Synthesis and radical ring-opening polymerization behavior of vinylcyclopropane bearing six-membered cyclic acetal moiety

Synthesis and radical ring-opening polymerization of vinylcyclopropane bearing six-membered cyclic acetal moiety, 1-vinyl-4,8-dioxaspiro[2.5]octane (1), were carried out. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and 1,3-propanediol in DMF in the presence of a base. Radical polymerization of 1 was carried out in the presence of an appropriate initiator (3 mol % vs. 1) at 60 and 120°C in degassed sealed ampoules for 20 h. A colorless transparent viscous polymer was obtained by the isolation with preparative HPLC. The structure of poly(1) was determined to consist of two 1,5-ring-opened units and a unit bearing no olefinic moiety. The difference of the activation energies for the ring-opening reaction of the cyclopropane ring calculated by the molecular orbital method could explain the selectivity in the direction of the cleavage of the cyclopropane ring. Acid hydrolysis of poly(1) afforded the corresponding polyketone in quantitative conversion. © 1996 John Wiley & Sons, Inc.     

Syntheses and radical polymerizations of novel optically active vinyl and isopropenyl carbamates having L-leucine structures

Syntheses and radical polymerizations of vinyl and isopropenyl carbamates having L -leucine methyl ester structures, N-vinyloxycarbonyl-L -leucine methyl ester (VOC-L-M) and N-isopropenyloxycarbonyl-L -leucine methyl ester (IOC-L-M), were carried out. VOC-L-M and IOC-L-M were prepared by the reactions of L -leucine methyl ester with vinyl and isopropenyl chloroformates in the presence of sodium hydrogen carbonate. The radical polymerization of VOC-L-M with AIBN (1 mol %) in bulk, chlorobenzene, methanol, and N,N-dimethylformamide afforded the corresponding polymer (poly(VOC-L-M)) with M _n 7,400–19,000. Meanwhile, IOC-L-M afforded no polymer with AIBN at 60°C but afforded a polymer having low molecular weight with BPO at 80°C. The glass transition temperatures of poly(VOC-L-M) and poly(IOC-L-M) were 53 and 65°C, respectively. The 10% weight loss temperatures of poly(VOC-L-M) and poly(IOC-L-M) under nitrogen were 255 and 173, respectively. The copolymerization parameters of VOC-L-M (M₁) and vinyl acetate (M₂) were evaluated as r₁ = 0.92 and r₂ = 0.63. © 1996 John Wiley & Sons, Inc.     

Speciation of Arsenic Compounds in the Urine of Rats Orally Exposed to Dimethylarsinic Acid Ion Chromatography with ICP–MS as an Element-Selective Detector

A combined ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP—MS) system as an element-selective detector has been used for the determination of arsenic compounds. Seven arsenic compounds were separated by cation-exchange chromatography. Subsequently, the separated arsenic compounds were directly introduced into the ICP—MS and were detected at m/z =75. Detection limits for the seven arsenic compounds ranged from 0.8 to 3.8 μg As/l. The IC–ICP–MS system was applied to the determination of arsenic compounds in the urine of dimethylarsinic acid (DMAA)-exposed rats. DMAA was the most abundant arsenic compound detected. Arsenous acid, monomethylarsonic acid and trimethylarsine oxide were also detected.     

Novel stability condition for delayed fractional-order composite systems based on vector Lyapunov function

Nonlinear Dynamics - This paper proposes a novel stability condition for delayed fractional-order composite systems. First, we extend the vector Lyapunov function to the fractional-order systems to...     

Theory of particle transport phenomena during fatigue and time-dependent fracture of materials based on mesoscale dynamics and their practical applications

In this work, the mesoscale mechanics of metals, which links their microscopic physics and macroscopic mechanics, was established. For practical applications, the laws for quantitatively predicting life of cycle and time-dependent fracture behavior such as fatigue, hydrogen embrittlement, and high-temperature creep were derived using particle transport phenomena theories such as dislocation group dynamics, hydrogen diffusion, and vacancy diffusion. Furthermore, these concepts were also applied for estimating the degree of viscoelastic deterioration of blood vessel walls, which is dominated by a time-dependent mechanism, and for the diagnosis of aneurysm accompanied by the viscoelastic deterioration of the blood vessel wall. In these theories, new mechanical indexes were derived as dominant factors for predicting the life of fatigue crack growth and the time-dependent fracture of notched specimens of materials such as hydrogen embrittlement and high-temperature creep. Furthermore, as an example of a practical application, these theories were applied to estimate the degree of viscoelastic deterioration and chaotic motions of blood vessel walls, which are closely related to blood vessel diseases such as atherosclerosis and aneurysm. Moreover, new indexes to diagnose them were also proposed for clinical applications.     

Microwave spectroscopic study of the SiF radical

The microwave spectrum of the SiF radical was observed in both ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ of the ground vibronic state. The SiF radical was produced by a dc discharge either in a $\text{SiF}{}_4\text{SiH}{}_4$ mixture or in a transient molecule SiF₂ generated by the reaction of SiF₄ with heated solid silicon. The latter gave twice as intense a spectrum. A least-squares fit to the observed spectrum showed the rotational constant and the centrifugal distortion constant to be 17 350.2752(63) and 0.03188(13) MHz, respectively, with three standard errors in parentheses applying to the last digits of the constants. The lambda-doubling parameter p₀ was found to be negative, ?87.67 MHz, indicating that the ²Σ⁺ excited state contributions dominate over those of ²Σ^?. All four hyperfine coupling constants a, b, c, and d were determined and were employed to discuss the unpaired-electron spin and orbital distributions in the SiF radical.     

Studies of phase characteristics of various photon echoes with a phase sensitive detection method

Various optical coherent transient signals in ruby have been examined by using an optical phase sensitive detection (PSD) technique. The PSD is performed by comparing the phase of the heterodyne beat signals obtained by the Stark switching technique with that of a local oscillator whose frequency is equal to the heterodyne beat frequency. The optical FID, two-pulse photon echoes, radiation locked echoes and notched echoes have been detected as υ-mode signals with small u-mode signals probably due to the asymmetry of the inhomogeneous broadening. The dependence of the phase of the radiation locked and notched echoes upon the driving pulses is also examined. The experimental results are in good agreement with theoretical predictions based on Bloch equations.     

Optical characteristics of Cr and Nd codoped Y3Al5O12 ceramics

The optical characteristics of Cr³⁺ and Nd³⁺ codoped Y₃Al₅O₁₂ (YAG) ceramics are measured. These measurements are done using two pumping sources, a 808 nm laser diode (LD) and a Xe short-arc lamp, to simulate solar radiation. The specimens used are 0.1%Cr³⁺/1.0%Nd³⁺ and 3.0%Cr³⁺/1.0%Nd³⁺ (atomic%) codoped YAG ceramics. A Nd:YAG crystal doped with 1.0%Nd³⁺ is used as a reference. The saturation intensities of the Cr/Nd:YAG ceramics pumped by the LD are the same as that of the Nd:YAG crystal, while they are higher when they are pumped by the Xe lamp. The saturation intensities are for the 0.1% Cr-doped ceramic and for the 3.0%Cr-doped ceramic. The small signal gains of the 0.1%Cr-doped and 3.0%Cr-doped ceramics are measured and found to be 1.8 times and 7.0 times higher than that of Nd:YAG for the same intensity of solar pumping, respectively. The quantum efficiency of energy transfer from Cr³⁺ to Nd³⁺ is estimated to be 0.88±0.09 for the 0.1%Cr-doped ceramic and 0.67±0.08 for the 3.0%Cr-doped ceramic.     

Bounded cohomology and non-uniform perfection of mapping class groups

Using the existence of certain symplectic submanifolds in symplectic 4-manifolds, we prove an estimate from above for the number of singular fibers with separating vanishing cycles in minimal Lefschetz fibrations over surfaces of positive genus. This estimate is then used to deduce that mapping class groups are not uniformly perfect, and that the map from their second bounded cohomology to ordinary cohomology is not injective. Oblatum 8-IX-2000 & 20-X-2000?Published online: 29 January 2001     

Low Power Penalty Operation of a Wide Input Dynamic Range Cross-Phase Modulation Wavelength Converter

We successfully demonstrated low power penalty operation of a cross-phase modulated (XPM) wavelength converter using a semiconductor optical amplifier (SOA) power equalizer. We also clarified the SOA equalizing level for more adaptive wavelength conversion and achieved a power penalty of less than 1 dB over the wide input dynamic range of 15 dB.