Hg(OTf)2-catalyzed vinylogous semi-pinacol rearrangement leading to 1,4-dihydroquinolines

An efficient method for the construction of dihydroquinoline derivatives possessing a quaternary carbon center is developed by an application of Hg(OTf)(2)-catalyzed vinylogous semi-pinacol-type rearrangement. The reaction was found to be specifically catalyzed by mercury salt and to proceed via a bicyclic aminal.     

Pedestal suppression of ultrashort pulses by using a birefringent nonlinear polarization rotation mirror

A new scheme for a birefringent nonlinear polarization rotation mirror is proposed for pedestal suppression of ultrashort pulses. Environmentally stable and precisely controllable operation is demonstrated. The main pulse and pedestal components are separated and picked out from the different ports. By use of the soliton effect and nonlinear polarization rotation, almost transform-limited pedestal-free 318 and 143 fs ultrashort pulses with peak powers of 0.9 and 1.7 kW are successfully generated. The maximum pedestal-suppression ratio is 24 dB, and the pick-out efficiency is up to 46% including coupling loss. The characteristics are analyzed both experimentally and numerically.     

High-resolution soft X-ray photoelectron spectroscopy of liquid water

High-resolution soft X-ray photoelectron spectra of liquid water (H(2)O and D(2)O) were measured using a liquid beam photoelectron spectrometer. The 1a(1) (O1s) band and the lowest valence 1b(1) band had single peaks, which is not consistent with the split 1b(1)→ 1a(1) of the X-ray emission band of liquid water if the splitting is assumed to originate from level shifts in two different hydrogen bonding structures. The second valence 3a(1) band of liquid water exhibited a flat top implying that two bands exist underneath a broad feature, which is similar to the case of the 3a(1) band of amorphous ice. The energy splitting between the two 3a(1) bands is estimated to be 1.38 eV (H(2)O) and 1.39 eV (D(2)O). Ab initio calculations suggest that the large splitting of the 3a(1) band is characteristic of water molecules that function as both proton donor and acceptor. The overall result is consistent with the conventional model of a tetrahedral hydrogen-bonding network in liquid water.     

Real-time, ultrahigh-resolution, optical coherence tomography with an all-fiber, femtosecond fiber laser continuum at 1.5 microm

Real-time, ultrahigh-resolution optical coherence tomography (OCT) is demonstrated in the 1.4-1.7-microm wavelength region with a stretched-pulse, passively mode-locked, Er-doped fiber laser and highly nonlinear fiber. The fiber laser generates 100-mW, linearly chirped pulses at a 51-MHz repetition rate. The pulses are compressed and then coupled into a normally dispersive highly nonlinear fiber to generate a low-noise supercontinuum with a 180-nm FWHM bandwidth and 38 mW of output power. This light source is stable, compact, and broadband, permitting high-speed, real-time, high-resolution OCT imaging. In vivo high-speed OCT imaging of human skin with approximately 5.5-microm resolution and 99-dB sensitivity is demonstrated.     

Development of THz wave oscillation and its application to molecular sciences

In 1967, a THz wave was generated for the first time using a free electron laser; however, the device was too expensive to be used widely. The author published the idea of THz wave generation by use of resonating vibration between paired atoms in polymer or crystal in 1965, and succeeded with K. Suto to generate a 12 THz wave in 1983. In 1999, the author invited K. Kawase and H. Ito to Sendai RIKEN to realize the concept by use of dielectrics; in 2000, they succeeded in realizing a sweep generator. In the same year, the author suggested the idea of applying the THz wave to cancer diagnosis and treatment, particularly by improving heating selectivity: This enhances the effect of medications by raising only the temperature of the cancer itself, not of the surrounding atomic pairs in the neighborhood. These applications are expected to spread quickly as powerful methodology based on molecular science. The reason for this is that the much improved waveform generated enables higher selectivity, allowing the detection of the existence of abnormal polymer near the paired atoms by measuring resonating frequency between paired atoms.     

Tapered waveguide semiconductor raman laser

Semiconductor Raman laser can act as a heterodyne demodulator of terahertz-band modulated light wave signals in wideband optical communication systems. We have been developing the semiconductor Raman laser with a waveguide structure composed of a GaP core and Al_xGa_1–xP cladding layers. The tapered waveguide structure can reduce the threshold pump power by increasing the internal pump power density. Fabricated tapered waveguide semiconductor Raman laser have shown the threshold pump power of 160 mW. Discussion is made on the origin of losses as well as the limit of the low pump power operation.     

Pulse trapping by ultrashort soliton pulses in optical fibers across zero-dispersion wavelength

A new phenomenon of pulse trapping by the ultrashort soliton pulse of an optical fiber has been experimentally observed. The trapped pulse in the normal-dispersion region copropagates with the soliton pulse in the anomalous-dispersion region along the fiber, and the wavelength of the trapped pulse is shifted to satisfy the condition of group-velocity matching. The wavelengths of the soliton pulse and the trapped pulse change almost continuously as the power of the soliton pulse is varied. Almost perfect conversion efficiencies are observed for soliton self-frequency shift and pulse trapping.     

Vacuum Ultraviolet and Soft X‐ray Photoelectron Spectroscopy of Liquid Beams Using a Hemispherical Photoelectron Spectrometer with a Multistage Differential Pumping System

We present photoelectron spectroscopy of liquid beams using a high‐resolution hemispherical photoelectron spectrometer with a multistage differential pumping system developed in our laboratory. Intense soft X‐ray synchrotron radiation (500‐1200 eV) at SPring‐8 and a relatively large detection solid angle (1.5 × 10^?2 π sr) of the spectrometer enable highly efficient measurements of X‐ray photoelectron spectra of liquids. Vacuum ultraviolet photoelectron spectroscopy using the same spectrometer provides sufficiently high spectral resolution to resolve rotational isomers of gas‐phase molecules.     

Total pressure‐controlled PVT SiC growth for polytype stability during using 2D nucleation theory

A total pressure‐controlled physical vapor transport growth method that stabilizes SiC polytype is proposed. The supersaturation of carbon during SiC growth changed as a function of the growth time due to changes in the temperature difference between the surfaces of the source and the grown crystal. Supersaturation also varied as a function of the pressure inside the furnace. Therefore, modification of the pressure as a function of growth time allowed for constant supersaturation during growth. The supersaturation was calculated based on classical thermodynamic nucleation theory using data for heat and species of Si₂C and SiC₂ transfer in a furnace obtained from a global model. Based on this analysis, a method for polytype‐stabilized SiC growth was proposed that involves decreasing the pressure as a function of growth time. The 4H‐SiC prepared using this pressure‐controlled method was more stable than that of 4H‐SiC formed using the conventional constant‐pressure method.