Stereospecific and asymmetric polymerization of 1-phenyldibenzosuberyl methacrylate with radical and anionic initiators

Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)₂ at 40°C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)-and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N′-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.     

Performance Test of CW 300?GHz Gyrotron FU CW I

A 300 GHz CW gyrotron FU CW I has been developed and installed in the Research Center for Development of Far-Infrared Region, University of Fukui as a power source of a high frequency material processing system. Its performance was tested and the maximum power of 1.75 kW / CW has been attained at the beam voltage of 15 kV and the beam current of 1A. The maximum window power efficiency of 15.5% has been obtained at the cathode voltage slightly lower than 15 kV. This gyrotron is designed to deliver a Gaussian beam after mode conversion from the oscillation mode TE_22,8 in the cavity with a complex of an internal radiator and beam shaping mirrors. The detailed measurement with an infrared camera has confirmed that a Gaussian beam is radiated when the magnetic field strength B _c at the cavity is adjusted at a proper value. However, within a range of B _c , the output power is emerged into multiple directions, which suggests simultaneous oscillation of competing cavity modes.     

Measurement Accuracy in Phase-Shifting Point Diffraction Interferometer with Two Optical Fibers

A phase-shifting point diffraction interferometer (PS/PDI) with point sources of two single mode optical fibers has been developed, which will be appropriate for the surface figure measurement of large aperture optics on a sub-nanometer scale. To reduce the measurement error factors, a fiber optic plate (FOP) is used as a projection plane for interference pattern. Errors caused by imperfection of optical alignment, such as position of point sources and tilt of FOP, are minimized by analyzing the measured phase data with an original method. Measurement accuracy in the PS/ PDI is estimated with the interference pattern produced by the two optical fiber sources. If inhomogeneity of the FOP and a systematic error of the PS/PDI are eliminated, the measurement accuracy of the present system is estimated to be less than 4nm P-V and 0.7nm rms, respectively, at a measurement wavelength of 632.8 nm.     

10-Gbit/s optical receiver using ICs with low-capacitance HBT technology

A 10-Gbit/s optical receiver is developed using low-capacitance HBT IC technology. The HBT allows a cutoff frequency of 45 GHz and a maximum oscillation frequency of 70 GHz. The receiver contains an automatic gain-control amplifier IC with a gain of 16 dB, a bandwidth of 10.7 GHz, and a decision-circuit IC with an ambiguity of 66 mVp-p at a data rate of 10 Gbit/s. The sensitivity of this receiver is -26.5 dBm at a bit error rate of 10^-9. Transmission over a 140-km fiber was achieved successfully.     

Effects of graded porous structure on local strain distribution under compression in silicone rubber

Silicone rubber samples with gradually changing pore sizes within the range of 70–610 μm are produced using an improved spacer method. The samples are scanned using an X‐ray computed tomography to evaluate their graded structure as compared to uniform rubber. A compressive test reveals that graded porous silicone rubber has characteristic stress–strain curves whose slope changes within a specific strain range depending on the porous structure. Analysis results of local strain based on a digital image correlation of the graded porous silicone rubber under compression demonstrate that the characteristic stress–strain properties are caused by shifts in the main deformation region in the graded structure. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1033–1042     

Coexistence of Spin–Lattice Relaxation and Phonon-Bottleneck Processes in GdIII–Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions

Gd³⁺ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd³⁺ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd³⁺ complexes, we have investigated the magnetic properties and heat capacities of two Gd³⁺-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd³⁺–Gd³⁺ interactions and the other does not. It was found that the Gd³⁺–Gd³⁺ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd³⁺ complexes into a large amount of diamagnetic Y³⁺ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.     

Kinetics of phase transformation from hBN to cBN in the presence of Mg3BN3 catalyst

Abstract

Transformation kinetics from hBN to cBN has been studied at 6 GPa with changing reaction temperature and content of catalyst mixed with hBN powder. At lower catalyst content (3–10 wt %), rate of transformation was extraordinary rapid between 1300 and 1350 C. At higher catalyst content (30–50 wt %), rate of transformation was decreased. Normal nucleation kinetics was observed at about 1500 C. The rapid transformation temperature region correlates characteristic behavior of the sintering process.     

N‐Heterocyclic Carbene Catalyzed (5+1) Annulations Exploiting a Vinyl Dianion Synthon Strategy

Direct polarity inversion of conjugate acceptors provides a valuable entry to homoenolates. N‐heterocyclic carbene (NHC) catalyzed reactions, in which β‐unsubstituted conjugate acceptors undergo homoenolate formation and C?C bond formation twice, have been developed. Specifically, the all‐carbon (5+1) annulations give a range of mono‐ and bicyclic cyclohexanones (31 examples). In the first family of annulations, β‐unsubstituted acrylates tethered to a divinyl ketone undergo cycloisomerization, providing hexahydroindenes and tetralins. In the second, partially untethered substrates undergo an intermolecular (5+1) annulation involving dimerization followed by cycloisomerization. While enantioselectivity was not possible with the former, the latter proved viable, allowing cyclohexanones to be produced with high levels of enantiopurity (most >95:5 e.r.) and exclusive diastereoselectivity (>20:1 d.r.). Derivatizations and mechanistic studies are also reported.