Stereoregular Polymerization of Alkyl Propiolate Catalyzed by Rh Complex

Abstract

The polymerizations of alkyl esters of propiolic acid by Rh complex catalysts were investigated. [Rh(norbornadiene)Cl]₂, which was the most active among the catalysts examined, gave rise to poly(alkyl propiolate) in a fairly high yield (～80%) in the presence of alcohol as the polymerization solvent. The polymers formed were a pale yellow powder soluble in common organic solvents except for poly(methyl propiolate). The structures of the polymers obtained were investigated by IR, ₁₃C-NMR, CP MAS ₁₃C-NMR, and laser Raman spectroscopies, together with the x-ray diffraction method. Based on these spectroscopic data, it was concluded that this Rh complex can be called a stereoregular polymerization catalyst of alkyl propiolate because the poly(alkyl propiolate) obtained has a cis-transoidal structure.     

Isotope-dependent crystalline phases at ambient temperature: Spectroscopic and calorimetric evidence for a deuteration-induced phase transition at 320 K in α-DCrO2

The heat capacities of HCrO₂ and DCrO₂ have been measured at temperatures between 5 and 360 K. A lambda anomaly occurred at 320 K for DCrO₂ but not for HCrO₂. Infrared spectra were recorded at temperatures between 5 and 405 K. The spectrum of DCrO₂ changed at 320 K with respect to the peak wave-number and splitting of some of the vibrations, while those of HCrO₂ depended smoothly on temperature. These experimental results are discussed in terms of a deuteration-induced phase transition.     

Infrared laser radar technique using heterodyne detection for range-resolved sensing of air pollutants

An infrared, pulsed heterodyne laser radar using differential absorption technique with tunable lasers is proposed as a practical means of measuring dispersed air pollutants with range resolution. A system analysis shows that this scheme offers an adequate sensitivity for ranges up to several km.     

Analysis of coherent Raman propagation effect

A theoretical analysis of coherent Raman propagation described by two classes of the well-known hyperbolic secant solution and elliptic solutions are presented.     

Evolution of the Hall coefficient and the peculiar electronic structure of the cuprate superconductors

Although the Hall coefficient R(H) is an informative transport property of metals and semiconductors, its meaning in the cuprate superconductors has been ambiguous because of its unusual characteristics. Here we show that a systematic study of R(H) in La2-xSrxCuO4 single crystals over a wide doping range establishes a qualitative understanding of its peculiar evolution, which turns out to reflect a two-component nature of the electronic structure caused by an unusual development of the Fermi surface recently uncovered by photoemission experiments.     

Frequency metrology with a turnkey all-fiber system

The repetition rate and carrier-envelope phase offset frequencies of a turnkey, all-fiber-based continuum generator were phase locked to a hydrogen maser. The frequency of the hydrogen maser was calibrated with a highly stable cesium atomic clock, and therefore a fully phase-locked optical frequency comb with well-defined absolute frequencies was obtained. In contrast with the commonly used Ti:sapphire-laser-based systems, we have accomplished a fully turnkey system with no user-adjustable parts. To evaluate the performance of this novel system, we performed absolute frequency measurements in the telecommunications region and at 1064 nm and compared them with our traditional Ti:sapphire-based comb.     

Broad-spectrum frequency comb generation and carrier-envelope offset frequency measurement by second-harmonic generation of a mode-locked fiber laser

A frequency comb spanning more than one octave has been achieved by injecting the second-harmonic generation (780 nm) of a mode-locked fiber laser (1.56 microm) into a photonic crystal fiber. We propose and realize a novel interferometric scheme for observing the carrier-envelope offset frequency of the frequency comb. Frequency noise has been observed on the measured carrier-envelope offset frequency, which has been confirmed to be generated in the photonic crystal fiber by comparing the measured beat frequencies between cw lasers and frequency combs before and after the photonic crystal fiber. The mode-locked fiber laser is considered to be an important candidate for the light source used in realizing a compact optical frequency measurement system including applications in the telecommunication bands.     

Magnetic-field-induced localization of quasiparticles in underdoped La(2-x)SrxCuO4 single crystals

Magnetic-field-induced ordering of electrons around vortices is a striking phenomenon recently found in high-T(c) cuprates. To identify its consequence in the quasiparticle dynamics, the magnetic-field (H) dependence of the low-temperature thermal conductivity kappa of La(2-x)SrxCuO4 crystals is studied for a wide doping range. It is found that the behavior of kappa(H) in the subkelvin region changes drastically across optimum doping, and the data for underdoped samples are indicative of unusual magnetic-field-induced localization of quasiparticles; this localization phenomenon is probably responsible for the unusual "insulating normal state" under high magnetic fields.     

Atomic and molecular spectroscopy with a continuous-wave, doubly resonant, monolithic optical parametric oscillator

Doppler-broadened atomic and molecular spectra were observed with a one octave tunable, continuous-wave, doubly resonant, monolithic optical parametric oscillator (OPO) using 5% MgO-doped LiNbO₃ as a non-linear crystal with a birefringent phase-matching configuration. By tuning the frequency of a pump laser, longitudinal mode selection over 20 successive modes, corresponding to a 60 GHz span, was possible, owing to the simple structure of the monolithic OPO. Continuous frequency tuning was achieved using an external waveguide-type electrooptic phase modulator (EOM). By changing the modulation frequency of the EOM, frequency tuning of the optical sidebands over 12 GHz was possible, which is larger than the one free spectral range of the monolithic cavity of 3 GHz. We could observe the Cs-D₁ (894 nm), Cs-D₂ (852 nm), Rb-D₁ (795 nm), acetylene R9 (1520 nm) and P9 (1530 nm) transitions with the single monolithic OPO.