Fast water transport and molecular sieving through ultrathin ordered conjugated-polymer-framework membranes.

The development of membranes that block solutes while allowing rapid water transport is of great importance. The microstructure of the membrane needs to be rationally designed at the molecular level to achieve precise molecular sieving and high water flux simultaneously. We report the design and fabrication of ultrathin, ordered conjugated-polymer-framework (CPF) films with thicknesses down to 1 nm via chemical vapour deposition and their performance as separation membranes. Our CPF membranes inherently have regular rhombic sub-nanometre (10.3 × 3.7 Å) channels, unlike membranes made of carbon nanotubes or graphene, whose separation performance depends on the alignment or stacking of materials. The optimized membrane exhibited a high water/NaCl selectivity of ∼6,900 and water permeance of ∼112 mol m-2 h-1 bar-1, and salt rejection >99.5% in high-salinity mixed-ion separations driven by osmotic pressure. Molecular dynamics simulations revealed that water molecules quickly and collectively pass through the membrane by forming a continuous three-dimensional network within the hydrophobic channels. The advent of ordered CPF provides a route towards developing carbon-based membranes for precise molecular separation.

Resonance-enhanced excitation and relaxation dynamics of coherent phonons in Fe1.14Te.

Lattice dynamics plays a significant role in manipulating the unique physical properties of materials. In this work, femtosecond transient optical spectroscopy is used to investigate the generation mechanism and relaxation dynamics of coherent phonons in Fe1.14Te-a parent compound of chalcogenide superconductors. The reflectivity time series consist of the exponential decay component due to hot carriers and damped oscillations caused by the A1g phonon vibration. The vibrational frequency and dephasing time of the A1g phonons are obtained as a function of temperature. With increasing temperature, the phonon frequency decreases and can be well described with the anharmonicity model. Dephasing time is independent of temperature, indicating that the phonon dephasing is dominated by phonon-defect scattering. The impulsive stimulated Raman scattering mechanism is responsible for the coherent phonon generation. Owing to the resonance Raman effect, the maximum photosusceptibility of the A1g phonons occurs at 1.590 eV, corresponding to an electronic transition in Fe1.14Te.

Quantifying Real-Time Sample Temperature Under the Gas Environment in the Transmission Electron Microscope Using a Novel MEMS Heater.

Accurate control and measurement of real-time sample temperature are critical for the understanding and interpretation of the experimental results from in situ heating experiments inside environmental transmission electron microscope (ETEM). However, quantifying the real-time sample temperature remains a challenging task for commercial in situ TEM heating devices, especially under gas conditions. In this work, we developed a home-made micro-electrical-mechanical-system (MEMS) heater with unprecedented small temperature gradient and thermal drift, which not only enables the temperature evolution caused by gas injection to be measured in real-time but also makes the key heat dissipation path easier to model to theoretically understand and predict the temperature decrease. A new parameter termed as "gas cooling ability (H)", determined purely by the physical properties of the gas, can be used to compare and predict the gas-induced temperature decrease by different gases. Our findings can act as a reference for predicting the real temperature for in situ heating experiments without closed-loop temperature sensing capabilities in the gas environment, as well as all gas-related heating systems.

Emerging new phase boundary in potassium sodium-niobate based ceramics.

Developing eco-friendly high-performance piezoceramics without lead has become one of the most advanced frontiers in interdisciplinary research. Although potassium sodium-niobate {(K,Na)NbO3, KNN} based ceramics are believed to be one of the most promising lead-free candidates, the relatively inferior piezoelectric properties and strong temperature dependency have hindered their development for more than 50 years since being discovered in the 1950s. It was not until 2014 that our group initially proposed a new phase boundary (NPB) that simultaneously improved the piezoelectric properties and temperature stability of non-textured KNN-based ceramics to the level of partly lead-based ceramics. The NPB has been then proved by some researchers and believed to pave the way for "lead-free at last" proposed by E. Cross (Nature, 2004, 432, 24). However, the understanding of the NPB is still in its infancy, leaving many controversies, including the phase structure and physical mechanisms at the NPB as well as the essential difference when compared with other phase boundaries. In this context, we systematically summarized the origin and development of the NPB, focusing on the construction, structure and intrinsic trait of the NPB, the effects of the NPB on the performance, and the validity and related incipient devices of the NPB. Particularly, we concluded the phase structure and domain structure locating at the NPB, analyzed the physical mechanisms in depth, proposed the possible methods to further improve the performance at the NPB, and demonstrated the validity and scope of the NPB as well as the device application. Finally, we gave out our perspective on the challenges and future research of KNN-based ceramics with NPB. Therefore, we believe that this review could promote the understanding of the NPB and guide the future work of KNN-based ceramics.

Creation of Single Chain of Nanoscale Skyrmion Bubbles with Record-High Temperature Stability in a Geometrically Confined Nanostripe.

Nanoscale topologically nontrivial spin textures, such as magnetic skyrmions, have been identified as promising candidates for the transport and storage of information for spintronic applications, notably magnetic racetrack memory devices. The design and realization of a single skyrmion chain at room temperature (RT) and above in the low-dimensional nanostructures are of great importance for future practical applications. Here, we report the creation of a single skyrmion bubble chain in a geometrically confined Fe3Sn2 nanostripe with a width comparable to the featured size of a skyrmion bubble. Systematic investigations on the thermal stability have revealed that the single chain of skyrmion bubbles can keep stable at temperatures varying from RT up to a record-high temperature of 630 K. This extreme stability can be ascribed to the weak temperature-dependent magnetic anisotropy and the formation of edge states at the boundaries of the nanostripes. The realization of the highly stable skyrmion bubble chain in a geometrically confined nanostructure is a very important step toward the application of skyrmion-based spintronic devices.

Localized Electrochemiluminescence from Nanoneedle Electrodes for Very-High-Density Electrochemical Sensing.

In this paper, localized electrochemiluminescence (ECL) was visualized from nanoneedle electrodes that achieved very-high-density electrochemical sensing. The localized luminescence at the nanometer-sized tip observed was ascribed to enhanced mass transfer of the luminescence probe at the tip than on the planar surface surrounding the tip, which provided higher luminescence at the tip. The size of the luminescence spots was restricted to 15 µm permitting the electrochemical analysis with a density over 4 × 103 spots/mm2. The positive correlation between the luminescence intensity at the tips and the concentration of hydrogen peroxide supported the quantitative ECL analysis using nanoneedle electrodes. The further modification of glucose oxidase at the electrode surface conceptually demonstrated that the concentration of glucose ranging from 0.5 to 5 mM could be quantified using the luminescence at the tips, which could be further applied for the detection of multiple molecules in the complex biosystem. This successful localized ECL offers a specific strategy for the development of very-high-density electrochemical arrays without the complicated chip design.

Thielavins W-Z7, New Antifouling Thielavins from the Marine-Derived Fungus Thielavia sp. UST030930-004.

Eleven new depsides-thielavins W-Z (1-4) and thielavins Z1-Z7 (5-11)-and also four known thielavins-A, H, J, and K (12-15)-were isolated from the ethyl acetate extract of a marine-derived fungal strain Thielavia sp UST030930-004. All of these compounds were evaluated for antifouling activity against cyprids of the barnacle Balanus (=Amphibalanus) amphitrite. The results showed that compounds 1-3 and 6-13 were active, with EC50 values ranging from 2.95 ± 0.59 to 69.19 ± 9.51 µM, respectively. The inhibitive effect of compounds 1-3 and 7 was reversible. This is the first description of the antifouling activity of thielavins against barnacle cyprids.

Bio-Inspired Carbon Monoxide Sensors with Voltage-Activated Sensitivity.

Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the strong specific interaction between CO and the iron porphyrin provides a highly selective and customizable sensor. We report the development of chemiresistive sensors with voltage-activated sensitivity for the detection of CO comprising iron porphyrin and functionalized single-walled carbon nanotubes (F-SWCNTs). Modulation of the gate voltage offers a predicted extra dimension for sensing. Specifically, the sensors show a significant increase in sensitivity toward CO when negative gate voltage is applied. The dosimetric sensors are selective to ppm levels of CO and functional in air. UV/Vis spectroscopy, differential pulse voltammetry, and density functional theory reveal that the in situ reduction of FeIII to FeII enhances the interaction between the F-SWCNTs and CO. Our results illustrate a new mode of sensors wherein redox active recognition units are voltage-activated to give enhanced and highly specific responses.

Atomic resolution observation of conversion-type anode RuO2 during the first electrochemical lithiation.

Transition metal oxides have attracted great interest as alternative anode materials for rechargeable lithium-ion batteries. Among them, ruthenium dioxide is considered to be a prototype material that reacts with the Li ions in the conversion type. In situ transmission electron microscopy reveals a two-step process during the initial lithiation of the RuO2 nanowire anode at atomic resolution. The first step is characterized by the formation of the intermediate phase LixRuO2 due to the Li-ion intercalation. The following step is manifested by the solid-state amorphization reaction driven by advancing the reaction front. The crystalline/amorphous interface is consisted of {011} atomic terraces, revealing the orientation-dependent mobility. In the crystalline matrix, lattice disturbance and dislocation are identified to be two major stress-induced distortions. The latter can be effective diffusion channels, facilitating transportation of the Li ions inside the bulk RuO2 crystal and further resulting in non-uniform Li-ion distribution. It is expected that the local enrichment of the Li ions may account for the homogeneous nucleation of dislocations in the bulk RuO2 crystal and the special island-like structures. These results elucidate the structural evolution and the phase transformation during electrochemical cycling, which sheds light on engineering RuO2 anode materials.

Real time hybridization studies by resonant waveguide gratings using nanopattern imaging for Single Nucleotide Polymorphism detection.

2D imaging of biochips is particularly interesting for multiplex biosensing. Resonant properties allow label-free detection using the change of refractive index at the chip surface. We demonstrate a new principle of Scanning Of Resonance on Chip by Imaging (SORCI) based on spatial profiles of nanopatterns of resonant waveguide gratings (RWGs) and its embodiment in a fluidic chip for real-time biological studies. This scheme allows multiplexing of the resonance itself by providing nanopattern sensing areas in a bioarray format. Through several chip designs we discuss resonance spatial profiles, dispersion and electric field distribution for optimal light-matter interaction with biological species of different sizes. Fluidic integration is carried out with a black anodized aluminum chamber, advantageous in term of mechanical stability, multiple uses of the chip, temperature control and low optical background. Real-time hybridization experiments are illustrated by SNP (Single Nucleotide Polymorphism) detection in gyrase A of E. coli K12, observed in evolution studies of resistance to the antibiotic ciprofloxacin. We choose a 100 base pairs (bp) DNA target (~30 kDa) including the codon of interest and demonstrate the high specificity of our technique for probes and targets with close affinity constants. This work validates the safe applicability of our unique combination of RWGs and simple instrumentation for real-time biosensing with sensitivity in buffer solution of ~10 pg/mm². Paralleling the success of RWGs sensing for cells sensing, our work opens new avenues for a large number of biological studies.

Magnetic Skyrmions above Room Temperature in a van der Waals Ferromagnet Fe3GaTe2.

2D van der Waals (vdW) ferromagnetic crystals are a promising platform for innovative spintronic devices based on magnetic skyrmions, thanks to their high flexibility and atomic thickness stability. However, room-temperature skyrmion-hosting vdW materials are scarce, which poses a challenge for practical applications. In this study, a chemical vapor transport (CVT) approach is employed to synthesize Fe3GaTe2 crystals and room-temperature Néel skyrmions are observed in Fe3GaTe2 nanoflakes above 58 nm in thickness through in situ Lorentz transmission electron microscopy (L-TEM). Upon an optimized field cooling procedure, zero-field hexagonal skyrmion lattices are successfully generated in nanoflakes with an extended thickness range (30-180 nm). Significantly, these skyrmion lattices remain stable up to 355 K, setting a new record for the highest temperature at which skyrmions can be hosted. The research establishes Fe3GaTe2 as an emerging above-room-temperature skyrmion-hosting vdW material, holding great promise for future spintronics.

A redox responsive, fluorescent supramolecular metallohydrogel consists of nanofibers with single-molecule width.

The integration of a tripeptide derivative, which is a versatile self-assembly motif, with a ruthenium(II)tris(bipyridine) complex affords the first supramolecular metallo-hydrogelator that not only self assembles in water to form a hydrogel but also exhibits gel-sol transition upon oxidation of the metal center. Surprisingly, the incorporation of the metal complex in the hydrogelator results in the nanofibers, formed by the self-assembly of the hydrogelator in water, to have the width of a single molecule of the hydrogelator. These results illustrate that metal complexes, besides being able to impart rich optical, electronic, redox, or magnetic properties to supramolecular hydrogels, also offer a unique geometrical control to prearrange the self-assembly motif prior to self-assembling. The use of metal complexes to modulate the dimensionality of intermolecular interactions may also help elucidate the interactions of the molecular nanofibers with other molecules, thus facilitating the development of supramolecular hydrogel materials for a wide range of applications.

Caspase-3-dependent apoptosis of citreamicin ε-induced HeLa cells is associated with reactive oxygen species generation.

Citreamicins, members of the polycyclic xanthone family, are promising antitumor agents that are produced by Streptomyces species. Two diastereomers, citreamicin ε A (1) and B (2), were isolated from a marine-derived Streptomyces species. The relative configurations of these two diastereomers were determined using NMR spectroscopy and successful crystallization of citreamicin ε A (1). Both diastereomers showed potent cytotoxic activity against HeLa (cervical cancer) and HepG2 (hepatic carcinoma) cells with IC50 values ranging from 30 to 100 nM. The terminal deoxynucleotidyl transferase dUTP nick-end labeling assay confirmed that citreamicin ε A (1) induced cellular apoptosis, and Western blot analysis showed that apoptosis occurred via activation of caspase-3. The 2,7-dichlorofluorescein diacetate assay indicated that citreamicin ε substantially increased the intracellular concentration of reactive oxygen species (ROS). To confirm the hypothesis that citreamicin ε induced apoptosis through an increase in the intracellular ROS concentration, the oxidized products, oxicitreamicin ε A (3) and B (4), were obtained from a one-step reaction catalyzed by Ag2O. These products, with a reduced capacity to increase the intracellular ROS concentration, exhibited a significantly weakened cytotoxicity in both HeLa and HepG2 cells compared with that of citreamicin ε A (1) and B (2).

Switching magnetic strip orientation using electric fields.

In spintronics, ordered magnetic domains are important for magnetic microdevices and controlling the orientation of ordered magnetic domains is important for applications such as domain wall resistance and spin wave propagation. Although a magnetic field or a current can reorient ordered magnetic domains, an energy-efficient electric-field-driven rotation of the ordered magnetic domains remains elusive. Here, using a nanotrenched polymeric layer, we obtain ordered magnetic strip domains in Ni films on a ferroelectric substrate. By applying electric fields to the ferroelectric substrate, we demonstrate that the ordered magnetic strip domains in Ni films are switched between the y- and x-axes driven by electric-fields. This switching of magnetic strip orientation is attributed to the electric-field-modulated in-plane magnetic anisotropies along the x- and y-axes of the Ni films, which are caused by the anisotropic biaxial strain of the ferroelectric substrate via strain-mediated magnetoelectric coupling. These results provide an energy-efficient approach for manipulating the ordered magnetic domains using electric fields.

Room-Temperature Magnetic Skyrmions and Large Topological Hall Effect in Chromium Telluride Engineered by Self-Intercalation.

Room-temperature magnetic skyrmion materials exhibiting robust topological Hall effect (THE) are crucial for novel nano-spintronic devices. However, such skyrmion-hosting materials are rare in nature. In this study, a self-intercalated transition metal dichalcogenide Cr1+ x Te2 with a layered crystal structure that hosts room-temperature skyrmions and exhibits large THE is reported. By tuning the self-intercalate concentration, a monotonic control of Curie temperature from 169 to 333 K and a magnetic anisotropy transition from out-of-plane to the in-plane configuration are achieved. Based on the intercalation engineering, room-temperature skyrmions are successfully created in Cr1.53 Te2 with a Curie temperature of 295 K and a relatively weak perpendicular magnetic anisotropy. Remarkably, a skyrmion-induced topological Hall resistivity as large as ≈106 nΩ cm is observed at 290 K. Moreover, a sign reversal of THE is also found at low temperatures, which can be ascribed to other topological spin textures having an opposite topological charge to that of the skyrmions. Therefore, chromium telluride can be a new paradigm of the skyrmion material family with promising prospects for future device applications.

Four new antibacterial xanthones from the marine-derived actinomycetes Streptomyces caelestis.

Four new polycyclic antibiotics, citreamicin θ A (1), citreamicin θ B (2), citreaglycon A (3), and dehydrocitreaglycon A (4), were isolated from marine-derived Streptomyces caelestis. The structures of these compounds were elucidated by 1D and 2D NMR spectra. All four compounds displayed antibacterial activity against Staphylococcus haemolyticus, Staphylococcus aureus, and Bacillus subtillis. Citreamicin θ A (1), citreamicin θ B (2) and citreaglycon A (3) also exhibited low MIC values of 0.25, 0.25, and 8.0 µg/mL, respectively, against methicillin-resistant Staphylococcus aureus (MRSA) ATCC 43300.

Hot carrier dynamics of BiTeI with large Rashba spin splitting.

We present a time-resolved ultrafast optical spectroscopy study on BiTeI, a noncentrosymmetric semiconductor with large spin-orbit splitting. By tuning the pump photon energy, hot carriers can be excited into different energy bands, and the hot carriers decay dynamics are measured. The hot carriers excited by an 1.544 eV photon induce a positive differential reflectivity following a single exponential decay, while the hot carriers excited by an 1.651 eV photon show a negative reflectivity following two exponential decays, i.e., the hot carriers excited by 1.544 eV and 1.651 eV photons show different decay dynamics. We also investigate hot carrier dynamics in each Rashba splitting band at the 1.544 eV and 1.651 eV photon pump, and there is no difference in hot carrier decay between the left and right Rashba splitting bands for both cases.

Electrically and optically erasable non-volatile two-dimensional electron gas memory.

The high-mobility two-dimensional electron gas (2DEG) generated at the interface between two wide-band insulators, LaAlO3 (LAO) and SrTiO3 (STO), is an extensively researched topic. In this study, we have successfully realized reversible switching between metallic and insulating states of the 2DEG system via the application of optical illumination and positive pulse voltage induced by the introduction of oxygen vacancies as reservoirs for electrons. The positive pulse voltage irreversibly drives the electron to the defect energy level formed by the oxygen vacancies, which leads to the formation of the insulating state. Subsequently, the metallic state can be achieved via optical illumination, which excites the trapped electron back to the 2DEG potential well. The ON/OFF state is observed to be robust with a ratio exceeding 106; therefore, the interface can be used as an electrically and optically erasable non-volatile 2DEG memory.

Magnetic Skyrmions with Unconventional Helicity Polarization in a Van Der Waals Ferromagnet.

Skyrmion helicity, which defines the spin swirling direction, is a fundamental parameter that may be utilized to encode data bits in future memory devices. Generally, in centrosymmetric ferromagnets, dipole skyrmions with helicity of -π/2 and π/2 are degenerate in energy, leading to equal populations of both helicities. On the other hand, in chiral materials where the Dzyaloshinskii-Moriya interaction (DMI) prevails and the dipolar interaction is negligible, only a preferred helicity is selected by the type of DMI. However, whether there is a rigid boundary between these two regimes remains an open question. Herein, the observation of dipole skyrmions with unconventional helicity polarization in a van der Waals ferromagnet, Fe5- δ GeTe2 , is reported. Combining magnetometry, Lorentz transmission electron microscopy, electrical transport measurements, and micromagnetic simulations, the short-range superstructures in Fe5- δ GeTe2 resulting in a localized DMI contribution, which breaks the degeneracy of the opposite helicities and leads to the helicity polarization, is demonstrated. Therefore, the helicity feature in Fe5- δ GeTe2 is controlled by both the dipolar interaction and DMI that the former leads to Bloch-type skyrmions with helicity of ±π/2 whereas the latter breaks the helicity degeneracy. This work provides new insights into the skyrmion topology in van der Waals materials.

Feasible Way to Achieve Multifunctional (K, Na)NbO3-Based Ceramics: Controlling Long-Range Ferroelectric Ordering.

It is challenging to achieve highly tunable multifunctional properties in one piezoelectric ceramic system through a simple method due to the complicated relationship between the microscopic structure and macroscopic property. Here, multifunctional potassium sodium niobate [(K, Na)NbO3 (KNN)]-based lead-free piezoceramics with tunable piezoelectric and electrostrictive properties are achieved by controlling the long-range ferroelectric ordering (LRFO) through antimony (Sb) doping. At a low Sb doping, the slightly distorted NbO6 octahedron and the softened B-O repulsion well maintain the LRFO and induce plenty of nanoscale domains coexisting with a few polar nanoregions (PNRs). Thereby, the diffused rhombohedral-orthorhombic-tetragonal (R-O-T) multiphase coexistence with distinct dielectric jumping is constructed near room temperature, by which the nearly 2-fold increase in the piezoelectric coefficient (d33 ∼ 539 pC/N) and the temperature-insensitive strain (the unipolar strain varies less than 8% at 27-120 °C) are obtained. At a high Sb doping, the LRFO is significantly destroyed, leading to predominant PNRs. Thus, a typical relaxor is obtained at the ferroelectric-paraelectric phase transition near room temperature, in which a large electrostrictive coefficient (Q33 = 0.035 m4/C2), independent of the electric field and temperature, is obtained and comparable to that of lead-based materials. Therefore, our results prove that controlling the LRFO is a feasible way to achieve high-performance multifunctional KNN-based ceramics and is beneficial to the future composition design for KNN-based ceramics.