Publications by authors named "Shin-ichi Wada"

Understanding electron transport in self-assembled monolayers on metal nanoparticles (NPs) is crucial for developing NP-based nanodevices. This study investigates ultrafast electron transport through aromatic molecules on NP surfaces resonant Auger electron spectroscopy (RAES) with a core-hole-clock (CHC) approach. Aromatic molecule-coated Au NPs are deposited to form condensed NP films, and flat monolayers are prepared for comparison.

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Time-resolved extreme ultraviolet spectroscopy was used to investigate photodissociation within the iodobenzene C-band. The carbon-iodine bond of iodobenzene was photolyzed at 200 nm, and the ensuing dynamics were probed at 10.3 nm (120 eV) over a 4 ps range.

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C-I bond extension and fission following ultraviolet (UV, 262 nm) photoexcitation of 2- and 3-iodothiophene is studied using ultrafast time-resolved extreme ultraviolet (XUV) ionization in conjunction with velocity map ion imaging. The photoexcited molecules and eventual I atom products are probed by site-selective ionization at the I 4d edge using intense XUV pulses, which induce multiple charges initially localized to the iodine atom. At C-I separations below the critical distance for charge transfer (CT), charge can redistribute around the molecule leading to Coulomb explosion and charged fragments with high kinetic energy.

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Objective: The prognostic value of electroneurography (ENoG) for predicting the incidence of synkinesis is reportedly about 40 % using the formal standard method (ENoG-SM). However, the prognostic value of ENoG using the newly developed midline method (ENoG-MM) has not been determined. The aim of this study was to demonstrate the optimal prognostic value and advantages of ENoG-MM for predicting the incidence of synkinesis.

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Young's double-slit interference experiments with undulator vortex radiation were conducted, focusing on photon-counting regime. To isolate the second harmonic radiation in the ultraviolet range emitted from the helical undulator and achieve successful counting measurements, an ultranarrow bandpass filter was utilized under an extremely low-current mode of the electron storage ring. It was observed that the photon spots on the detector, after passing through the double slits, appeared to be randomly distributed.

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To understand the mechanism underlying the high radio-sensitisation of living cells possessing brominated genomic DNA, X-ray photoelectron spectroscopy (XPS) using synchrotron X-rays with energies of 2000 or 2500 eV was used to study brominated and nonbrominated nucleobases, nucleosides and nucleotides. The bromine atom significantly reduced the energy gap between the valence and conduction states, although the core level states were not greatly affected. This finding was supported by quantum chemical calculation for the nucleobases and nucleosides.

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Objective: To determine the optimal current intensity for supramaximal stimulation during electroneurography (ENoG) for facial palsy.

Methods: Forty patients with unilateral facial palsy (32 Bell's palsy, 7 Ramsay Hunt syndrome, and 1 temporal bone fracture) were enrolled. All patients were initially treated with intravenous steroid injections and examined using ENoG.

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Purpose: To clarify the radiosensitization mechanism masking the Auger effect of the cells possessing brominated DNA, the electronic properties of DNA-related molecules containing Br were investigated by X-ray spectroscopy and specific heat measurement.

Materials And Methods: X-ray absorption near-edge structure (XANES) and X-ray photoemission spectroscopy (XPS) were used to measure the electronic properties of the nucleotides with and without Br. We determined the specific heat of 5-bromouracil crystals with thymine as a reference molecule at low temperatures of 3-48 K to calculate the microscopic state numbers.

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Article Synopsis
  • The study focuses on improving methods to reconstruct the structure of nanoscale samples using coherent diffractive imaging with X-ray free-electron lasers, even when the quality of the diffraction data is low.
  • A new refinement method is introduced that uses a gradient search technique, which takes into account gaps in the diffraction patterns and limited photon detection, enhancing convergence by starting with an initial structure estimate.
  • The method was successfully applied to experimental data from an Xe cluster at the SACLA facility, demonstrating effective reconstruction of electron density from challenging diffraction patterns, thereby aiding in the analysis of samples with low scattering power.
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Using electron spectroscopy, we investigated the nanoplasma formation process generated in xenon clusters by intense soft x-ray free electron laser (FEL) pulses. We found clear FEL intensity dependence of electron spectra. Multistep ionization and subsequent ionization frustration features are evident for the low FEL-intensity region, and the thermal electron emission emerges at the high FEL intensity.

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We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, ScN@C, using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition.

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Objective: Electroneurography (ENoG) reliably predicts the prognosis of facial palsy. However, the results of ENoG are dependent on the location, where the wave is detected, as a compound muscle action potential (CMAP) arising from the facial muscles. To minimize errors in prognostic prediction, we analysed the latencies of facial CMAPs.

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Article Synopsis
  • Researchers measured the momenta of ions produced from diiodomethane molecules after they were ionized multiple times using soft-X-ray free-electron-laser pulses.
  • They utilized covariance methods to analyze the correlations between the ion momenta in a time-of-flight spectroscopy setup for multiparticle systems.
  • The study discusses the rapid dynamics of the dissociating ions and interprets the findings through simulations grounded in a classical Coulomb explosion model that accounts for changes in charge.
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The degree of distress caused by the sequelae of peripheral facial nerve palsy usually depends on the severity of synkinesis. To clarify whether electroneurography (ENoG) can predict the severity of synkinesis after peripheral facial nerve palsy. One-hundred and fourteen patients treated for facial nerve palsy at our hospital from April 2014-September 2016 were retrospectively reviewed.

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The increasing availability of X-ray free-electron lasers (XFELs) has catalyzed the development of single-object structural determination and of structural dynamics tracking in real-time. Disentangling the molecular-level reactions triggered by the interaction with an XFEL pulse is a fundamental step towards developing such applications. Here we report real-time observations of XFEL-induced electronic decay via short-lived transient electronic states in the diiodomethane molecule, using a femtosecond near-infrared probe laser.

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We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays.

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Coulomb explosion of diiodomethane CHI molecules irradiated by ultrashort and intense X-ray pulses from SACLA, the Japanese X-ray free electron laser facility, was investigated by multi-ion coincidence measurements and self-consistent charge density-functional-based tight-binding (SCC-DFTB) simulations. The diiodomethane molecule, containing two heavy-atom X-ray absorbing sites, exhibits a rather different charge generation and nuclear motion dynamics compared to iodomethane CHI with only a single heavy atom, as studied earlier. We focus on charge creation and distribution in CHI in comparison to CHI.

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Objective: Marginal mandibular nerve paralysis is the most frequent complication of benign parotid tumor surgery and results in cosmetic deformity. The purpose of this study was to develop a new electroneurography method for marginal mandibular nerve paralysis using electroneurography (ENoG) and judge its usefulness for clinical practice.

Methods: Twenty-seven patients who underwent surgery for benign parotid tumor were enrolled.

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We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor.

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In recent years, free-electron lasers operating in the true X-ray regime have opened up access to the femtosecond-scale dynamics induced by deep inner-shell ionization. We have investigated charge creation and transfer dynamics in the context of molecular Coulomb explosion of a single molecule, exposed to sequential deep inner-shell ionization within an ultrashort (10 fs) X-ray pulse. The target molecule was CH3I, methane sensitized to X-rays by halogenization with a heavy element, iodine.

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X-ray free-electron lasers (FELs) enable crystallographic data collection using extremely bright femtosecond pulses from microscopic crystals beyond the limitations of conventional radiation damage. This diffraction-before-destruction approach requires a new crystal for each FEL shot and, since the crystals cannot be rotated during the X-ray pulse, data collection requires averaging over many different crystals and a Monte Carlo integration of the diffraction intensities, making the accurate determination of structure factors challenging. To investigate whether sufficient accuracy can be attained for the measurement of anomalous signal, a large data set was collected from lysozyme microcrystals at the newly established `multi-purpose spectroscopy/imaging instrument' of the SPring-8 Ångstrom Compact Free-Electron Laser (SACLA) at RIKEN Harima.

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Conclusion: The midline electroneurography (ENoG) method might reflect total facial nerve degeneration.

Objective: We compared ENoG values in patients with facial palsy using two different methods, the midline method and five electroneurogram recordings, to reveal whether the ENoG value obtained with the midline method reflects total facial nerve degeneration.

Methods: Forty patients with facial palsy were enrolled.

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All matter exposed to intense femtosecond x-ray pulses from the Linac Coherent Light Source free-electron laser is strongly ionized on time scales competing with the inner-shell vacancy lifetimes. We show that for nanoscale objects the environment, i.e.

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Theory predicts that double-core-hole (DCH) spectroscopy can provide a new powerful means of differentiating between similar chemical systems with a sensitivity not hitherto possible. Although DCH ionization on a single site in molecules was recently measured with double- and single-photon absorption, double-core holes with single vacancies on two different sites, allowing unambiguous chemical analysis, have remained elusive. Here we report that direct observation of double-core holes with single vacancies on two different sites produced via sequential two-photon absorption, using short, intense X-ray pulses from the Linac Coherent Light Source free-electron laser and compare it with theoretical modeling.

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