Flat-surface-assisted and self-regulated oxidation resistance of Cu(111).

Oxidation can deteriorate the properties of copper that are critical for its use, particularly in the semiconductor industry and electro-optics applications1-7. This has prompted numerous studies exploring copper oxidation and possible passivation strategies8. In situ observations have, for example, shown that oxidation involves stepped surfaces: Cu2O growth occurs on flat surfaces as a result of Cu adatoms detaching from steps and diffusing across terraces9-11. But even though this mechanism explains why single-crystalline copper is more resistant to oxidation than polycrystalline copper, the fact that flat copper surfaces can be free of oxidation has not been explored further. Here we report the fabrication of copper thin films that are semi-permanently oxidation resistant because they consist of flat surfaces with only occasional mono-atomic steps. First-principles calculations confirm that mono-atomic step edges are as impervious to oxygen as flat surfaces and that surface adsorption of O atoms is suppressed once an oxygen face-centred cubic (fcc) surface site coverage of 50% has been reached. These combined effects explain the exceptional oxidation resistance of ultraflat Cu surfaces.

Capturing Coherent Magnons by Tip-Assisted Terahertz Spectroscopy.

Our study highlights the versatility of tip-assisted terahertz spectroscopy in probing coherent magnons, the elementary quanta of spin waves in magnetic materials. We identify two distinct coherent magnon types in canted antiferromagnet YFeO3. The remarkable consistency with far-field terahertz spectroscopy in crucial magnon parameters, such as coherence time and resonance frequency, firmly establishes the credibility of tip-assisted terahertz spectroscopy. Notably, we capture more coherent ferromagnetic magnons near the sample surface, underscoring the strength of the technique. This approach paves the way for local, free-standing, and real-space investigations of spin waves in solid magnets.

Subwavelength Terahertz Resonance Imaging (STRING) for Molecular Fingerprinting.

Subwavelength terahertz (THz) imaging methods are highly desirable for biochemical sensing as well as materials sciences, yet sensitive spectral fingerprinting is still challenging in the frequency domain due to weak light-matter interactions. Here, we demonstrate subwavelength THz resonance imaging (STRING) that overcomes this limitation to achieve ultrasensitive molecular fingerprinting. STRING combines individual ring-shaped coaxial single resonators with near-field spectroscopy, yielding considerable sensitivity gains from both local field enhancement and the near-field effect. As an initial demonstration, we obtained spectral fingerprints from isomers of α-lactose and maltose monohydrates, achieving sensitivity that was enhanced by up to 10 orders of magnitude compared to far-field THz measurements with pelletized samples. Our results show that the STRING platform could enable the development of THz spectroscopy as a practical and sensitive tool for the fingerprinting and spectral imaging of molecules and nanoparticles.

Magneto-optical and thermal characteristics of magnetite nanoparticle-embedded DNA and CTMA-DNA thin films.

Recently, DNA molecules embedded with magnetite (Fe3O4) nanoparticles (MNPs) drew much attention for their wide range of potential usage. With specific intrinsic properties such as low optical loss, high transparency, large band gap, high dielectric constant, potential for molecular recognition, and their biodegradable nature, the DNA molecule can serve as an effective template or scaffold for various functionalized nanomaterials. With the aid of cetyltrimethylammonium (CTMA) surfactant, DNA can be used in organic-based applications as well as water-based ones. Here, DNA and CTMA-DNA thin films with various concentrations of MNPs fabricated by the drop-casting method have been characterized by optical absorption, refractive index, Raman, and cathodoluminescence measurements to understand the binding, dispersion, chemical identification/functional modes, and energy transfer mechanisms, respectively. In addition, magnetization was measured as a function of either applied magnetic field or temperature in field cooling and zero field cooling. Saturation magnetization and blocking temperature demonstrate the importance of MNPs in DNA and CTMA-DNA thin films. Finally, we examine the thermal stabilities of MNP-embedded DNA and CTMA-DNA thin films through thermogravimetric analysis, derivative thermogravimetry, and differential thermal analysis. The unique optical, magnetic, and thermal characteristics of MNP-embedded DNA and CTMA-DNA thin films will prove important to fields such as spintronics, biomedicine, and function-embedded sensors and devices.

Potentiation of decursinol angelate on pentobarbital-induced sleeping behaviors via the activation of GABAA-ergic systems in rodents.

Angelicae Gigantis Radix (AGR, Angelica gigas) has been used for a long time as a traditional folk medicine in Korea and oriental countries. Decursinol angelate (DCA) is structurally isomeric decursin, one of the major components of AGR. This study was performed to confirm whether DCA augments pentobarbital-induced sleeping behaviors via the activation of GABAA-ergic systems in animals. Oral administration of DCA (10, 25 and 50 mg/kg) markedly suppressed spontaneous locomotor activity. DCA also prolonged sleeping time, and decreased the sleep latency by pentobarbital (42 mg/kg), in a dose-dependent manner, similar to muscimol, both at the hypnotic (42 mg/kg) and sub-hypnotic (28 mg/kg) dosages. Especially, DCA increased the number of sleeping animals in the sub-hypnotic dosage. DCA (50 mg/kg, p.o.) itself modulated sleep architectures; DCA reduced the counts of sleep/wake cycles. At the same time, DCA increased total sleep time, but not non-rapid eye movement (NREM) and rapid eye movement (REM) sleep. In the molecular experiments. DCA (0.001, 0.01 and 0.1 µg/ml) increased intracellular Cl- influx level in hypothalamic primary cultured neuronal cells of rats. In addition, DCA increased the protein expression of glutamic acid decarboxylase (GAD65/67) and GABAA receptors subtypes. Taken together, these results suggest that DCA potentiates pentobarbital-induced sleeping behaviors through the activation of GABAA-ergic systems, and can be useful in the treatment of insomnia.

Re-order parameter of interacting thermodynamic magnets.

Phase diagrams of materials are typically based on a static order parameter, but it faces challenges when distinguishing subtle phase changes, such as re-ordering. Here, we report a dynamic nonequilibrium order parameter termed re-order parameter to determine subtle phases and their transitions in interacting magnets. The dynamical precession of magnetization, so-called magnon, premises as a reliable re-order parameter of strong spin-orbit coupled magnets. We employ orthoferrites YFeO3 and its Mn-doped variations, where diverse magnetic phases, including canted antiferromagnetic (Γ4) and collinear antiferromagnetic (Γ1) states, have been well-established. Low-energy magnon uncovers the spin-orbit coupling-induced subtle magnetic structures, resulting in distinct terahertz emissions. The temporal and spectral parameters of magnon emission exhibit characteristics akin to BCS-type order parameters, constructing the magnetic phase diagram of Mn-doped YFeO3. This approach further reveals a concealed ferrimagnetic phase within the Γ1 state, underscoring its potential to search for hidden phases of materials, completing their phase diagrams.

Probing Interfacial Charge Transfer between Amyloid-ß and Graphene during Amyloid Fibrillization Using Raman Spectroscopy.

Charge transfer plays a key role in the structural transformation of amyloid-ß proteins (Aßs), as it fibrillizes from small monomers to intermediate oligomers and to ordered fibrils. While the protein fibrillization states have been identified using cryo-electron microscopy, X-ray diffraction, Raman, infrared, terahertz spectroscopies, etc., there is little known about the electronic states during the fibrilization of Aß protein. Here, we probe the charge transfer of Aß42 proteins at different aggregation stages adsorbed on monolayer graphene (Gr) and molybdenum disulfide (MoS2) using Raman spectroscopy. Monomers, oligomers, and fibrils prepared in buffer solutions were deposited and dried separately on Gr and MoS2 where well-established characteristic Raman modes (G, 2D for Gr and E2g, A1g for MoS2) were monitored. The shifts in Raman parameters showed that the small Aß monomers withdraw electrons, whereas fibrils donate electrons to Gr and MoS2. Oligomers undergo transient charge states near the neutrality point. This is explained in terms of modulated carrier concentration in Gr and MoS2. This finding provides insight into the electronic properties of Aßs that could be essential to identifying the onset of toxic fibril forms and developing a straightforward, label-free diagnosis using Gr and MoS2.

Non-Hermitian chiral degeneracy of gated graphene metasurfaces.

Non-Hermitian degeneracies, also known as exceptional points (EPs), have been the focus of much attention due to their singular eigenvalue surface structure. Nevertheless, as pertaining to a non-Hermitian metasurface platform, the reduction of an eigenspace dimensionality at the EP has been investigated mostly in a passive repetitive manner. Here, we propose an electrical and spectral way of resolving chiral EPs and clarifying the consequences of chiral mode collapsing of a non-Hermitian gated graphene metasurface. More specifically, the measured non-Hermitian Jones matrix in parameter space enables the quantification of nonorthogonality of polarisation eigenstates and half-integer topological charges associated with a chiral EP. Interestingly, the output polarisation state can be made orthogonal to the coalesced polarisation eigenstate of the metasurface, revealing the missing dimension at the chiral EP. In addition, the maximal nonorthogonality at the chiral EP leads to a blocking of one of the cross-polarised transmission pathways and, consequently, the observation of enhanced asymmetric polarisation conversion. We anticipate that electrically controllable non-Hermitian metasurface platforms can serve as an interesting framework for the investigation of rich non-Hermitian polarisation dynamics around chiral EPs.

Self-Oxidation Resistance of the Curved Surface of Achromatic Copper.

Copper surfaces that exhibit a wide range of achromatic colors while still metallic have not been studied, despite advancements in antireflection coatings. A series of achromatic copper films grown with [111] preferred orientation by depositing 3D porous nanostructures is introduced via coherent/incoherent atomic sputtering epitaxy. The porous copper nanostructures self-regulate the giant oxidation resistance by constructing a curved surface that generates a series of monoatomic steps, followed by shrinkage of the lattice spacing of one or two surface layers. First-principles calculations confirm that these structural components cooperatively increase the energy barrier against oxygen penetration. The achromaticity of the single-crystalline porous copper films is systematically tuned by geometrical parameters such as pore size distribution and 3D linkage. The optimized achromatic copper films with high oxidation resistance show an unusual switching effect between superhydrophilicity and superhydrophobicity. The tailored 3D porous nanostructures can be a candidate material for numerous applications, such as antireflection coatings, microfluidic devices, droplet tweezers, and reversible wettability switches.

Coherent consolidation of trillions of nucleations for mono-atom step-level flat surfaces.

Constructing a mono-atom step-level ultra-flat material surface is challenging, especially for thin films, because it is prohibitively difficult for trillions of clusters to coherently merge. Even though a rough metal surface, as well as the scattering of carriers at grain boundaries, limits electron transport and obscures their intrinsic properties, the importance of the flat surface has not been emphasised sufficiently. In this study, we describe in detail the initial growth of copper thin films required for mono-atom step-level flat surfaces (MSFSs). Deposition using atomic sputtering epitaxy leads to the coherent merging of trillions of islands into a coplanar layer, eventually forming an MSFS, for which the key factor is suggested to be the individual deposition of single atoms. Theoretical calculations support that single sputtered atoms ensure the formation of highly aligned nanodroplets and help them to merge into a coplanar layer. The realisation of the ultra-flat surfaces is expected to greatly assist efforts to improve quantum behaviour by increasing the coherency of electrons.

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.

Real-space imaging and control of chiral anomaly induced current at room temperature in topological Dirac semimetal.

Chiral fermions (CFs) in condensed matters, distinguished by right (+) or left (-) handedness, hold a promise for emergent quantum devices. Although a chiral anomaly induced current, Jchiral = J(+) - J(-), occurs in Weyl semimetals due to the charge imbalance of the CFs, monitoring spatial flow and temporal dynamics of Jchiral has not been demonstrated yet. Here, we report real-space imaging and control of Jchiral on the topological Dirac semimetal KZnBi at room temperature (RT) by near-field terahertz (THz) spectroscopy, establishing a relation for an electromagnetic control of Jchiral. In THz electric and external magnetic fields, we visualize a spatial flow of coherent Jchiral in macroscopic length scale and monitor its temporal dynamics in picosecond time scale, revealing its ultralong transport length around 100 micrometers. Such coherent Jchiral is further found to be controlled according to field directions, suggesting the feasibility of information science with topological Dirac semimetals at RT.

High-temperature differences in plasmonic broadband absorber on PET and Si substrates.

The characteristics of a plasmonic resonator with a metal-dielectric-metal structure is influenced by the size, shape, and spacing of the nanostructure. The plasmonic resonators can be used in various applications such as color filters, light emitting diodes, photodetectors, and broadband absorbers. In particular, broadband absorbers are widely used in thermophotovoltaics and thermoelectrics. To achieve a higher photothermal conversion efficiency, it is important to provoke a larger temperature difference in the absorber. The absorption and thermal conductance of the absorber has a great impact on the temperature difference, but in order to further improve the temperature difference of the absorber, the thermal conductivity of the substrate should be considered carefully. In this study, we designed Cr/SiO2/Cr absorbers on different substrates, i.e., polyethylene terephthalate (PET) and silicon. Although their optical properties do not change significantly, the temperature difference of the absorber on the PET substrate is considerably higher than that on the Si substrate under laser illumination, i.e., 164 K for ΔTPET and 3.7 K for ΔTSi, respectively. This is attributed to the thermal conductance of the substrate materials, which is confirmed by the thermal relaxation time. Moreover, the Seebeck coefficient of graphene on the absorber, 9.8 µV/K, is obtained by photothermoelectrics. The proposed Cr/SiO2/Cr structure provides a clear scheme to achieve high performance in photothermoelectric devices.

Security use of the chiral photonic film made of helical liquid crystal structures.

The color change of photonic crystals (PCs) has been widely studied due to their beauty and anti-counterfeiting applications. Herein, we demonstrated security codes based on chiral PCs that cannot be easily mimicked and are quite different from the conventional technology used currently. The chiral PCs can be made by self-assembly and the structural colors change based on the polarization of the light in the transmission mode. These color changes are easily detected in real-time and are useful in the fabrication of anti-counterfeiting patterns that show beautiful and diverse color changes with rotating polarizers. We believe this can provide a new platform in various security and color-based applications.

Identifying Fibrillization State of Aß Protein via Near-Field THz Conductance Measurement.

Progressive Alzheimer's disease is correlated with the oligomerization and fibrillization of the amyloid beta (Aß) protein. We identify the fibrillization stage of the Aß protein through label-free near-field THz conductance measurements in a buffer solution. Frequency-dependent conductance was obtained by measuring the differential transmittance of the time-domain spectroscopy in the THz range with a molar concentration of monomer, oligomer, and fibrillar forms of the Aß protein. Conductance at the lower frequency limit was observed to be high in monomers, reduced in oligomers, and dropped to an insulating state in fibrils and increased proportionally with the Aß protein concentration. The monotonic decrease in the conductance at low frequency was dominated by a simple Drude component in the monomer with concentration and nonlinear conductance behaviors in the oligomer and fibril. By extracting the structural localization parameter, a dimensionless constant, with the modified Drude-Smith model, we defined a dementia quotient (DQ) value (0 < De < 1) as a discrete metric for a various Aß proteins at a low concentration of 0.1 µmol/L; DQ = 1.0 ± 0.002 (fibril by full localization, mainly by Smith component), DQ = 0.64 ± 0.013 (oligomer by intermixed localization), and DQ = 0.0 ± 0.000 (monomer by Drude component). DQ values were discretely preserved independent of the molar concentration or buffer variation. This provides plenty of room for the label-free diagnosis of Alzheimer's disease using the near-field THz conductance measurement.

Phase-change like process through bond switching in distorted and resonantly bonded crystal.

Although some methods to improve phase-change memory efficiency have been proposed, an effective experimental approach to induce a phase-change like process without external heat energy has not yet been reported. Herein we have shown that GeTe is a prototype phase-change material, which can exhibit a non-thermal phase-change-like process under uniaxial stress. Due to its structural characteristics like directional structural instability and resonance bonding under 1% uniaxial stress, we observed that bond switching in the GeTe film between short and long bonds is possible. Due to this phase change, GeTe displays the same phase-change as crystal layer rotation. Crystal layer rotation has not been observed in the conventional phase change process using intermediate states, but it is related to the structural characteristics required for maintaining local coordination. Moreover, since the resonance bonding characteristics are effectively turned off upon applying uniaxial stress, the high-frequency dielectric constant can be significantly decreased. Our results also show that the most significant process in the non-thermal phase transition of phase-change materials is the modulation of the lattice relaxation process after the initial perturbation, rather than the method inducing the perturbation itself. Finally, these consequences suggest that a new type of phase-change memory is possible through changes in the optical properties under stress.

A Chest-Laminated Ultrathin and Stretchable E-Tattoo for the Measurement of Electrocardiogram, Seismocardiogram, and Cardiac Time Intervals.

Seismocardiography (SCG) is a measure of chest vibration associated with heartbeats. While skin soft electronic tattoos (e-tattoos) have been widely reported for electrocardiogram (ECG) sensing, wearable SCG sensors are still based on either rigid accelerometers or non-stretchable piezoelectric membranes. This work reports an ultrathin and stretchable SCG sensing e-tattoo based on the filamentary serpentine mesh of 28-µm-thick piezoelectric polymer, polyvinylidene fluoride (PVDF). 3D digital image correlation (DIC) is used to map chest vibration to identify the best location to mount the e-tattoo and to investigate the effects of substrate stiffness. As piezoelectric sensors easily suffer from motion artifacts, motion artifacts are effectively reduced by performing subtraction between a pair of identical SCG tattoos placed adjacent to each other. Integrating the soft SCG sensor with a pair of soft gold electrodes on a single e-tattoo platform forms a soft electro-mechano-acoustic cardiovascular (EMAC) sensing tattoo, which can perform synchronous ECG and SCG measurements and extract various cardiac time intervals including systolic time interval (STI). Using the EMAC tattoo, strong correlations between STI and the systolic/diastolic blood pressures, are found, which may provide a simple way to estimate blood pressure continuously and noninvasively using one chest-mounted e-tattoo.

Sleep-Aids Derived from Natural Products.

Although drugs such as barbiturates and benzodiazepines are often used for the treatment of insomnia, they are associated with various side effects such as habituations, tolerance and addiction. Alternatively, natural products with minimal unwanted effects have been preferred for the treatment of acute and/or mild insomnia, with additional benefits of overall health-promotion. Basic and clinical researches on the mechanisms of action of natural products have been carried out so far in insomnia treatments. Recent studies have been focusing on diverse chemical components available in natural products, with an interest of developing drugs that can improve sleep duration and quality. In the last 15 years, our co-workers have been actively looking for candidate substances from natural products that can relieve insomnia. This review is, therefore, intended to bring pharmacological data regarding to the effects of natural products on sleep duration and quality, mainly through the activation of GABAA receptors. It is imperative that phytochemicals will provide useful information during electroencephalography (EEG) analysis and serve as an alternative medications for insomnia patients who are reluctant to use conventional drugs.

Sinomenine, an Alkaloid Derived from Sinomenium acutum Potentiates Pentobarbital-Induced Sleep Behaviors and Non-Rapid Eye Movement (NREM) Sleep in Rodents.

Sinomenium acutum has been long used in the preparations of traditional medicine in Japan, China and Korea for the treatment of various disorders including rheumatism, fever, pulmonary diseases and mood disorders. Recently, it was reported that Sinomenium acutum, has sedative and anxiolytic effects mediated by GABA-ergic systems. These experiments were performed to investigate whether sinomenine (SIN), an alkaloid derived from Sinomenium acutum enhances pentobarbital-induced sleep via γ-aminobutyric acid (GABA)-ergic systems, and modulates sleep architecture in mice. Oral administration of SIN (40 mg/kg) markedly reduced spontaneous locomotor activity, similar to diazepam (a benzodiazepine agonist) in mice. SIN shortened sleep latency, and increased total sleep time in a dose-dependent manner when co-administrated with pentobarbital (42 mg/kg, i.p.). SIN also increased the number of sleeping mice and total sleep time by concomitant administration with the sub-hypnotic dosage of pentobarbital (28 mg/kg, i.p.). SIN reduced the number of sleep-wake cycles, and increased total sleep time and non-rapid eye movement (NREM) sleep. In addition, SIN also increased chloride influx in the primary cultured hypothalamic neuronal cells. Furthermore, protein overexpression of glutamic acid decarboxylase (GAD65/67) and GABAA receptor subunits by western blot were found, being activated by SIN. In conclusion, SIN augments pentobarbital-induced sleeping behaviors through GABAA-ergic systems, and increased NREM sleep. It could be a candidate for the treatment of insomnia.

Chemical and Physical Characteristics of Doxorubicin Hydrochloride Drug-Doped Salmon DNA Thin Films.

Double-stranded salmon DNA (SDNA) was doped with doxorubicin hydrochloride drug molecules (DOX) to determine the binding between DOX and SDNA, and DOX optimum doping concentration in SDNA. SDNA thin films were prepared with various concentrations of DOX by drop-casting on oxygen plasma treated glass and quartz substrates. Fourier transform infrared (FTIR) spectroscopy was employed to investigate the binding sites for DOX in SDNA, and electrical and photoluminescence (PL) analyses were used to determine the optimum doping concentration of DOX. The FTIR spectra showed that up to a concentration of 30 µM of DOX, there was a tendency for binding with a periodic orientation via intercalation between nucleosides. The current and PL intensity increased as the DOX concentration increased up to 30 µM, and then as the concentration of DOX further increased, we observed a decrease in current as well as PL quenching. Finally, the optical band gap and second band onset of the transmittance spectra were analyzed to further verify the DOX binding and optimum doping concentration into SDNA thin films as a function of the DOX concentration.