Exploring the ultrafast and isomer-dependent photodissociation of iodothiophenes via site-selective ionization.

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. At greater C-I separations, beyond the critical distance, CT is no longer possible and the measured kinetic energies of the charged iodine atoms report on the neutral dissociation process. The time and momentum resolved measurements allow determination of the timescales and the respective product momentum and kinetic energy distributions for both isomers, which are interpreted in terms of rival 'direct' and 'indirect' dissociation pathways. The measurements are compared with a classical over the barrier model, which reveals that the onset of the indirect dissociation process is delayed by ∼1 ps relative to the direct process. The kinetics of the two processes show no discernible difference between the two parent isomers, but the branching between the direct and indirect dissociation channels and the respective product momentum distributions show isomer dependencies. The greater relative yield of indirect dissociation products from 262 nm photolysis of 3-iodothiophene (cf. 2-iodothiophene) is attributed to the different partial cross-sections for (ring-centred) π∗ ← π and (C-I bond localized) σ∗ ← (n/π) excitation in the respective parent isomers.

Prognostic value of electroneurography using the midline method for predicting the development of synkinesis after peripheral facial palsy.

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. METHODS: Participants were 573 patients treated for peripheral facial palsy including Bell's palsy or Ramsay Hunt syndrome. We investigated the clinical presence of any oral-ocular or ocular-oral synkinesis from the medical records. ENoG-MM and ENoG-SM were performed 10-14 days after symptom onset. In ENoG-MM, compound muscle action potentials were recorded by placing the anode on the mental protuberance and the cathode on the philtrum. In ENoG-SM, electrodes were placed on the nasolabial fold. Synkinesis was clinically assessed at the end of follow-up or at >1 year after onset. The sensitivity and specificity of ENoG values for predicting the incidence of synkinesis were compared between ENoG-MM and ENoG-SM at every 5 % around 40 % (range, 30-50 %). RESULTS: At every 5 % of ENoG values around 40 %, ENoG-MM provided higher sensitivity and lower specificity for predicting the incidence of synkinesis compared with ENoG-SM. In particular, when the cut-off value was set at 45 %, sensitivity was 100 % and 95.3 % with ENoG-MM and ENoG-SM, respectively. CONCLUSION: In peripheral facial palsy, ENoG-MM offered higher sensitivity than ENoG-SM for predicting synkinesis. ENoG-MM is useful for screening patients at risk of developing synkinesis. In clinical practice, an ENoG-MM cut-off value of 45 % must be the optimal prognostic value because of the 100 % sensitivity.

Young's double-slit experiment with undulator vortex radiation in the photon-counting regime.

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. However, upon integrating these photon spots, it was confirmed that interference fringes with characteristic features of optical vortices, such as dark and broken/distorted stripes in the center, were formed. The reproducibility of these interference fringes was confirmed by calculating the optical path difference for the optical vortex reaching the double slits, as well as the optical path difference resulting from normal double-slit interference. Consequently, these findings indicate that even in the state of a single photon, the radiation emitted spontaneously by a high-energy electron in spiral motion possesses the nature of an optical vortex, characterized by a spiral wavefront.

Incorporation of a bromine atom into DNA-related molecules changes their electronic properties.

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. Our findings strongly indicate that the energy gaps between the valence and conduction levels of the molecules are significantly reduced by bromination. Furthermore, the brominated molecules are more likely to produce inelastic scattering low energy electrons upon exposure to 2000 or 3000 eV X-rays. This modification of electronic properties around the brominated group may both facilitate electron transfer to the brominated site in DNA and increase the probability of reaction with low energy electrons. These processes can induce DNA damage, presumably resulting in debromination of the uracil moiety and a subsequent cytotoxic effect.

Electronic properties of DNA-related molecules containing a bromine atom.

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. RESULTS: Obtained XANES and XPS spectra indicated that both the lowest unoccupied molecular orbital (LUMO) and the core-levels were not affected by the Br incorporation. The state numbers of 5-bromouracil calculated from the specific heats obtained around 25 K was about 1.5 times larger than that for thymine below 20 K, although the numbers were almost the same below 5 K. DISCUSSION: Our results suggest that the Br atom may not contribute substantially to the LUMO and core-level electronic states of the molecule, but rather to the microscopic states related to the excitation of lattice vibrations, which may be involved in valence electronic states.

Optimal current intensity for supramaximal stimulation during electroneurography for facial palsy.

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. Compound muscle action potentials (CMAPs) of the orbicularis oris muscle were measured on the paralyzed and healthy sides. Stimulation current intensity was varied every 5 mA from 20 mA to 50 mA using two recording methods (the midline and standard methods). The CMAPs of both sides were monitored to see whether they would saturate under the high current intensity stimulation or not. RESULTS: No obvious saturation of CMAPs was observed in either side with the midline or standard methods. Statistically, a current of 35 mA and above in the healthy side, and 30 mA and above in the paralytic side, resulted in no difference to each side when using the midline recording method. On the other hand, a current of 35 mA and above in the healthy side, and 25 mA and above in the paralytic side, resulted in no difference to each side when using the standard recording method. CONCLUSIONS: These results indicate that a current intensity of at least 35 mA is required to achieve supramaximal stimulation on the healthy side in a patient with unilateral facial nerve palsy. Clinically, for simplicity or standardization purposes, if the same current intensity is introduced bilaterally for ENoG measurements, adopting 40 mA (35 mA plus 10-20%) stimulation would be appropriate for supramaximal stimulation, while being cognizant of the potential effects of artifacts from other muscles.

Refinement for single-nanoparticle structure determination from low-quality single-shot coherent diffraction data.

With the emergence of X-ray free-electron lasers, it is possible to investigate the structure of nanoscale samples by employing coherent diffractive imaging in the X-ray spectral regime. In this work, we developed a refinement method for structure reconstruction applicable to low-quality coherent diffraction data. The method is based on the gradient search method and considers the missing region of a diffraction pattern and the small number of detected photons. We introduced an initial estimate of the structure in the method to improve the convergence. The present method is applied to an experimental diffraction pattern of an Xe cluster obtained in an X-ray scattering experiment at the SPring-8 Angstrom Compact free-electron LAser (SACLA) facility. It is found that the electron density is successfully reconstructed from the diffraction pattern with a large missing region, with a good initial estimate of the structure. The diffraction pattern calculated from the reconstructed electron density reproduced the observed diffraction pattern well, including the characteristic intensity modulation in each ring. Our refinement method enables structure reconstruction from diffraction patterns under difficulties such as missing areas and low diffraction intensity, and it is potentially applicable to the structure determination of samples that have low scattering power.

Multi-particle momentum correlations extracted using covariance methods on multiple-ionization of diiodomethane molecules by soft-X-ray free-electron laser pulses.

Momenta of ions from diiodomethane molecules after multiple ionization by soft-X-ray free-electron-laser pulses are measured. Correlations between the ion momenta are extracted by covariance methods formulated for the use in multiparticle momentum-resolved ion time-of-flight spectroscopy. Femtosecond dynamics of the dissociating multiply charged diiodomethane cations is discussed and interpreted by using simulations based on a classical Coulomb explosion model including charge evolution.

Electron spectroscopic study of nanoplasma formation triggered by intense soft x-ray pulses.

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. The present FEL intensity dependence of the electron spectra is well addressed by the frustration parameter introduced by Arbeiter and Fennel [New J. Phys. 13, 053022 (2011)].

Photo-ionization and fragmentation of Sc3N@C80 following excitation above the Sc K-edge.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, Sc3N@C80, 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. In contrast to previous studies, no intermediate regime of C2 evaporation from the carbon cage is observed. A time-delayed, hard x-ray pulse (hν = 5.0 keV) was used to attempt to probe the electron transfer dynamics between the encapsulated Sc species and the carbon cage. A small but significant change in the intensity of Sc-containing fragment ions and coincidence counts for a delay of 100 fs compared to 0 fs, as well as an increase in the yield of small carbon fragment ions, may be indicative of incomplete charge transfer from the carbon cage on the sub-100 fs time scale.

Latency shift in compound muscle action potentials during electroneurography in facial palsy.

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. MATERIALS AND METHODS: Fifty-seven patients with unilateral peripheral facial palsy and 24 healthy volunteers were enrolled. Amplitudes, negative peak latencies (NPL), and rise latencies (RL) of CMAPs were measured on the paralysed and healthy sides in patients and in healthy volunteers. The relationships of these latencies with ENoG values and the lowest House-Brackmann (H-B) scores were also analysed. RESULTS: The amplitude of CMAP on the paralysed side was smaller, and NPL and RL were longer, than those on the healthy side in patients and healthy volunteers (p < 0.01). In patients, there was no difference in NPL between the ENoG < 40% group and the ENoG ≥ 40% group. Conversely, there was a significant difference in RL between the ENoG < 40% group and ENoG ≥ 40% group (p = 0.03). No relationships were observed between NPL or RL and the lowest H-B score. CONCLUSIONS: NPL and RL of CMAP on the paralysed side were equivalent or longer than those on the healthy side. During ENoG for facial palsy, CMAP should be measured on the healthy side first, and then detected (and the amplitude measured) on the paralysed side with reference to CMAP latency on the healthy side, to reduce errors in detecting facial CMAPs.

Electroneurography value as an indicator of high risk for the development of moderate-to-severe synkinesis after Bell's palsy and Ramsay Hunt syndrome.

Background: The degree of distress caused by the sequelae of peripheral facial nerve palsy usually depends on the severity of synkinesis. Objective: To clarify whether electroneurography (ENoG) can predict the severity of synkinesis after peripheral facial nerve palsy. Materials and methods: One-hundred and fourteen patients treated for facial nerve palsy at our hospital from April 2014-September 2016 were retrospectively reviewed. ENoG was performed 10-16 days after symptom onset. Patients were classified into Groups A (ENoG value 10%-20%, n = 9) and B (ENoG value <10%, n = 21). Eight months after symptom onset, electrophysiological and symptomatic outcomes were evaluated as the aberrant regeneration ratio of the blink reflex and the total synkinesis score of the Sunnybrook facial grading system, respectively. The outcomes of the groups were compared. Results: Group B had a significantly higher median aberrant regeneration ratio (0% versus 87%, p=.015), median total synkinesis score (1 versus 3, p < .001), and incidence of moderate-to-severe synkinesis (0% versus 57.2%, p=.003) than did Group A. Conclusions and significance: Patients with an ENoG value of <10% have higher risks of aberrant regeneration and moderate-to-severe synkinesis than those with an ENoG value of 10%-20%. Patients with ENoG values of <10% may require rehabilitation to prevent synkinesis.

Real-time observation of X-ray-induced intramolecular and interatomic electronic decay in CH2I2.

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. We determine the lifetimes of the transient states populated during the XFEL-induced Auger cascades and find that multiply charged iodine ions are issued from short-lived (∼20 fs) transient states, whereas the singly charged ones originate from significantly longer-lived states (∼100 fs). We identify the mechanisms behind these different time scales: contrary to the short-lived transient states which relax by molecular Auger decay, the long-lived ones decay by an interatomic Coulombic decay between two iodine atoms, during the molecular fragmentation.

Radiation-Induced Chemical Dynamics in Ar Clusters Exposed to Strong X-Ray Pulses.

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. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to "damage and destroy" molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

Ultrafast Coulomb explosion of a diiodomethane molecule induced by an X-ray free-electron laser pulse.

Coulomb explosion of diiodomethane CH2I2 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 CH3I with only a single heavy atom, as studied earlier. We focus on charge creation and distribution in CH2I2 in comparison to CH3I. The release of kinetic energy into atomic ion fragments is also studied by comparing SCC-DFTB simulations with the experiment. Compared to earlier simulations, several key enhancements are made, such as the introduction of a bond axis recoil model, where vibrational energy generated during charge creation processes induces only bond stretching or shrinking. We also propose an analytical Coulomb energy partition model to extract the essential mechanism of Coulomb explosion of molecules from the computed and the experimentally measured kinetic energies of fragment atomic ions by partitioning each pair Coulomb interaction energy into two ions of the pair under the constraint of momentum conservation. Effective internuclear distances assigned to individual fragment ions at the critical moment of the Coulomb explosion are then estimated from the average kinetic energies of the ions. We demonstrate, with good agreement between the experiment and the SCC-DFTB simulation, how the more heavily charged iodine fragments and their interplay define the characteristic features of the Coulomb explosion of CH2I2. The present study also confirms earlier findings concerning the magnitude of bond elongation in the ultrashort X-ray pulse duration, showing that structural damage to all but C-H bonds does not develop to a noticeable degree in the pulse length of ∼10 fs.

A new electroneurography as a prognostic tool for marginal mandibular nerve paralysis after parotid gland surgery: A preliminary evaluation.

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. We proposed and use the mandibular angle method, in which the recording electrode was placed on the skin above the depressor anguli oris muscle while the reference electrode was placed on the skin of the parietal region, and percutaneous electrical stimulation was applied to enclose the mandibular angle that could measure the function of the marginal mandibular nerve solely. Preoperative and postoperative ENoG values were compared in paralytic and non-paralytic patients. RESULTS: The mean postoperative ENoG value (35.0%) was lower than the preoperative value (90.5%) in paralytic patients, whereas no difference was observed between preoperative (79.3%) and postoperative (69.5%) ENoG values in non-paralytic patients. CONCLUSION: A new ENoG method (mandibular angle method) was thought to reflect marginal mandibular nerve injury and might be useful for determining the likelihood of paralysis.

Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles.

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. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs' surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials.

Charge and Nuclear Dynamics Induced by Deep Inner-Shell Multiphoton Ionization of CH3I Molecules by Intense X-ray Free-Electron Laser Pulses.

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. Time-of-flight ion spectroscopy and coincident ion analysis was employed to investigate, via the properties of the atomic fragments, single-molecule charge states of up to +22. Experimental findings have been compared with a parametric model of simultaneous Coulomb explosion and charge transfer in the molecule. The study demonstrates that including realistic charge dynamics is imperative when molecular Coulomb explosion experiments using short-pulse facilities are performed.

Anomalous signal from S atoms in protein crystallographic data from an X-ray free-electron laser.

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. Anomalous difference density maps calculated from these data demonstrate that serial femtosecond crystallography using a free-electron laser is sufficiently accurate to measure even the very weak anomalous signal of naturally occurring S atoms in a protein at a photon energy of 7.3 keV.

The midline electroneurography method for facial palsy reflects total nerve degeneration.

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. Compound muscle action potentials (CMAPs) were recorded using the midline method, in which the anode was placed on the mental protuberance and the cathode was placed on the philtrum. Additionally, five electroneurogram recordings were obtained by placing the anode on the skin of the parietal region and five cathodes on the skin over five facial muscles (frontalis, orbicularis oculi, nasalis, orbicularis oris, and depressor anguli oris muscles). ENoG values recorded using the two methods were compared. RESULTS: The ENoG values of the five facial muscles did not differ from those obtained using the midline method. The total ENoG value calculated by summing five CMAPs from five facial muscles, which is considered to reflect total facial nerve degeneration, was not significantly different from that using midline methods; moreover, a strong positive correlation coefficient (r = 0.87) was found between them.