Van Hove annihilation and nematic instability on a kagome lattice.

A nematic phase breaks the point-group symmetry of the crystal lattice and is known to emerge in correlated materials. Here we report the observation of an intra-unit-cell nematic order and associated Fermi surface deformation in the kagome metal ScV6Sn6. Using scanning tunnelling microscopy and scanning tunnelling spectroscopy, we reveal a stripe-like nematic order breaking the crystal rotational symmetry within the kagome lattice itself. Moreover, we identify a set of Van Hove singularities adhering to the kagome-layer electrons, which appear along one direction of the Brillouin zone and are annihilated along other high-symmetry directions, revealing rotational symmetry breaking. Via detailed spectroscopic maps, we further observe an elliptical deformation of the Fermi surface, which provides direct evidence for an electronically mediated nematic order. Our work not only bridges the gap between electronic nematicity and kagome physics but also sheds light on the potential mechanism for realizing symmetry-broken phases in correlated electron systems.

Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides.

Lattice oxygen redox offers an unexplored way to access superior electrochemical properties of transition metal oxides (TMOs) for rechargeable batteries. However, the reaction is often accompanied by unfavourable structural transformations and persistent electrochemical degradation, thereby precluding the practical application of this strategy. Here we explore the close interplay between the local structural change and oxygen electrochemistry during short- and long-term battery operation for layered TMOs. The substantially distinct evolution of the oxygen-redox activity and reversibility are demonstrated to stem from the different cation-migration mechanisms during the dynamic de/intercalation process. We show that the π stabilization on the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of cation migrations; however, the π-interacting oxygen is gradually replaced by σ-interacting oxygen that triggers the formation of O-O dimers and structural destabilization as cycling progresses. More importantly, it is revealed that the distinct cation-migration paths available in the layered TMOs govern the conversion kinetics from π to σ interactions. These findings constitute a step forward in unravelling the correlation between the local structural evolution and the reversibility of oxygen electrochemistry and provide guidance for further development of oxygen-redox layered electrode materials.

Lead-Free Piezoelectric Acceleration Sensor Built Using a (K,Na)NbO3 Bulk Ceramic Modified by Bi-Based Perovskites.

Piezoelectric accelerometers using a lead-free (K,Na)NbO3 (KNN) piezoceramic modified by a mixture of two Bi-based perovskites, Bi(Na,K,Li)ZrO3 (BNKLZ) and BiScO3 (BS), were designed, fabricated and characterized. Ring-shaped ceramics were prepared using a conventional solid-state reaction method for integration into a compression-mode accelerometer. A beneficial rhombohedral-tetragonal (R-T) phase boundary structure, especially enriched with T phase, was produced by modifying intrinsic phase transition temperatures, yielding a large piezoelectric charge coefficient d33 (310 pC/N) and a high Curie temperature Tc (331 °C). Using finite element analyses with metamodeling techniques, four optimum accelerometer designs were obtained with high magnitudes of charge sensitivity Sq and resonant frequency fr, as evidenced by two key performance indicators having a trade-off relation. Finally, accelerometer sensor prototypes based on the proposed designs were fabricated using the KNN-BNKLZ-BS ceramic rings, which exhibited high levels of Sq (55.1 to 223.8 pC/g) and mounted fr (14.1 to 28.4 kHz). Perfect charge-to-acceleration linearity as well as broad flat frequency ranges were achieved with excellent reliability. These outstanding sensing performances confirm the potential application of the modified-KNN ceramic in piezoelectric sensors.

Nanoscale Phenomena in Lithium-Ion Batteries.

The electrochemical properties and performances of lithium-ion batteries are primarily governed by their constituent electrode materials, whose intrinsic thermodynamic and kinetic properties are understood as the determining factor. As a part of complementing the intrinsic material properties, the strategy of nanosizing has been widely applied to electrodes to improve battery performance. It has been revealed that this not only improves the kinetics of the electrode materials but is also capable of regulating their thermodynamic properties, taking advantage of nanoscale phenomena regarding the changes in redox potential, solid-state solubility of the intercalation compounds, and reaction paths. In addition, the nanosizing of materials has recently enabled the discovery of new energy storage mechanisms, through which unexplored classes of electrodes could be introduced. Herein, we review the nanoscale phenomena discovered or exploited in lithium-ion battery chemistry thus far and discuss their potential implications, providing opportunities to further unveil uncharted electrode materials and chemistries. Finally, we discuss the limitations of the nanoscale phenomena presently employed in battery applications and suggest strategies to overcome these limitations.

Reactive Oxygen Species and Folate Receptor-Targeted Nanophotosensitizers Composed of Folic Acid-Conjugated and Poly(ethylene glycol)-Chlorin e6 Tetramer Having Diselenide Linkages for Targeted Photodynamic Treatment of Cancer Cells.

Folic acid-conjugated nanophotosensitizers composed of folic acid (FA), poly(ethylene glycol) (PEG) and chlorin e6 (Ce6) tetramer were synthesized using diselenide linkages for reactive oxygen species (ROS)- and folate receptor-specific delivery of photosensitizers. Ce6 was conjugated with 3-[3-(2-carboxyethoxy)-2,2-bis(2-carboxyethoxymethyl)propoxy]propanoic acid (tetra acid, or TA) to make Ce6 tetramer via selenocystamine linkages (TA-sese-Ce6 conjugates). In the carboxylic acid end group of the TA-sese-Ce6 conjugates, FA-PEG was attached again using selenocystamine linkages to make FA-PEG/TA-sese-Ce6 conjugates (abbreviated as FAPEGtaCe6 conjugates). Nanophotosensitizers were fabricated by a dialysis procedure. In the morphological observations, they showed spherical shapes with small diameters of less than 200 nm. Stability of the aqueous FAPEGtaCe6 nanophotosensitizer solution was maintained (i.e., their particle sizes were not significantly changed until 7 days later). When H2O2 was added to the nanophotosensitizer solution, the particle size distribution was changed from a monomodal pattern to a multimodal pattern. In addition, the fluorescence intensity and Ce6 release rate from the nanophotosensitizers were also increased by the addition of H2O2. These results indicated that the nanophotosensitizers had ROS-sensitive properties. In an in vitro cell culture study, an FAPEGtaCe6 nanophotosensitizer treatment against cancer cells increased the Ce6 uptake ratio, ROS generation and light-irradiated cytotoxicity (phototoxicity) compared with Ce6 alone against various cancer cells. When the folic acid was pretreated to block the folate receptors of the Y79 cells and KB cells (folate receptor-overexpressing cells), the intracellular Ce6 uptake, ROS generation and thereby phototoxicity were decreased, while the MCF-7 cells did not significantly respond to blocking of the folate receptors. These results indicated that they could be delivered by a folate receptor-mediated pathway. Furthermore, an in vivo pulmonary metastasis model using Y79 cells showed folate receptor-specific delivery of FAPEGtaCe6 nanophotosensitizers. When folic acid was pre-administered, the fluorescence intensity of the lungs was significantly decreased, indicating that the FAPEGtaCe6 nanophotosensitizers had folate receptor specificity in vitro and in vivo. We suggest that FAPEGtaCe6 nanophotosensitizers are promising candidates for a targeted photodynamic therapy (PDT) approach against cancer cells.

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes.

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

Combinatorial Effect of Cold Atmosphere Plasma (CAP) and the Anticancer Drug Cisplatin on Oral Squamous Cell Cancer Therapy.

Cold atmospheric plasma (CAP) has been extensively investigated in the local treatment of cancer due to its potential of reactive oxygen species (ROS) generation in biological systems. In this study, we examined the synergistic effect of combination of CAP and cisplatin-mediated chemotherapy of oral squamous cell carcinoma (OSCC) in vitro. SCC-15 OSCC cells and human gingival fibroblasts (HGF-1) cells were treated with cisplatin, and then, the cells were irradiated with CAP. Following this, viability and apoptosis behavior of the cells were investigated. The viability of SCC-15 cells was inhibited by cisplatin with a dose-dependent manner and CAP treatment time. HGF-1 cells also showed decreased viability by treatment with cisplatin and CAP. Combination of 1 µM cisplatin plus 3 min of CAP treatment or 3 µM cisplatin plus 1 min of CAP treatment showed a synergistic anticancer effect with appropriate cytotoxicity against normal cells. ROS generation and dead cell staining were also increased by the increase in CAP treatment time. Furthermore, tumor-suppressor proteins and apoptosis-related enzymes also increased according to the treatment time of CAP. We showed the synergistic effect of cisplatin and CAP treatment against SCC-15 cells with low cytotoxicity against normal cells.

Redox-Sensitive Facet Dependency in Etching of Ceria Nanocrystals Directly Observed by Liquid Cell TEM.

Defining the redox activity of different surface facets of ceria nanocrystals is important for designing an efficient catalyst. Especially in liquid-phase reactions, where surface interactions are complicated, direct investigation in a native environment is required to understand the facet-dependent redox properties. Using liquid cell TEM, we herein observed the etching of ceria-based nanocrystals under the control of redox-governing factors. Direct nanoscale observation reveals facet-dependent etching kinetics, thus identifying the specific facet ({100} for reduction and {111} for oxidation) that governs the overall etching under different chemical conditions. Under each redox condition, the contribution of the predominant facet increases as the etching reactivity increases.

Decyl Glucoside Synthesized by Direct Glucosidation of D-Glucose Over Zeolite Catalysts and Its Estrogenicity as Non-Endocrine Disruptive Surfactant.

The estrogenicity of decyl glucoside was asserted as a non-endocrine disruptive surfactant with its preparation method using zeolite catalysts. Its estrogenicity was estimated using E-assay method. The decyl glucoside was synthesized by direct glucosidation from D-glucose with 1-decanol. The conversion and yield were improved with increasing of amount of acid sites of the zeolite catalysts. The decyl glucopyranoside is more hydrophilic than nonylphenol and has a high wettability. The decyl glucopyranosides exhibited extremely lower proliferation of estrogenic cell compared with nonylphenol.

Oxygen and Acrylic Acid Plasma Treatment on Titanium Mesh for Improving the Hydroxyapatite Formation.

Customized titanium (Ti) meshes were treated with O2 plasma and acrylic acid plasmapolymerization (PPAAc). The optimum conditions for PPAAc were as follows: 20 W, 15 mTorr, and 5 min. Hydroxyapatite formation increased in Ti meshes treated with O2 and PPAAc compared with that in untreated Ti meshes. Moreover, MC3T3-E1 cells exhibited improved cell spreading, attachment, proliferation in PPAAc treated Ti mesh than in untreated Ti mesh. This result revealed that O2 and PPAAc surface treatment on Ti mesh was potential tool for improving the bone formation on the Ti mesh clinically application.

Estrogenicity of Octyl Glucoside Synthesized by Direct Glucosidation as Non-Endocrine Disruptive Surfactant.

The estrogenicity of octyl glucoside was studied with its preparation method using microporous zeolites. Its estrogenicity was estimated using E-assay method to confirm the possibility as non-endocrine disruptive surfactant. The octyl glucoside was synthesized from D-glucose with 1-octanol by direct glucosidation. The high conversion of D-glucose was obtained on H-FAU zeolite which has a mild acid strength. The conversion and yield were improved with increasing of acid site amount of the zeolite catalysts. The octyl glucopyranoside is more hydrophilic than nonylphenol and has a high wettability. The octyl glucosides represented extremely lower estrogenic cell proliferation compared with nonylphenol.

Fabrication and Characterization of Finite-Size DNA 2D Ring and 3D Buckyball Structures.

In order to incorporate functionalization into synthesized DNA nanostructures, enhance their production yield, and utilize them in various applications, it is necessary to study their physical stabilities and dynamic characteristics. Although simulation-based analysis used for DNA nanostructures provides important clues to explain their self-assembly mechanism, structural function, and intrinsic dynamic characteristics, few studies have focused on the simulation of DNA supramolecular structures due to the structural complexity and high computational cost. Here, we demonstrated the feasibility of using normal mode analysis for relatively complex DNA structures with larger molecular weights, i.e., finite-size DNA 2D rings and 3D buckyball structures. The normal mode analysis was carried out using the mass-weighted chemical elastic network model (MWCENM) and the symmetry-constrained elastic network model (SCENM), both of which are precise and efficient modeling methodologies. MWCENM considers both the weight of the nucleotides and the chemical bonds between atoms, and SCENM can obtain mode shapes of a whole structure by using only a repeated unit and its connectivity with neighboring units. Our results show the intrinsic vibrational features of DNA ring structures, which experience inner/outer circle and bridge motions, as well as DNA buckyball structures having overall breathing and local breathing motions. These could be used as the fundamental basis for designing and constructing more complicated DNA nanostructures.

Oxygen Plasma Treatment on 3D-Printed Chitosan/Gelatin/Hydroxyapatite Scaffolds for Bone Tissue Engineering.

The 3D hydroxyapatite/gelatin/chitosan composite scaffolds were fabricated by 3D printing technique. The scaffolds were treated by oxygen plasma to improve the bioactivity and its surface characterization and in vitro cell culture were investigated. The scaffolds exhibited the good porosity and interconnectivity of pores. After oxygen plasma etching, roughness and wettability on the scaffolds surface are increased. Plasma treated scaffolds showed higher proliferation than that of untreated scaffolds. Oxygen plasma treatment could be used as potential tool to enhance the biocompatibility on the 3D composite scaffolds.

In Vitro Study on the Plasma-Polymerization of Propionaldehyde and Allylglycidyl Ether for Immobilization of Recombinant Human Bone Morphogenetic Protein-2.

In this study, recombinant human bone morphogenetic protein-2 (rhBMP-2) was directly immobilized on the plasma-polymerized propionaldehyde (PA) and allylglycidyl ether (AGE) surface through the imine bonding and epoxy-amine bonding, respectively. Aldehyde and epoxide plasma-polymerization were carried out at plasma power 60 W for 10 min and monomers were used to PA and AGE. After the plasma-polymerization and rhBMP-2 immobilization, substrate surfaces were characterized by contact angle, field emission scanning electron microscopy, and attenuated total reflectance Fourier transform infrared. In addition, the biological activities of MC3T3-E1 cells were evaluated by initial adhesion and alkaline phosphate (ALP) activity. The rhBMP-2 immobilized PA and AGE surfaces promoted significantly higher ALP activity of MC3T3-E1 cells than pristine surface.

Using irregularly spaced current peaks to generate an isolated attosecond X-ray pulse in free-electron lasers.

A method is proposed to generate an isolated attosecond X-ray pulse in free-electron lasers, using irregularly spaced current peaks induced in an electron beam through interaction with an intense short-pulse optical laser. In comparison with a similar scheme proposed in a previous paper, the irregular arrangement of current peaks significantly improves the contrast between the main and satellite pulses, enhances the attainable peak power and simplifies the accelerator layout. Three different methods are proposed for this purpose and achievable performances are computed under realistic conditions. Numerical simulations carried out with the best configuration show that an isolated 7.7 keV X-ray pulse with a peak power of 1.7 TW and pulse length of 70 as can be generated. In this particular example, the contrast is improved by two orders of magnitude and the peak power is enhanced by a factor of three, when compared with the previous scheme.

Cell Proliferation on Macro/Nano Surface Structure and Collagen Immobilization of 3D Polycaprolactone Scaffolds.

In this study, 3D polycaprolactone (PCL) scaffolds were fabricated by 3D printing technique. The macro/nano morphology of, 3D PCL scaffolds surface was etched with oxygen plasma. Acrylic acid (AA) plasma-polymerization was performed to functionalize the macro/nano surface with carboxyl groups and then collagen was immobilized with plasma-polymerized 3D PCL scaffolds. After O2 plasma and AA plasma-polymerization, contact angles were decreased. The FE-SEM and AFM results showed that O2 plasma is increased the surface roughness. The MTT assay results showed that proliferation of the M3CT3-E1 cells increased on the oxygen plasma treated and collagen immobilized 3D PCL scaffolds.

O2/Ar Plasma Treatment for Enhancing the Biocompatibility of Hydroxyapatite Nanopowder and Polycaprolactone Composite Film.

In this study we performed O2/Ar plasma treatment to remove the polycaprolactone on hydroxyapatite nanopowder and polycaprolactone (HAp-NP/PCL) composite film. After plasma ashing, the HAp-NP was exposed on the composite film. The 25 wt% HAp-NP/PCL treated with plasma showed the hydrophilic surface property with reducing the aging effect. The MTT and ALP results indicated that the plasma etching increased the biocompatibility of HAp-NP/PCL composite film. The present simple plasma etching technique can be applicable in a development of biomaterials.

Characteristics of Plasma Treated Electrospun Polycaprolactone (PCL) Nanofiber Scaffold for Bone Tissue Engineering.

Polycaprolactone (PCL) nanofibers (PCL-NF) with uniform fibrous structure were fabricated by electrospinning. However, PCL-NF has hydrophobic surface, lacks functional groups and hence it is not a good substrate for cell adhesion. To improve the cell adhesion, PCL-NF surfaces were modified by low pressure RF discharge plasma treatment using monomer such as acrylic acid or oxygen gas. The plasma treated PCL-NFs improved the wettability and cell proliferation.

Oxygen and Nitrogen Gas Plasma Surface Treatments on Titanium for Initial Adhesion and Proliferation of Preosteoblast Cells.

In this study, titanium (Ti) surface was treated through the use of oxygen and nitrogen plasma for improving the initial adhesion and proliferation of preosteoblast cells. The plasma treated Ti surface demonstrated hydrophilic surface property and promoted initial adhesion and proliferation of preosteoblast cells.

Fabrication of 3D Scaffolds with Nano-Hydroxyapatite for Improving the Preosteoblast Cell-Biological Performance.

Three-dimensional (3D) scaffolds fabricated by rapid prototyping techniques have many merits for tissue engineering applications, due to its controllable properties such as porosity, pore size and structural shape. Nonetheless, low cell seeding efficiency remains drawback. In this study, poly-caprolactone (PCL) composite 3D extruded scaffolds were modified with nano hydroxyapatite (n-HAp). PCL/n-HAp 3D scaffold surface was treated with oxygen plasma to improve the preosteoblast cell seeding efficiency and proliferation. The results indicate that oxygen plasma is useful technique to improve the cell affinity.