Mid-infrared Free Electron Laser Research Articles

Measurement of temporal evolution of antiferromagnetic domain change in nickel oxide driven by 2TO phonon mode excitation via pump-probe experiment

The temporal evolution of antiferromagnetic domain pattern changes under resonant excitation of the second-order transverse optical phonon mode in nickel oxide was investigated using mid-infrared free electron laser (MIR-FEL) pulses and visible nanosecond probe laser pulses at room temperature. We visualized the domain patterns through magneto-optical polarized microscopy in transmission and observed their temporal variation after the phonon excitation via MIR-FEL. We evaluated the differences throughout the timeline using the structural similarity index measure technique from domain images with and without MIR-FEL irradiation. We found that the MIR-FEL irradiation induces significant structural changes in the domain patterns. The maximum difference was observed at the timing of the MIR-FEL irradiation and exponentially recovered with the time constant of 1.4 ± 0.2 ms. This rather long-time constant could be owing to the spin relaxation, whilst further investigation is needed to confirm the underlying mechanism.

Beam characterization of mid-infrared free electron laser to drive high-harmonic generation

The maximum energy of photons from high-harmonic generation (HHG) increases with the wavelength of the driving laser. A free electron laser (FEL) is a continuously tunable light source in the mid-IR wavelength range and it is useful for investigating the extension of the accessible photon energy in HHG. Recently, the undulator magnets of the IR FEL at the Laboratory for Electron Beam Research and Application (LEBRA), Nihon University, have been replaced, and then the output power of the FEL has increased. Here, we evaluate the pulse duration and focal beam size of the FEL and show that the LEBRA FEL with 2 and 3 μm laser wavelengths under a 44 MHz bunch repetition mode can drive HHG.

Formation of Periodic Surface Structures on Semiconductors under Mid-Infrared Free-Electron Laser Irradiation

Formation of Periodic Surface Structures on Semiconductors under Mid-Infrared Free-Electron Laser Irradiation

Dissociation process of polyalanine aggregates by free electron laser irradiation.

Polyalanine (polyA) disease-causative proteins with an expansion of alanine repeats can be aggregated. Although curative treatments for polyA diseases have not been explored, the dissociation of polyA aggregates likely reduces the cytotoxicity of polyA. Mid-infrared free electron laser (FEL) successfully dissociated multiple aggregates. However, whether the FEL dissociates polyA aggregates like other aggregates has not been tested. Here, we show that FEL at 6.1 μm experimentally weakened the extent of aggregation of a peptide with 13 alanine repeats (13A), and the irradiated 13A exerted lesser cytotoxicity to neuron-like cells than non-irradiated 13A. Then, we applied molecular dynamics (MD) simulation to follow the dissociation process by FEL. We successfully observed how the intermolecular β-sheet of polyA aggregates was dissociated and separated into monomers with helix structures upon FEL irradiation. After the dissociation by FEL, water molecules inhibited the reformation of polyA aggregates. We recently verified the same dissociation process using FEL-treated amyloid-β aggregates. Thus, a common mechanism underlies the dissociation of different protein aggregates that cause different diseases, polyA disease and Alzheimer's disease. However, MD simulation indicated that polyA aggregates are less easily dissociated than amyloid-β aggregates and require longer laser irradiation due to hydrophobic alanine repeats.

Radiation and Emission Phenomena in Combination

Radiation and Emission Phenomena in Combination

Construction and tests of phosphor view screen station for monitoring transverse profile of electron beam at PCELL

Development of an accelerator-based light source for generating coherent terahertz (THz) and mid-infrared (MIR) free-electron laser (FEL) is ongoing at the PBP-CMU Electron Linac Laboratory (PCELL). For producing high quality radiation, suitable electron beam property is necessary. In particle accelerator technology, transverse beam distribution and profile can be measured by using several techniques. The beam monitoring using view screen station is one of popular and effective methods. At PCELL, we use stations consisting of phosphor screen equipped with CCD camera to monitor, measure and record the beam image along the accelerator system and beamlines. The phosphor screen was chosen due to its high spatial resolution. The phosphor film is uniformly coated on a thin aluminium plate. Its green emission when electrons hitting the screen is matched well with the respond of the CCD camera. The screen can be moved in and out from the vacuum chamber using the air pressurized linear actuator. This paper presents about design, construction and tests of the screen stations at PCELL. The resolution of measurements for beam transverse profile and emittance is also be discussed.

Investigation of bactericidal effect of a mid-infrared free electron laser on Escherichia coli

The rapid increase in the number of bacteria that are resistant to many commonly used antimicrobial agents and their global spread have become a major problem worldwide. In particular, for periodontal disease, which is a localized infection, there is a growing need for treatment methods that do not primarily involve antimicrobial agents, and antimicrobial photodynamic therapy (aPDT) is attracting attention. In this study, the bactericidal effects of a mid-infrared free electron laser (MIR-FEL) on E. coli were investigated as a basic study to examine the applicability of MIR-FELs, which can selectively excite molecular vibrations due to their wavelength tunability, to aPDT. The optimal irradiation wavelengths to be examined in this study were determined from the infrared spectrum of the bacteria, which was obtained using Fourier transform infrared spectroscopy. Five irradiation wavelengths (6.62, 6.88, 7.14, 8.09 and 9.26 µm) were selected from the FT-IR spectrum, and we found that the bactericidal effects at a wavelength of 6.62 µm were markedly stronger than those observed at the other wavelengths. At this wavelength corresponding to the Amide II band, the bacterial survival rate decreased significantly as the irradiation time increased. On the contrary, irradiation of a neodymium-doped yttrium aluminum garnet (Nd: YAG) laser at 1.06 µm exhibited no distinct bactericidal effect. No morphological changes were observed after MIR-FEL irradiation, suggesting that a bacterial organelle molecule may be the target of MIR-FEL irradiation, but the exact target was not identified. Furthermore, the temperature change induced in the culture medium by the laser irradiation was ± 1.5 °C at room temperature. These results suggest that the bactericidal effects of MIR-FEL are derived from photochemical reactions involving infrared photons, since E. coli is usually killed by heating it to 75 °C for 1 min or longer.

Suppression of Prostate Cancer Cell Growth by Mid-Infrared Rays

Experiments using rubber/resin foam (RB) have already shown that far-infrared rays suppress the proliferation of cancer cells. We will report as a follow up to these findings. When RB was used, the temperature of the culture solution increased by about 0.4°C. This time, with a focus on this temperature rise, a new heating plate was manufactured, and culture experiments were conducted without using RB. It was determined that the suppression of growth was because of heat transfer, not due to the special action of RB. The distribution of heat was calculated using Planck’s formula, and it was speculated that mid-infrared rays around 4.8 µm are involved in the inhibition of cancer cell proliferation. Furthermore, irradiation with a 4.8 µm mid-infrared free electron laser confirmed that the ratio of α-helix to β-sheet changed, providing corroborative evidence for growth suppression.

Stacking Is Favored over Hydrogen Bonding in Azaphenanthrene Dimers.

N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.

Enhancement of Oxidation of Silicon Carbide Originating from Stacking Faults Formed by Mode-Selective Phonon Excitation Using a Mid-Infrared Free Electron Laser.

Silicon carbide (SiC) is a promising material for wide applications due to its excellent material properties including high physical and chemical stability as well as great electronic properties of a wide bandgap. The high stability, however, makes its surface processing difficult. Especially, electrochemical processing is not well-established because of low electrochemical reactivity. Here, we show that selective phonon excitation by a mid-infrared free electron laser (MIR-FEL) enhances the anodic reactions. The selective excitation of two different vibration modes of the Si-C bond induces two different stacking faults, which act as a current path. As an application, we discovered that MIR-FEL irradiation enables Pt electroless deposition. This work reveals the interactions among phonons, lattice defects, and electrochemical reactions, encouraging further development of not only electrochemical surface processing but also a new application of MIR-FEL.

Mode-selective excitation of an infrared-inactive phonon mode in diamond using mid-infrared free electron laser

The direct demonstration was achieved for the selective excitation of the infrared-inactive T 2g mode (1332 cm−1) in the single crystal diamond by two-photon excitation using a mid-infrared free electron laser (MIR-FEL) as pump light. Anti-Stokes Raman scattering light at around −1339 cm−1 was observed with cooling at 5 K only when MIR-FEL whose wavenumber was that of one-half of the T 2g mode, 666 cm−1, was irradiated. Update of the probe system, i.e. the introduction of the image intensified CCD, made it possible to probe the scattering signal with a lower laser power density compared to our previous study, and it relieved the surface damage on the sample accompanied by laser irradiations which induced a red-shift and a band broadening of the mode in the previous study.

Application of mid-infrared free-electron laser for structural analysis of biological materials.

A mid-infrared free-electron laser (MIR-FEL) is a synchrotron-radiation-based femto- to pico-second pulse laser. It has unique characteristics such as variable wavelengths in the infrared region and an intense pulse energy. So far, MIR-FELs have been utilized to perform multi-photon absorption reactions against various gas molecules and protein aggregates in physical chemistry and biomedical fields. However, the applicability of MIR-FELs for the structural analysis of solid materials is not well recognized in the analytical field. In the current study, an MIR-FEL is applied for the first time to analyse the internal structure of biological materials by using fossilized inks from cephalopods as themodel sample. Two kinds of fossilized inks that were collected from different strata were irradiated at the dry state by tuning the oscillation wavelengths of the MIR-FEL to the phosphoryl stretching mode of hydroxyapatite (9.6 µm) and to the carbonyl stretching mode of melanin (5.8 µm), and the subsequent structural changes in those materials were observed by using infrared microscopy and far-infrared spectroscopy. The structural variation of these biological fossils is discussed based on the infrared-absorption spectral changes that were enhanced by the MIR-FEL irradiation, and the potential use of MIR-FELs for the structural evaluation of biomaterials is suggested.

Investigation of electron energy spread effects on the intracavity MIR-FEL power at the PBP-CMU electron linac laboratory

At the PBP-CMU Electron Linac Laboratory, the existing linear accelerator system is under developing to produce electron beams with suitable properties for generation of oscillator mid-infrared free-electron laser (MIR-FEL) and super-radiant terahertz (THz) undulator radiation. This work focuses on the simulation of the oscillator MIR-FEL with expected electron beam energy of 20 – 25 MeV to evaluate the required electron beam parameters. To achieve FEL saturation, the single-pass FEL simulation using the code GENESIS 1.3 was performed to estimate the laser wavelength, FEL gain and electron macro-pulse duration. In the simulation, electron beams with energy spread of 0, 0.5 and 1.0 %, and the electron peak current of 25 and 50 A were considered. As a result, the electron beam with energy of 20 – 25 MeV can produce the FEL wavelengths of 13.5 – 21.2 µm using a 1.6-m undulator with maximum undulator parameter of 1.07. The largest FEL gain is 216% when using electron beam energy and peak current of 20 ± 0% MeV and 50 A, which requires the electron macro-pulse duration of 1.6 µs to saturate FEL. Due to the possible macro-pulse duration at our facility of 6 µs, the operation of electron beam with energy spread of 0.5% and peak current of higher than 25 A is required to saturate FEL. Results from this single-pass simulation can be used as a based information for further practical consideration with multi-pass simulation.

Record high extraction efficiency of free electron laser oscillator

The highest extraction efficiency (9.4%) of a free electron laser (FEL) oscillator has been achieved at the midinfrared FEL facility of Kyoto University. Because of the interaction between the electron beam and FEL electromagnetic field, a maximum electron energy decrease of 16% was observed. The measured energy decrease was consistent with the measured FEL spectrum. An FEL micropulse energy of ∼100 μJ with the expected few-cycle pulse duration at a wavelength of 11 μm was observed. This result is an important milestone for the high-extraction-efficiency FEL oscillator and will contribute to the strong-field physics of atoms and molecules.

Infrared Laser-Induced Amyloid Fibril Dissociation: A Joint Experimental/Theoretical Study on the GNNQQNY Peptide.

Neurodegenerative diseases are usually characterized by plaques made of well-ordered aggregates of distinct amyloid proteins. Dissociating these very stable amyloid plaques is a critical clinical issue. In this study, we present a joint mid-infrared free electron laser experiment/nonequilibrium molecular dynamics simulation to understand the dissociation process of a representative example GNNQQNY fibril. By tuning the laser frequency to the amide I band of the fibril, the resonance takes place and dissociation is occurred. With the calculated and observed wide-angle X-ray scattering profiles and secondary structures before and after laser irradiation being identical, we can propose a dissociation mechanism with high confidence from our simulations. We find that dissociation starts in the core of the fibrils by fragmenting the intermolecular hydrogen bonds and separating the peptides and then propagates to the fibril extremities leading to the formation of unstructured expanded oligomers. We suggest that this should be a generic mechanism of the laser-induced dissociation of amyloid fibrils.

Cellulose Degradation by Infrared Free Electron Laser

We introduce a green approach to obtain glucose and low-molecular-weight saccharides directly from the cellulose aggregate by using near- and mid-infrared free electron lasers (IR-FELs). The IR-FEL...

Degradation of Human Serum Albumin by Infrared Free Electron Laser Enhanced by Inclusion of a Salen-Type Schiff Base Zn (II) Complex.

A salen-type Schiff base Zn(II) complex included in human serum albumin (HSA) protein was examined by UV-Vis, circular dichroism (CD), and fluorescence (PL) spectra. The formation of the composite material was also estimated by a GOLD program of ligand–protein docking simulation. A composite cast film of HSA and Zn(II) complex was prepared, and the effects of the docking of the metal complex on the degradation of protein molecules by mid-infrared free electron laser (IR-FEL) were investigated. The optimum wavelengths of IR-FEL irradiation to be used were based on experimental FT-IR spectra and vibrational analysis. Using TD-DFT results with 6-31G(d,p) and B3LYP, the IR spectrum of Zn(II) complex could be reasonably assigned. The respective wavelengths were 1652 cm−1 (HSA amide I), 1537 cm−1 (HSA amide II), and 1622 cm−1 (Zn(II) complex C=N). Degradation of HSA based on FT-IR microscope (IRM) analysis and protein secondary structure analysis program (IR-SSE) revealed that the composite material was degraded more than pure HSA or Zn(II) complex; the inclusion of Zn(II) complex enhanced destabilization of folding of HSA.

Two-photon selective excitation of phonon-mode in diamond using mid-infrared free-electron laser

Two-photon selective excitation of an infrared (IR)-inactive phonon mode by a mid-infrared tunable free-electron laser (FEL) was accomplished. The mode-selective phonon excitation of IR-active mode by one-photon excitation using FEL (Yoshida et al. (2013) [20]) was extended to the IR-inactive mode excitation. The T2g optical phonon mode in single-crystal diamond at 1,332cm−1 was selected, and the FEL photon energy corresponding to the oscillation wavelength was tuned to the half of the target phonon energy. The successful mode excitation was confirmed by anti-Stokes Raman scattering signal of T2g for the sample at cryogenic temperature, where all other modes were suppressed. The signal was observed at T2g phonon energy with red-shift of the peak to 1,306cm−1, which was accompanied by surface damage induced by intense laser irradiations.

Study on Irradiation Effect of Mid-Infrared Free Electron Laser on Hen Egg-White Lysozyme by Using Terahertz-Time Domain Spectroscopy and Synchrotron-Radiation Vacuum-Ultraviolet Circular-Dichroism Spectroscopy

Mid-infrared free-electron laser (MIR-FEL) is potentially applicable for tissue ablation and dissociation of pathological peptide aggregates in medicine. However, it is still poorly understood how the MIR-FEL irradiation influences on functional proteins such as enzymes. In the current study, the effect of MIR-FEL on both aggregate and non-aggregate (= native) states of hen egg-white lysozyme (HEWL) as a representative enzyme has been investigated. Absorption intensity at terahertz region (0.3–1.2 THz, 10–40 cm−1) of the aggregate of HEWL was lower than that of the native HEWL, but the former was increased nearly to the same level with the latter after the MIR-FEL irradiation tuned to 6 μm that corresponds to carbonyl stretching vibrational mode of amide bonds (amide I). This indicates that the aggregate of HEWL was converted to the native state by the irradiation. On the other hand, synchrotron-radiation vacuum-ultraviolet circular-dichroism spectroscopy showed that protein conformation of the native HEWL, which was rich in α-helix, was little changed after the MIR-FEL irradiation under the same condition with the case of the aggregate of HEWL. Furthermore, the enzymatic hydrolysis activity of the native HEWL against bacterial glycan was not remarkably decreased by the irradiation. Therefore, it can be estimated that the native structure of HEWL is little damaged although the aggregate state can be easily dissociated by the resonant excitation at amide bonds.

Wavelength Dependence of Poly(<i>p</i>-hydroxystyrene) Ablation by Mid-Infrared Free-Electron Laser

Ablation of polymer thin films for resists was studied using a mid-Infrared (IR) Free-Electron Laser (FEL). Irradiation fluence of the IR light in the mid-IR region (5.6 to 8.0 μm) to a thin film of poly(p-hydroxystyrene) (PHOST) on a silicon wafer increased to cause PHOST ablation. The ablated spot size was smaller than the irradiated area calculated by wave optics, because the ablation is a multiphoton absorption process. The ablation threshold energy was determined using the irradiation area calculated by the wave optics. The threshold energy depended upon the film thickness of PHOST and irradiation wavelength of FEL. The threshold energy of thin PHOST film with 61 nm increased at the wavelength of vibrational modes of phenyl ring. It associates the durability of phenyl ring to photon decomposition.