Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper,Silver, and a Brønsted Acid

The cooperative catalysis of copper, silver, and Brønsted acid is presented as a new strategy for olefin functionalization. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided a straightforward and efficient approach for preparing 4,5‐unsaturated alcohols. Synthetically useful functional groups, such as Cl, Br, carbonyl, and chloromethyl, remained intact during the functionalization reaction.     

Towards beyond-1 GHz solution NMR: internal 2H lock operation in an external current mode

We have commenced a project to develop a beyond-1 GHz solution NMR spectrometer using a HTS coil. Due to a small residual resistance present in the HTS conductor and joint resistance between conductors, a stable persistent current sufficient for NMR measurements is unlikely. Therefore, a current has to be supplied to the HTS coil from an external power supply. The ripple of an external power supply causes a field fluctuation which must be stabilized. In this study we show results of NMR measurements using a 500-600 MHz NMR in such an external current mode: the field fluctuations are stabilized by an internal 2H lock. The field fluctuation from the external power supply comprises a major field fluctuation component at low frequencies, 0.003-0.005 Hz, and superimposed minor field ripples at 2 Hz and 50 Hz. The former limits the time interval of the internal 2H lock, while the latter generates sidebands in the NMR spectrum. Sideband and baseline noise are controlled by appropriate selection of the feedback loop parameters of the lock. The quality of the 1D-solution NMR spectra observed in external current mode is equivalent to that obtained in persistent current mode. However, if the feedback loop time is as short as the gradient pulse width, refocusing of the NMR signal is lost and NMR peaks disappear. The 2D-NOESY and the 2D-HSQC spectra of ubiquitin in an external current mode have been acquired. The quality of the 2D spectra is equivalent to those obtained in persistent current mode; i.e. the internal 2H lock operates stably over an experimental time interval of 40-50 min. To realize a beyond-1 GHz NMR spectrometer, further investigations must be made of (i) the long term stability of a DC power supply, (ii) the enhancement of the compensation field limit for the internal 2H lock, (iii) the extension of the helium refill time interval, and (iv) a method to correct the field homogeneity in the external current mode.     

Photochromism induced by infrared two-photon absorption

An IR laser of 940 nm wavelength induced photochromic reaction in acrylate that contained both spirobenzopyran and rare-earth doped oxide (Gd(2)O(2)S:YbEr). The rare-earth elements were excited by two 940 nm photons and emitted a 550 nm photon, which caused photochromic isomerization of spirobenzopyran. This acrylate turned to its original orange color by either thermal relaxation or ultraviolet irradiation, and was bleached again by IR laser irradiation.     

Secondary ion species containing nitrogen atoms from plasma-enhanced chemical vapor deposited silicon oxide films on silicon

Secondary ion species from plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Comparative studies of PECVD SiO₂ films prepared using a mixture of SiH₄/N₂O reaction gas at 400 °C with thermally oxidized SiO₂ films grown at 900 °C were carried out in the mid-range mass spectra from 95 to 165 amu. Small amounts of ion species containing nitrogen atoms, including Si₂O₂N⁺, Si₃O₂N⁺and Si₃O₃N⁺, were detected in the SiO₂ bulk from the PECVD SiO₂ films. Furthermore, large amounts of Si₃O₂N⁺ and Si₂O₃N⁻ were found at the interface between silicon and the SiO₂ films. Depth analysis showed that the intensity peak shapes of these ion species containing nitrogen atoms at the interface were closely coincident with those of Si₃O₃⁺ corrected by subtracting the influence of the SiO₂ matrix. The variation in the spectra of these ion species clearly indicates that two types of structures of oxynitride exist for the PECVD SiO₂ films in the SiO₂ bulk films and at the interface. These are likely produced by the reaction of reactive gas with SiO₂ and silicon surfaces where dangling bonds of silicon may exist in the different form.     

Stereoselective Complex Formation between Polybutadiene and Cyclodextrins in Bulk

Polybutadienes (PBs) are found to form inclusion complexes with cyclodextrins (CDs) stereoselectively to give crystalline compounds in bulk. These complexes have been isolated and characterized by means of ¹H NMR and ¹³C CP/MAS NMR spectroscopy, and X‐ray diffraction. Although α‐CD did not form inclusion complexes with any kinds of PBs in aqueous solutions, α‐CD did form inclusion complexes with PBs having 1,4‐cis‐ and 1,4‐trans‐butadiene units in bulk by heating at 100 °C. On the other hand, PB having 79% of a 1,2‐structure did not form inclusion complexes with α‐CD. The yield of the inclusion complexes increases with an increase in the content of the 1,4‐cis‐structure of PB and decreases with the molecular weights of the PBs.

     

Ac vortex-dependent torsional oscillation response and onset temperature T0 in solid 4He

Detailed studies of ac velocity V_{ac} and T dependence of torsional oscillator responses of solid 4He are reported. A characteristic onset temperature T_{0} approximately 0.5 K is found, below which a significant V_{ac}-dependent change occurs in the energy dissipation for the samples at approximately 32 bar and for one at 49 bar. A V_{ac} dependence of the so-called "nonclassical rotational inertia" fraction also appears below approximately T_{0}. The log(V_{ac}) linear dependence, which suggests involvement of quantized vorticies, was examined in the nonclassical rotational inertia fraction. We find a common 1/T;{2} dependence for this linear slope change in all of the samples for 30相似文献   

Detection of Label Area by Comb-Shaped Illumination

We have developed a non-contacting technique to detect small steps on a surface such as label edges on a letter by using a spatially modulated illumination. Steps can be detected correctly with this new technique even if there are printed patterns on the same surface. Thus the technique is effective for determining label areas that are often seen on pieces of direct mail.This paper was originally presented at the 2nd International Conference on Optical Design and Fabrication, ODF2000 which was held on November 15–17, at the International Conference Center, Tokyo, Waseda University, Japan.     

Error analysis for the computation of zeros of regular Coulomb wave function and its first derivative

In 1975 one of the coauthors, Ikebe, showed that the problem of computing the zeros of the regular Coulomb wave functions and their derivatives may be reformulated as the eigenvalue problem for infinite matrices. Approximation by truncation is justified but no error estimates are given there.

The class of eigenvalue problems studied there turns out to be subsumed in a more general problem studied by Ikebe et al. in 1993, where an extremely accurate asymptotic error estimate is shown.

In this paper, we apply this error formula to the former case to obtain error formulas in a closed, explicit form.

     

Evaluation of gas sorption parameters and prediction of sorption isotherms in glassy polymers

A model of continuous‐site distribution for gas sorption in glassy polymers is examined with sorption data of CO₂ and Ar in polycarbonate. A procedure is presented for determining from a measured isotherm the number of sorption sites in a polymer, an important parameter that previously had to be assumed. With this parameter value and solubility data obtained at zero pressure, the model can reasonably predict sorption isotherms of CO₂ in glassy polycarbonate for a wide temperature range. The number of sorption sites and the average site volume evaluated from CO₂ sorption isotherms are employed for the prediction of Ar sorption isotherms with zero‐pressure solubility data and the independently measured partial molar volume of Ar. A reasonable fit to the measured isotherms of Ar is achieved. With the proposed procedure, the continuous‐site model shows several advantages over the conventional dual‐mode sorption model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 883–888, 2000