Observing ice structure of micron-sized vapor-deposited ice with an x-ray free-electron laser.

The direct observation of the structure of micrometer-sized vapor-deposited ice is performed at Pohang Accelerator Laboratory x-ray free electron laser (PAL-XFEL). The formation of micrometer-sized ice crystals and their structure is important in various fields, including atmospheric science, cryobiology, and astrophysics, but understanding the structure of micrometer-sized ice crystals remains challenging due to the lack of direct observation. Using intense x-ray diffraction from PAL-XFEL, we could observe the structure of micrometer-sized vapor-deposited ice below 150 K with a thickness of 2-50 µm grown in an ultrahigh vacuum chamber. The structure of the ice grown comprises cubic and hexagonal sequences that are randomly arranged to produce a stacking-disordered ice. We observed that ice with a high cubicity of more than 80% was transformed to partially oriented hexagonal ice when the thickness of the ice deposition grew beyond 5 µm. This suggests that precise temperature control and clean deposition conditions allow µm-thick ice films with high cubicity to be grown on hydrophilic Si3N4 membranes. The low influence of impurities could enable in situ diffraction experiments of ice nucleation and growth from interfacial layers to bulk ice.

Ultra-wideband transmission filter based on guided-mode resonances in two terahertz metasurfaces.

This paper reports on a broadband transmission filter that employs the guided mode resonances pertaining to a terahertz metasurface composed of metallic gold disks with a quartz slab. Unlike structures involving conventional metasurfaces, two identical metasurfaces are placed on the upper and lower sides of a thick quartz slab. This structure can excite both even and odd guided mode resonances. The interaction of the two resonances at similar frequencies produces a broadband transmission peak. The sharp spectral feature of each resonance leads to the abrupt degradation of the transmission at the spectral edge, which can enable the development of the filter application. The proposed scheme can facilitate practical applications such as those of broadband filters at a terahertz frequency.

Switching to Hidden Metallic Crystal Phase in Phase-Change Materials by Photoenhanced Metavalent Bonding.

Metavalent bonding is crucial for the determination of phase transition and improvement of device performance in phase-change materials, which are attracting interest for use in memory devices. Although monitoring dielectric and phononic parameters provides a direct measure of the metavalent bonding, the control of phase-change phenomena and metavalent bonding in the dynamical regime has yet to be demonstrated. This study reports the photoenhanced metavalent bonding and resulting hidden metallic crystalline state of Ti-doped Sb2Te3, a representative phase-change material with ultralong sustainability. Using ultrafast terahertz spectroscopy, Ti0.4Sb2Te3 was discovered to possess ultralong pump-probe dynamics, which is retained over hundreds of picoseconds, unlike the short-lived state of undoped Sb2Te3. Moreover, for Ti0.4Sb2Te3 during the long-lived transmission change, the infrared-active phonon is highly softened, even more than the amount of a thermal phonon shift, indicating the photoenhancement of lattice anharmonicity. Such a long-lived relaxation implies photoinduced transition into a crystalline state of ultrastrong metavalent bonding in Ti0.4Sb2Te3, on the basis of comparisons of the dynamical dielectric constant and temporal phonon shift. Our results show the realization of photoengineering of phase-change materials by tuning electron sharing or transferring.

Remote impacts of 2009 and 2015 El Niño on oceanic and biological processes in a marginal sea of the Northwestern Pacific.

The significance of long-term teleconnections derived from the anomalous climatic conditions of El Niño has been a highly debated topic, where the remote response of coastal hydrodynamics and marine ecosystems to El Niño conditions is not completely understood. The 14-year long data from a ship-borne acoustic Doppler current profiler was used to examine the El Niño's impact, in particular, 2009 and 2015 El Niño events, on oceanic and biological processes in coastal regions across the Korea/Tsushima Strait. Here, it was revealed that the summer volume transport could be decreased by 8.7% (from 2.46 ± 0.39 to 2.24 ± 0.26 Sv) due to the anomalous northerly winds in the developing year of El Niño. Furthermore, the fall mean volume backscattering strength could be decreased by 1.8% (from - 97.09 ± 2.14 to - 98.84 ± 2.10 dB) due to the decreased surface solar radiation after the El Niño events. Overall, 2009 and 2015 El Niño events remotely affected volume transport and zooplankton abundance across the Korea/Tsushima Strait through climatic teleconnections.

Blockade of translationally controlled tumor protein attenuated the aggressiveness of fibroblast-like synoviocytes and ameliorated collagen-induced arthritis.

Histamine releasing factor/translationally controlled tumor protein (HRF/TCTP) stimulates cancer progression and allergic responses, but the role of HRF/TCTP in rheumatoid arthritis (RA) remains undefined. In this study, we explored the pathogenic significance of HRF/TCTP and evaluated the therapeutic effects of HRF/TCTP blockade in RA. HRF/TCTP transgenic (TG) and knockdown (KD) mice with collagen-induced arthritis (CIA) were used to determine the experimental phenotypes of RA. HRF/TCTP levels in the sera of RA patients were measured and compared to those from patients with osteoarthritis (OA), ankylosing spondylitis, Behçet's disease, and healthy controls. HRF/TCTP expression was also assessed in the synovium and fibroblast-like synoviocytes (FLSs) obtained from RA or OA patients. Finally, we assessed the effects of HRF/TCTP and dimerized HRF/TCTP-binding peptide-2 (dTBP2), an HRF/TCTP inhibitor, in RA-FLSs and CIA mice. Our clinical, radiological, histological, and biochemical analyses indicate that inflammatory responses and joint destruction were increased in HRF/TCTP TG mice and decreased in KD mice compared to wild-type littermates. HRF/TCTP levels in the sera, synovial fluid, synovium, and FLSs were higher in patients with RA than in control groups. Serum levels of HRF/TCTP correlated well with RA disease activity. The tumor-like aggressiveness of RA-FLSs was exacerbated by HRF/TCTP stimulation and ameliorated by dTBP2 treatment. dTBP2 exerted protective and therapeutic effects in CIA mice and had no detrimental effects in a murine tuberculosis model. Our results indicate that HRF/TCTP is a novel biomarker and therapeutic target for the diagnosis and treatment of RA.

Time-resolved resonant elastic soft x-ray scattering at Pohang Accelerator Laboratory X-ray Free Electron Laser.

Resonant elastic x-ray scattering has been widely employed for exploring complex electronic ordering phenomena, such as charge, spin, and orbital order, in particular, in strongly correlated electronic systems. In addition, recent developments in pump-probe x-ray scattering allow us to expand the investigation of the temporal dynamics of such orders. Here, we introduce a new time-resolved Resonant Soft X-ray Scattering (tr-RSXS) endstation developed at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). This endstation has an optical laser (wavelength of 800 nm plus harmonics) as the pump source. Based on the commissioning results, the tr-RSXS at PAL-XFEL can deliver a soft x-ray probe (400 eV-1300 eV) with a time resolution of ∼100 fs without jitter correction. As an example, the temporal dynamics of a charge density wave on a high-temperature cuprate superconductor is demonstrated.

Universal field-tunable terahertz emission by ultrafast photoinduced demagnetization in Fe, Ni, and Co ferromagnetic films.

We report a universal terahertz (THz) emission behavior from simple Ni, Fe, and Co metallic ferromagnetic films, triggered by the femtosecond laser pulse and subsequent photoinduced demagnetization on an ultrafast time scale. THz emission behavior in ferromagnetic films is found to be consistent with initial magnetization states controlled by external fields, where the hysteresis of the maximal THz emission signal is observed to be well-matched with the magnetic hysteresis curve. It is experimentally demonstrated that the ultrafast THz emission by the photoinduced demagnetization is controllable in a simple way by external fields as well as pump fluences.

Toll-like receptor 4 signaling-mediated responses are critically engaged in optimal host protection against highly virulent Mycobacterium tuberculosis K infection.

Toll-like receptors (TLRs) play critical roles in the innate recognition of Mycobacterium tuberculosis (Mtb) by host immune cells. However, controversy has arisen regarding the role of TLR4 in determining the outcomes of Mtb infection. To address this controversy, the function of TLR4 in the induction of an optimal protective immune response against the highly virulent Mtb K-infection was comparatively investigated in C3 H/HeJ (TLR4-deficient mutant) and C3 H/HeN (TLR4-competent wild-type) mice. Interestingly, following Mtb infection, C3 H/HeJ mice showed a more severe disease phenotype than C3 H/HeN mice, exhibiting reduced weight and a marked increase in bacterial burden along with necrotic lung inflammation. Analysis of the immune cell composition revealed significantly increased neutrophils in the lung and significant production of IL-10 accompanied by the impairment of the protective Th1 response in C3 H/HeJ mice. Reducing the neutrophil numbers by treating C3 H/HeJ mice with an anti-Ly6 G monoclonal antibody (mAb) and blocking IL-10 signaling with an anti-IL-10 receptor mAb reduced the excessive lung inflammation and bacterial burden in C3 H/HeJ mice. Therefore, abundant IL-10 signaling and neutrophils have detrimental effects in TLR4-deficient mice during Mtb infection. However, the blockade of IL-10 signaling produced an increase in the CD11bhiLy6 Ghi neutrophil population, but the phenotypes of these neutrophils were different from those of the CD11bintLy6 Gint neutrophils from mice with controlled infections. Collectively, these results show that TLR4 positively contributes to the generation of an optimal protective immunity against Mtb infection. Furthermore, investigating the TLR4-mediated response will provide insight for the development of effective control measures against tuberculosis.

Plant-Produced N-glycosylated Ag85A Exhibits Enhanced Vaccine Efficacy Against Mycobacterium tuberculosis HN878 Through Balanced Multifunctional Th1 T Cell Immunity.

Tuberculosis (TB) is one of the deadliest infectious diseases worldwide and is caused by Mycobacterium tuberculosis (Mtb). An effective vaccine to prevent TB is considered the most cost-effective measure for controlling this disease. Many different vaccine antigen (Ag) candidates, including well-known and newly identified Ags, have been evaluated in clinical and preclinical studies. In this study, we took advantage of a plant system of protein expression using Nicotiana benthamiana to produce N-glycosylated antigen 85A (G-Ag85A), which is one of the most well-characterized vaccine Ag candidates in the field of TB vaccines, and compared its immunogenicity and vaccine efficacy with those of nonglycosylated Ag85A (NG-Ag85A) produced with an Escherichia coli system. Notably, G-Ag85A induced a more robust IFN-γ response than NG-Ag85A, which indicated that G-Ag85A is well recognized by the host immune system during Mtb infection. We subsequently compared the vaccine potential of G-Ag85A and NG-Ag85A by evaluating their immunological features and substantial protection efficacies. Interestingly, G-Ag85A yielded moderately enhanced long-term protective efficacy, as measured in terms of bacterial burden and lung inflammation. Strikingly, G-Ag85A-immunized mice showed a more balanced proportion of multifunctional Th1-biased immune responses with sustained IFN-γ response than did NG-Ag85A-immunized mice. Collectively, plant-derived G-Ag85A could induce protective and balanced Th1 responses and confer long-term protection against a hypervirulent Mtb Beijing strain infection, which indicated that plant-produced G-Ag85A might provide an excellent example for the production of an Mtb subunit vaccine Ag and could be an effective platform for the development of anti-TB vaccines.

Tempo-spatial variations of the Ryukyu Current southeast of Miyakojima Island determined from mooring observations.

The origin, structure, and variability of the Ryukyu Current (RC) have long been debated, mostly due to limited observations. A mooring array, deployed for two years southeast of Miyakojima in the southern portion of the Ryukyu Island chain, has provided, for the first time, data confirming the existence and revealing the characteristics of the RC in that upstream region, including its velocity structure and variability. The observations show a shoreward-intensified current flowing northeastward, with a subsurface core located near the 1,000 m isobath and having a record-long mean speed of up to 19.4 cm s-1 at 500 m depth. Estimated volume transport across the observation section had mean 9.0 Sv (1 Sv = 106 m3 s-1) and standard deviation 8.7 Sv. The RC shows significant barotropic character compared with other similar mid-latitude currents.

Poleward-propagating near-inertial waves enabled by the western boundary current.

Near-inertial waves (NIWs), which have clockwise (anticlockwise) rotational motion in the Northern (Southern) Hemisphere, exist everywhere in the ocean except at the equator; their frequencies are largely determined by the local inertial frequency, f. It is thought that they supply about 25% of the energy for global ocean mixing through turbulence resulting from their strong current shear and breaking; this contributes mainly to upper-ocean mixing which is related to air-sea interaction, typhoon genesis, marine ecosystem, carbon cycle, and climate change. Observations and numerical simulations have shown that the low-mode NIWs can travel many hundreds of kilometres from a source region toward the equator because the lower inertial frequency at lower latitudes allows their free propagation. Here, using observations and a numerical simulation, we demonstrate poleward propagation of typhoon-induced NIWs by a western boundary current, the Kuroshio. Negative relative vorticity, meaning anticyclonic rotational tendency opposite to the Earth's spin, existing along the right-hand side of the Kuroshio path, makes the local inertial frequency shift to a lower value, thereby trapping the waves. This negative vorticity region works like a waveguide for NIW propagation, and the strong Kuroshio current advects the waves poleward with a speed ~85% of the local current. This finding emphasizes that background currents such as the Kuroshio and the Gulf Stream play a significant role in redistribution of the NIW energy available for global ocean mixing.

Vaccine efficacy of a Mycobacterium tuberculosis Beijing-specific proline-glutamic acid (PE) antigen against highly virulent outbreak isolates.

Bacillus Calmette-Guerin vaccine confers insufficient pulmonary protection against tuberculosis (TB), particularly the Mycobacterium tuberculosis (Mtb) Beijing strain infection. Identification of vaccine antigens (Ags) by considering Mtb genetic diversity is crucial for the development of improved TB vaccine. MTBK_20640, a new Beijing genotype-specific proline-glutamic acid-family Ag, was identified by comparative genomic analysis. Its immunologic features were characterized by evaluating interactions with dendritic cells (DCs), and immunogenicity and vaccine efficacy were determined against highly virulent Mtb Beijing outbreak Korean Beijing (K) strain and HN878 strain in murine infection model. MTBK_20640 induced DCs via TLR2 and downstream MAPK and NF-κB signaling pathways, effectively promoting naive CD4-positive (CD4+) T-cell proliferation and IFN-γ production. Different IFN-γ response was observed in mice infected with Mtb K or reference H37Rv strain. Significant induction of T helper type 1 cell-polarized Ag-specific multifunctional CD4+ T cells and a marked Ag-specific IgG2c response were observed in mice immunized with MTBK_20640/glucopyranosyl lipid adjuvant-stable emulsion. The immunization conferred long-term protection against 2 Mtb Beijing outbreak strains, as evidenced by a significant reduction in colony-forming units in the lung and spleen and reduced lung inflammation. MTBK_20640 vaccination conferred long-term protection against highly virulent Mtb Beijing strains. MTBK_20640 may be developed into a novel Ag component in multisubunit TB vaccines in the future.-Kwon, K. W., Choi, H.-H., Han, S. J., Kim, J.-S., Kim, W. S., Kim, H., Kim, L.-H., Kang, S. M., Park, J., Shin, S. J. Vaccine efficacy of a Mycobacterium tuberculosis Beijing-specific proline-glutamic acid (PE) antigen against highly virulent outbreak isolates.

PAL-XFEL soft X-ray scientific instruments and X-ray optics: First commissioning results.

We report an overview of soft X-ray scientific instruments and X-ray optics at the free electron laser (FEL) of the Pohang Accelerator Laboratory, with selected first-commissioning results. The FEL exhibited a pulse energy of 200 µJ/pulse, a pulse width of <50 fs full width at half maximum, and an energy bandwidth of 0.44% at a photon energy of 850 eV. Monochromator resolving power of 10 500 was achieved. The estimated total time resolution between optical laser and X-ray pulses was <270 fs. A resonant inelastic X-ray scattering spectrometer was set up; its commissioning results are also reported.

Electromagnon with Sensitive Terahertz Magnetochromism in a Room-Temperature Magnetoelectric Hexaferrite.

An electromagnon in the magnetoelectric (ME) hexaferrite Ba_{0.5}Sr_{2.5}Co_{2}Fe_{24}O_{41} (Co_{2}Z-type) single crystal is identified by time-domain terahertz (THz) spectroscopy. The associated THz resonance is active on the electric field (E^{ω}) of the THz light parallel to the c axis (∥ [001]), whose spectral weight develops at a markedly high temperature, coinciding with a transverse conical magnetic order below 410 K. The resonance frequency of 1.03 THz at 20 K changes -8.7% and +5.8% under external magnetic field (H) of 2 kOe along [001] and [120], respectively. A model Hamiltonian describing the conical magnetic order elucidates that the dynamical ME effect arises from antiphase motion of spins which are coupled with modulating electric dipoles through the exchange striction mechanism. Moreover, the calculated frequency shift points to the key role of the Dzyaloshinskii-Moriya interaction that is altered by static electric polarization change under different H.

Oxidation Mechanism of Si1-xGex Nanowires with Au Catalyst Tip as a Function of Ge Content.

Si1-xGex nanowires (NWs) (0.22 ≤ x ≤ 0.78) were synthesized using a vapor-liquid-solid procedure with a Au catalyst. We measured the intrinsic physical, chemical, and electrical properties of the oxidized Si1-xGex NWs using several techniques, including transmission electron microscopy, X-ray photoemission spectroscopy, and optical pump-THz probe spectroscopy. We suggest two distinct oxidation mechanisms depending on the Ge content in the Si1-xGex NWs: (i) when the Ge content is around 0.22, a Au catalytic effect brings about oxidation in both the axial and lateral directions; and (ii) when the Ge content is greater than 0.22, the Au tip is detached from the NW body and does not act as a catalyst, which is a result of the high degree of Ge-atom participation in the oxidation process. Additionally, we measured the photoconductivity decay time distribution for the Si1-xGex NWs before and after oxidation process; the decay time is significantly shortened in oxidized Si1-xGex NWs (0.22 < x), whereas it is maintained for Si-rich Si1-xGex NWs (x ≈ 0.22) as compared to the as-grown Si1-xGex NWs. It indicates that the number of defect states is generated with the formation of defective Ge oxide at the oxide-shell-layer/Si1-xGex-core-NW interface.

Ultrafast photocarrier dynamics related to defect states of Si1-xGex nanowires measured by optical pump-THz probe spectroscopy.

Slightly tapered Si1-xGex nanowires (NWs) (x = 0.29-0.84) were synthesized via a vapor-liquid-solid procedure using Au as a catalyst. We measured the optically excited carrier dynamics of Si1-xGex NWs as a function of Ge content using optical pump-THz probe spectroscopy. The measured -ΔT/T0 signals of Si1-xGex NWs were converted into conductivity in the THz region. We developed a fitting formula to apply to indirect semiconductors such as Si1-xGex, which explains the temporal population of photo-excited carriers in the band structure and the relationship between the trapping time and the defect states on an ultrafast time scale. From the fitting results, we extracted intra- and inter-valley transition times and trapping times of electrons and holes of Si1-xGex NWs as a function of Ge content. On the basis of theoretical reports, we suggest a physical model to interpret the trapping times related to the species of interface defect states located at the oxide/NW: substoichiometric oxide states of Si(Ge)0+,1+,2+, but not Si(Ge)3+, could function as defect states capturing photo-excited electrons or holes and could determine the different trapping times of electrons and holes depending on negatively or neutrally charged states.

Temperature dependent CO2 behavior in microporous 1-D channels of a metal-organic framework with multiple interaction sites.

The MOF with the encapsulated CO2 molecule shows that the CO2 molecule is ligated to the unsaturated Cu(II) sites in the cage using its Lewis basic oxygen atom via an angular η1-(OA) coordination mode and also interacts with Lewis basic nitrogen atoms of the tetrazole ligands using its Lewis acidic carbon atom. Temperature dependent structure analyses indicate the simultaneous weakening of both interactions as temperature increases. Infrared spectroscopy of the MOF confirmed that the CO2 interaction with the framework is temperature dependent. The strength of the interaction is correlated to the separation of the two bending peaks of the bound CO2 rather than the frequency shift of the asymmetric stretching peak from that of free CO2. The encapsulated CO2 in the cage is weakly interacting with the framework at around ambient temperatures and can have proper orientation for wiggling out of the cage through the narrow portals so that the reversible uptake can take place. On the other hand, the CO2 in the cage is restrained at a specific orientation at 195 K since it interacts with the framework strong enough using the multiple interaction sites so that adsorption process is slightly restricted and desorption process is almost clogged.

Enhancement of carrier lifetime by spin-orbit coupling in a topological insulator of an Sb2Te3 thin film.

Electrons and phonons in chalcogenide-based materials are important factors in the performance of optical data-storage media and thermoelectric devices. However, the fundamental kinetics of carriers in chalcogenide materials remains controversial, and active debate continues over the mechanism responsible for carrier relaxation. In this study, we used optical-pump terahertz-probe spectroscopy, which permits the relationship between structural phase transition and optical property transitions to be examined, to investigate the ultrafast carrier dynamics in a multilayered [Sb(3 Å)/Te(9 Å)]n thin film during the transition from the disordered to crystalline phase. Using terahertz time-domain spectroscopy and a contact-free optical technique, we demonstrated that the optical conductance and carrier concentration vary as functions of annealing temperature. Moreover, we observed that the topological surface state (TSS) affects the enhancement of the carrier lifetime, which is closely related to the degree of spin-orbit coupling (SOC). The combination of the optical technique and proposed carrier relaxation mechanism provides a powerful tool for monitoring TSS and SOC. Consequently, it was determined that the response of the disordered phase is dominated by an electron-phonon coupling effect, while that of the crystalline structure is controlled by a Dirac surface state and SOC effects. These results are important for understanding the fundamental physics of phase change materials and for optimizing and designing materials with better performance in optoelectronic devices.

Tuning the Fermi level with topological phase transition by internal strain in a topological insulator Bi2Se3 thin film.

In a three-dimensional topological insulator Bi2Se3, a stress control for band gap manipulation was predicted but no systematic investigation has been performed yet due to the requirement of large external stress. We report herein on the strain-dependent results for Bi2Se3 films of various thicknesses that are grown via a self-organized ordering process. Using small angle X-ray scattering and Raman spectroscopy, the changes of d-spacings in the crystal structure and phonon vibration shifts resulted from stress are clearly observed when the film thickness is below ten quintuple layers. From the UV photoemission/inverse photoemission spectroscopy (UPS/IPES) results and ab initio calculations, significant changes of the Fermi level and band gap were observed. The deformed band structure also exhibits a Van Hove singularity at specific energies in the UV absorption experiment and ab initio calculations. Our results, including the synthesis of a strained ultrathin topological insulator, suggest a new direction for electronic and spintronic applications for the future.