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Tanaka, Yoshihito

Publications and source records attributed to Tanaka, Yoshihito.

X-ray beam transfer between hollow fibers for long-distance transport

Fiber optics for controlling the x-ray beam trajectory has been examined at the synchrotron facility of SPring-8. Up to now, we have achieved beam deflection by several tens of milli-radian and axis shift of around 75 mm with a 1.5 m-long flexible hollow glass capillary. The achievable beam deflecting angle, axis shift, and timing delay are, in principle, proportional to the length, the square of length and the cube of length, respectively. Thus, for further applications, requiring larger beam shift and pulse delay, longer fibers are indispensable. In order to achieve long-distance transport using the fiber, we thus examined the connection transferring x-rays between fibers in an experimental hutch. The acceptance angle at the input end and the throughput efficiency of the second fiber is consistent with the consideration of the output beam divergence of the first fiber. The enhancement of the transfer efficiency is also discussed for the cases of a closer joint and the use of a refractive lens as a coupler.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H- motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate a low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. Lastly, the present methodology is also relevant to characterizing Fe–H moieties in other important natural and synthetic catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O 2 -tolerant NAD + -reducing [NiFe] hydrogenase

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H 2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by 57 Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD+-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective 13 C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

System of laser pump and synchrotron radiation probe microdiffraction to investigate optical recording process

We have developed a system of laser-pump and synchrotron radiation probe microdiffraction to investigate the phase-change process on a nanosecond time scale of Ge{sub 2}Sb{sub 2}Te{sub 5} film embedded in multi-layer structures, which corresponds to real optical recording media. The measurements were achieved by combining (i) the pump-laser system with a pulse width of 300 ps, (ii) a highly brilliant focused microbeam with wide peak-energy width ({Delta}E/E {approx} 2%) made by focusing helical undulator radiation without monochromatization, and (iii) a precise sample rotation stage to make repetitive measurements. We successfully detected a very weak time-resolved diffraction signal by using this system from 100-nm-thick Ge{sub 2}Sb{sub 2}Te{sub 5} phase-change layers. This enabled us to find the dependence of the crystal-amorphous phase change process of the Ge{sub 2}Sb{sub 2}Te{sub 5} layers on laser power.

36 MATERIALS SCIENCE↗

Development of soft x-ray time-resolved photoemission spectroscopy system with a two-dimensional angle-resolved time-of-flight analyzer at SPring-8 BL07LSU

We have developed a soft x-ray time-resolved photoemission spectroscopy system using synchrotron radiation (SR) at SPring-8 BL07LSU and an ultrashort pulse laser system. Two-dimensional angle-resolved measurements were performed with a time-of-flight-type analyzer. The photoemission spectroscopy system is synchronized to light pulses of SR and laser using a time control unit. The performance of the instrument is demonstrated by mapping the band structure of a Si(111) crystal over the surface Brillouin zones and observing relaxation of the surface photo-voltage effect using the pump (laser) and probe (SR) method.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Pump-probe X-ray Diffraction Technique for Irreversible Phase Change Materials

We have developed a pump-probe X-ray diffraction measurement system for a sample with irreversible reaction at BL40XU in the SPring-8. The system mainly consists of a time-resolved measurement system, a sample disk rotation system, and an X-ray microbeam system. The time-resolved measurement system gives time resolution of 50 ps in laser-pump and X-ray probe method. A sample disk rotation system for repetitive measurements was made to give a virgin sample for every measurement. The number of repetitions for one sample disk was increased by using the X-ray microbeam technique. To keep the overlap of the X-ray microbeam and the laser beam on the sample surface during the disk rotation, the sample disk rotation system was constructed by a low-eccentric spindle motor. By using this system, the pump-probe X-ray diffraction measurement was demonstrated for a crystallization process of a DVD material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-Precision Time Delay Control with Continuous Phase Shifter for Pump-Probe Experiments Using Synchrotron Radiation Pulses

Brilliant pulsed x-ray synchrotron radiation (SR) is useful for pump-probe experiment such as time-resolved x-ray diffraction, x-ray absorption fine structure, and x-ray spectroscopy. For laser pump-SR x-ray probe experiments, short pulsed lasers are generally synchronized to the SR master oscillator controlling the voltage for acceleration of electron bunches in an accelerator, and the interval between the laser and the SR pulses is changed around the time scale of target phenomenon. Ideal delay control produces any time delay as keeping the time-precision and pointing-stability of optical pulses at a sample position. We constructed the time delay control module using a continuous phase shifter of radio frequency signal and a frequency divider, which can produce the delayed trigger pulses to the laser without degradation of the time precision and the pointing stability. A picoseconds time-resolved x-ray diffraction experiment was demonstrated at SPring-8 storage ring for fast lattice response by femtosecond pulsed laser irradiation, and suggested the possibility of accurate sound velocity measurement. A delay control unit operating with subpicosecond precision has also been designed for femtosecond pump-probe experiments using a free electron laser at SPring-8 campus.

43 PARTICLE ACCELERATORS↗