ceramics of n -type iron disilicide with modified local compositions have been developed. Sintering and annealing of the composite powder composed of iron disilicide and precipitated cobalt (II) hydroxide resulted in the dissolution of excess Co and oxygen into the iron disilicide phase. Excess Co segregated to the grain boundary region, while interstitially incorporated oxygen was distributed homogeneously in the microstructure. The maximum figure of merit achieved was 5.2 × 10⁻⁴/K at 673 K.     

Prostaglandin-like substances formed during autoxidation of methyl linolenate

Prostaglandin-like substances other than 3-(2-ethyl-5-hydroxy-3-oxo)-cyclopentanyl-2-propenal (compound I), which upon reacting with amino acids form reddish pigments, were purified, and their chemical structures were determined. Three red pigment-forming substances (RPS) in autoxidized methyl linolenate were purified successively by gel chromatography on Sephadex LH-20, column chromatography and thin layer chromatography on Silica Gel 60, and by high performance liquid chromatography on μ-Porasil. IR spectra of the RPS showed the absorption of an ester group (νC=O 1730 cm⁻¹ in CHCl₃) and of a longer branched chain (νC-H 2800–3100 cm⁻¹), in addition to the absorption bands observed in compound I. Electron impact mass spectra of the trimethylsilyl ethers obtained after reduction with NaBH₄ and NaBD₄ were analyzed in detail and compared with those of compound I. The structures of the RPS were identified as stereoisomeric methyl 8-[2-(2-formylvinyl)-3-hydroxy-5-oxo-cyclopentanyl]-octanoates derived from methyl 12-hydroperoxy-linolenate. Presented at the general meeting of the Japanese Society of Scientific Fisheries, held at Tohoku University, Sendai, Japan, October 1984.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. I. Comparison of the inhibitory effects

The effects of chlorophyll and pheophytin on the autoxidation of oils in the dark were investigated by oven tests. The results indicated that both chlorophyll and pheophytin show antioxidant activity when methyl linoleate is used as substrate. Furthermore, chlorophyll retarded the oxidative deterioration of triglycerides in rapeseed and soybean oils at 30 C. Among the four chlorophyll derivatives (chlorophylls a and b and pheophytins a and b), chlorophyll a showed the strongest antioxidant activity. The antioxidant effects of chlorophyll and pheophytin depended on the storage temperature and the kinds of oil used as substrate.     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

Low-Temperature Synthesis of ZrC Powder by Cyclic Reaction of Mg in ZrO2–Mg–CH4

We investigated the conditions for low-temperature synthesis of ZrC fine powder from ZrO₂–Mg–CH₄. The synthesis utilizes a thermite-type reaction, with Mg as the reducing agent, and a reaction between Mg and CH₄ gas as a carbon source. The Mg/ZrO₂ molar ratio as well as the heating rate were varied. Because C can be continuously fed into the reaction group by the cyclic reaction of Mg through the formation and decomposition of Mg₂C₃ (2Mg + 3CH₄→ Mg₂C₃+ 6H₂→ 2Mg + 3C), a molar ratio of 2.2 for Mg/ZrO₂ was sufficient for the synthesis of single-phase ZrC. ZrC powders were synthesized under the following conditions: Mg/ZrO₂ molar ratio = 2.2, heating rate = 20°C/min, and temperature maintained at 750°C for 30 min. The amount of reaction heat produced in the reduction reaction of ZrO₂ by Mg depended on the Mg/ZrO₂ molar ratio, specifically, the amount of ZrO₂ contained. Moreover, the cyclic reaction of Mg-Mg₂C₃–Mg was influenced by the amount of reaction heat described above and by the heating rate. The ZrC fine powder showed little aggregation and high dispersibility.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.