Determination of optical purity and absolute configuration of natural 12‐hydroxystearic acid by the 1H NMR anisotropy method

The enantiopure of (R)‐(?) MαNPA was allowed to react with racemic 18‐(tert‐butyldimethylsilyloxy)‐5‐octadecayne‐7‐ol which was derived from dodecane‐1,12‐diol, yielding diastereomeric esters mixture. These racemic esters were easily separated by HPLC on silica‐gel. The absolute configurations of the first‐eluted diastereomeric esters from the separated esters were determined using ¹H NMR anisotropy method. Analysis on ¹H NMR spectra and HPLC elution time of the synthesized esters and those of MαNP ester derived from natural methyl‐12‐hydroxystealate showed that the absolute configuration of natural 12‐hydroxystearic acid was R form, and the enantiomeric excess was over 99%.     

A theoretically reproduced phase diagram for vinylidene fluoride and trifluoroethylene copolymers

The phase diagram of ferroelectric copolymers of vinylidene fluoride and trifluoroethylene is reproduced theoretically using a simple model for ferroelectric polymers. The copolymerization ratio dependencies of the intramolecular interaction and the intermolecular interaction are induced to reproduce the phase diagram. These interactions have the following effects on the ferroelectric phase transition of the copolymers. The intermolecular interaction between vinylidene fluoride segments is dominant in the ferroelectric phase transition. The intramolecular interaction, discriminating between different chain conformations, gives the phase transition a variety of characters, including first and second order phase transitions. The copolymerization ratio dependence of the intermolecular interaction is also numerically estimated by summing the interaction energy between all atoms. Comparing these two results, we discuss the size of a segment carrying an elementary process of the phase transition.     

Effects of Spraying Ozonated Water on the Severity of Powdery Mildew Infection on Cucumber Leaves

Effects of spraying ozonated water on the severity of powdery mildew infection, visible disorder/injury occurrence, and net photosynthesis in cucumbers were investigated. The severity in the ozonated water treatment was contained to almost the same level throughout the 14-day period of the experiment, while the severity steadily increased in the non-treated control and distilled water treatment. Neither visible disorder/injury on the leaves nor a large difference in net photosynthesis between before and after spraying the ozonated water was observed. The results indicate that ozonated water can be at least a partial alternative to agricultural chemical fungicides for powdery mildew on cucumber leaves.     

Adsorption characteristics of superplasticizers on cement component minerals

Adsorption characteristics of various superplasticizers on portland cement component minerals were investigated. Adsorption isotherms of various types of superplasticizers and ζ-potentials of cement component minerals at the maximum adsorption of the superplasticizers were measured. The value of the adsorption isotherm was calculated from the amount of the superplasticizer adsorbed on a cement component mineral in an equilibrated solution. The maximum amounts of adsorption and the adsorption isotherms varied with types of component mineral and superplasticizer. For all types of superplasticizers, a larger amount of superplasticizer was adsorbed on C₃A and C₄AF than C₃S and C₂S. However, the equilibrated concentration of each superplasticizer at the maximum adsorption was not influenced by types of superplasticizer. Without superplasticizer, C₃S and C₂S had negative ζ-potential. On the contrary, C₃A and C₄AF had positive ζ-potential. Therefore, accelerated coagulation of cement particles might occur due to their electrostatic potentials that are opposite each other. However, all component minerals of cement had negative ζ-potential when they were mixed with any superplasticizer. Fluidity of fresh cement paste is improved due to electrostatic repulsion acting between particles.     

Monomer recycling for vulcanized silicone rubbers in the form of cyclosiloxane monomers. Role of acid buffers

The KOH-catalyzed depolymerization of vulcanized silicone rubbers to reproduce cyclosiloxane monomers was studied. First, the depolymerization was carried out in toluene with varying amounts of KOH to find that the yield of monomers first increased and then decreased with the increment of KOH, the highest yield was 65% at the molar ratio KOH/(Si–O) UNITS=0.08. At the molar ratio 0.13 in the absence of solvent, the monomers yield was 46%. However, when an acid buffer such as KH₂PO₄ and KCOOC₆H₄COOH was added after the KOH-catalyzed depolymerization was over, the product yield was increased remarkably to more than 80%.     

Recovery of monomers and fillers from high-temperature-vulcanized silicone rubbers—combined effects of solvent, base and fillers

The depolymerization of high-temperature-vulcanized (HTV) silicone rubbers containing filler silica and alumina into cyclosiloxane monomers and spontaneous recovery of fillers were studied. First, HTV silicone rubber was treated with different types of solvents in the presence of KOH to find that a triad mixture of diethylamine, methanol and hexane was appropriate not only to dissolve the silicone rubber to a suspension but also to separate fillers completely by filtration. The filtrate was distilled to remove solvent first and then give pure cyclosiloxane monomers in 76–84% yields. Second, the rubbers were treated with other types of triad mixture of solvents and bases, e.g. tetramethylammonium hydroxide, hexane and diethylamine. After filtration, residue was again treated with the amine and hexane to recover clean fillers in 83–93% yields. Cyclosiloxane monomers were also obtained from the combined filtrates in 67–78% yields.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

Gibbs Energy Change of Carbothermal Nitridation Reaction of Al2O3 to Form AlN and Reassessment of Thermochemical Properties of AlN

The experimental method for the high-temperature reaction equilibria in the AlN-Al₂O₃ system has been established. The equilibrium N₂-CO gas compositions coexisting with AlN- Al₂O₃-graphite have been successfully measured by quadrupole mass spectrometry and gas chromatography. From the obtained results, the standard Gibbs energy change of the forming reaction of AlN by carbothermal nitridation is determined at temperatures ranging from 1723 to 1899 K:
From the obtained result, the standard Gibbs energy of formation of AlN and the third-law enthalpy of formation of AlN at 298.15 K are derived as
The disagreement between the present results and values in the NIST–JANAF thermodynamic table is discussed.