Phase transition in the family LaxBi4−xTi3O12: In relation to lattice symmetry and distortion

The ferroelectric phase transition in the family La_xBi_4?xTi₃O₁₂ was investigated by X-ray diffractometry and differential scanning calorimetry. The crystal symmetry is orthorhombic in the range of 1 > x ≥ 0 and tetragonal in x ? 1. It was found that the shift of the phase-transition temperature is closely related to crystallographic symmetry and lattice distortion. (1) As the value of x increases, the ratio of lattice parameters, $\text{a}\text{b}$, decreases toward 1. (2) In the range of 1 > x ≥ 0, the lattice distortion increases with increasing x; just before x exceeds about 1, the distortion reaches a maximum. (3) As x exceeds about 1, the distortion decreases distinctively. (4) In the orthorhombic region, the phase-transition temperature decreases with increasing x. (5) In the tetragonal region, the transition does not occur. (6) The relation of transition temperature T_c to x is represented by a nonlinear function.     

Synthesis of 3-cyano-2-methylpyridines substituted with heteroaromatics

A series of title compounds were easily prepared by the sonication of α,β-unsaturated carbonyl compound in acetonitrile in the presence of potassium t-butoxide.     

A novel immobilized-enzyme system utilizing microcapsules

A novel immobilized-enzyme system that has glucoamylase on the surface of, and glucose oxidase within, polyurea microcapsules was developed. This system was found to carry out its sequential enzymatic reaction effectively. It was also demonstrated that the use of microcapsules was useful for this immobilized-enzyme system since a large amount of the second enzyme, glucose oxidase, was required for the sequential reaction to proceed efficiently. In addition, this system was found helpful for making the size of reaction batches smaller.     

Fiber spinning from the nematic melt. II. Effect of thermal history on spinning of the copolyester of polyethylene terephthalate and p-oxybenzoate

Fibers were spun from the nematic phase of the copolymer of polyethylene terephthalate having 60 mol % of p-oxybenzoate units. A capillary rheometer was used for spinning with a shear rate at the wall of 6.4 sec^?1, and capillary (length/diameter) ratio of 14.1. The spinning temperature was varied from 250° to 300°C and, at each temperature, the spin-draw ratio was examined as a variable. Spinning was performed under two conditions. When spinning from the melt without preheating, the initial modulus of the fibers increased with spin-draw ratio and increased with increasing spinning temperature for a fixed spin-draw ratio. In the second case, the melt was preheated and then cooled to the desired temperature before spinning the fibers. The preheating temperature was 280°C for spinning at 250°C, and 300°C for spinning at 280°C. Preheating increased the fiber modulus to the value obtained by spinning at the preheating temperature. A reduction of the viscosity due to the melting of poly(p-hydroxybenzoic acid) (PHB) crystallites produces better orientation and higher modulus. However, with increasing spin-draw ratio, the modulus of the preheated fibers decreased to the values expected for the spinning temperature. This decrease in modulus is due to recrystallization of PHB in the threadline.     

Weak infeasibility in second order cone programming

The objective of this work is to study weak infeasibility in second order cone programming. For this purpose, we consider a sequence of feasibility problems which mostly preserve the feasibility status of the original problem. This is used to show that for a given weakly infeasible problem at most m directions are needed to get arbitrarily close to the cone, where m is the number of Lorentz cones. We also tackle a closely related question and show that given a bounded optimization problem satisfying Slater’s condition, we may transform it into another problem that has the same optimal value but it is ensured to attain it. From solutions to the new problem, we discuss how to obtain solution to the original problem which are arbitrarily close to optimality. Finally, we discuss how to obtain finite certificate of weak infeasibility by combining our own techniques with facial reduction. The analysis is similar in spirit to previous work by the authors on SDPs, but a different approach is required to obtain tighter bounds on the number of directions needed to approach the cone.     

Polaron dynamics of heavily doped regioregular and regiorandom poly(3-alkylthiophenes) revealed by electron spin resonance spectroscopy

Electron spin resonance (ESR) features in heavily doped conjugated polymers are investigated through the comparison of temperature dependences of ESR spectra between head-to-tail coupled regioregular (RR) and regiorandom (RRa) poly(3-octylthiophenes) (P3OTs). RR-P3OT, used as a model of having crystalline grains in the solid film, is found to exhibit anisotropic ESR spectra, whereas RRa-P3OT gives almost isotropic ESR spectra similar to those of usual heavily doped conjugated polymers. This difference in the degree of spectral anisotropy primarily arises from a difference in their film morphology. Spectral simulations show the anisotropy observed in RR-P3OT to be caused by g-anisotropy. The presence of the g-anisotropy in RR-P3OT indicates that its polarons spend most of the time within a single crystalline grain that has some domains with a common direction of the g-tensor. The g-anisotropy turns out to decrease with increasing temperature. This result is explained by thermally activated hopping motions between crystalline grains. We emphasize that the decrease in the g-anisotropy with temperature should be associated with its activated type of temperature dependence of conductivity. In RRa-P3OT, its isotropic ESR spectra are suggested to be caused by the interchain motion as well as the intrachain one.     

Carbocyclization reaction of omega-iodo- and 1,omega-diiodo-1-alkynes without the loss of iodine atoms through a carbenoid-chain process

Atom-economical carbocyclization reactions of omega-iodo-1-alkynes and 1,omega-diiodo-1-alkynes to give products with incorporation of iodine atoms is described. Cycloisomerization of 2-(2-propynyloxy)ethyl iodides is initiated by a catalytic amount of LDA to give 3-(iodomethylene)tetrahydrofurans in high yields. Upon treatment of with a catalytic amount of 1-hexynyllithium, 1,omega-diiodo-1-alkynes efficiently undergo cycloisomerization to give (diiodomethylene)cycloalkanes. The diiodomethylene products are also obtained by iodine atom-transfer-type cyclization of omega-iodo-1-alkynes, using 1-iodo-1-hexyne as an external iodine atom source. Bromine atom-transfer and proton-transfer cyclization proceed as well by employing 1-bromo-1-octyne and 1-octyne, respectively. These reactions are proposed to proceed through a carbenoid-chain process involving exo-cyclization of the lithium acetylide intermediates to give Li,I-alkylidene carbenoids. It is shown that the exo-cyclization proceeded stereospecifically through inversion of the stereochemistry at the electrophilic carbon.     

Total synthesis of (−)-2-epi-lentiginosine by use of chiral 5-hydroxy-1,5-dihydropyrrol-2-one as a building block

We have developed a practical synthesis of the chiral lactam as a new chiral building block for alkaloid synthesis. Lipase-catalyzed kinetic resolution of hydroxylactam 8, followed by isolation-racemization of the chiral acetoxylactam 9 provided the optically pure hydroxylactam 8 in 96.0% yield with >99% ee after five cycles of kinetic resolution-racemization process. Chemical transformation of (S)-hydroxylactam 8 furnished chiral (−)-2-epi-lentiginosine (1) in 20% yield in 10 steps with no loss of enantiomeric excess.     

Measurement of the eta-meson mass using psi(2S) --> etaJ/psi

We measure the mass of the eta meson using psi(2S) --> etaJ/psi events acquired with the CLEO-c detector operating at the CESR e(+)e(-) collider. Using the four decay modes eta --> gamma gamma, 3pi(0), pi(+)pi(-)pi(0), and pi(+)pi(-)gamma, we find M(eta) = 547.785 +/- 0.017 +/- 0.057 MeV, in which the first uncertainty is statistical and the second systematic. This result has an uncertainty comparable to the two most precise previous measurements and is consistent with that of NA48, but is inconsistent at the level of 6.5 sigma with the much smaller mass obtained by GEM.