Structure-Controlled Carbon Hosts for Dendrite-Free Aqueous Zinc Batteries.

The surging demand for environmental-friendly and safe electrochemical energy storage systems has driven the development of aqueous zinc (Zn)-ion batteries (ZIBs). However, metallic Zn anodes suffer from severe dendrite growth and large volume change, resulting in a limited lifetime for aqueous ZIB applications. Here, it is shown that 3D mesoporous carbon (MC) with controlled carbon and defect configurations can function as a highly reversible and dendrite-free Zn host, enabling the stable operation of aqueous ZIBs. The MC host has a structure-controlled architecture that contains optimal sp2 -carbon and defect sites, which results in an improved initial nucleation energy barrier and promotes uniform Zn deposition. As a consequence, the MC host shows outstanding Zn plating/stripping performance over 1000 cycles at 2 mA cm-2 and over 250 cycles at 6 mA cm-2 in asymmetric cells. Density functional theory calculations further reveal the role of the defective sp2 -carbon surface in Zn adsorption energy. Moreover, a full cell based on Zn@MC900 anode and V2 O5 cathode exhibits remarkable rate performance and cycling stability over 3500 cycles. These results establish a structure-mechanism-performance relationship of the carbon host as a highly reversible Zn anode for the reliable operation of ZIBs.

Unexpected Penetration of CO Molecule into Zeolitic Micropores Almost Plugged by CuCl via π-Complexation of CO-CuCl.

Carbon monoxide (CO) is a key reactant in several Fischer-Tropsch processes, including those used in light olefin and methanol syntheses. However, it is highly toxic and causes serious poisoning of noble metal catalysts. Thus, a solid adsorbent that can selectively capture CO, especially at low concentrations, is required. In this study, zeolite Y-based adsorbents in which Cu(I) ions occupy the supercage cation sites (CuCl/Y) are prepared via solid-state ion exchange. Volumetric adsorption measurements reveal that the Cu(I) ions significantly enhance CO adsorption in the low-pressure range by π-complexation. Furthermore, unexpected molecular sieving behavior, with extremely high CO/CO2 selectivity, is observed when excess CuCl homogeneously covers the zeolite pore structures. Thus, although CO has a larger kinetic diameter, it can penetrate the zeolite supercage while smaller molecules (i.e., Ar and CO2) cannot. Density functional theory calculations reveal that CO molecules can remain adsorbed in pseudoblocked pores by CuCl, thanks to the strong interaction of C 2p and Cu 3d states, resulting in the high CO/CO2 selectivity. One of the prepared adsorbents, CuCl/Y with 50 wt % CuCl, is capable of selectively capturing 3.04 mmol g-1 of CO with a CO/CO2 selectivity of >3370.

Colossal Dielectric Perovskites of Calcium Copper Titanate (CaCu3 Ti4 O12 ) with Low-Iridium Dopants Enables Ultrahigh Mass Activity for the Acidic Oxygen Evolution Reaction.

Oxygen evolution reaction (OER) under acidic conditions becomes of significant importance for the practical use of a proton exchange membrane (PEM) water electrolyzer. In particular, maximizing the mass activity of iridium (Ir) is one of the maiden issues. Herein, the authors discover that the Ir-doped calcium copper titanate (CaCu3Ti4O12, CCTO) perovskite exhibits ultrahigh mass activity up to 1000 A gIr -1 for the acidic OER, which is 66 times higher than that of the benchmark catalyst, IrO2 . By substituting Ti with Ir in CCTO, metal-oxygen (M-O) covalency can be significantly increased leading to the reduced energy barrier for charge transfer. Further, highly polarizable CCTO perovskite referred to as "colossal dielectric", possesses low defect formation energy for oxygen vacancy inducing a high number of oxygen vacancies in Ir-doped CCTO (Ir-CCTO). Electron transfer occurs from the oxygen vacancies and Ti to the substituted Ir consequentially resulting in the electron-rich Ir and -deficient Ti sites. Thus, favorable adsorptions of oxygen intermediates can take place at Ti sites while the Ir ensures efficient charge supplies during OER, taking a top position of the volcano plot. Simultaneously, the introduced Ir dopants form nanoclusters at the surface of Ir-CCTO, which can boost catalytic activity for the acidic OER.

Lagerstroemia indica extract regulates human hair dermal papilla cell growth and degeneration via modulation of ß-catenin, Stat6, and TGF-ß signaling pathway.

BACKGROUND: Lagerstroemia indica (L. indica) is reported to have diverse biological activities including anti-inflammatory, anti-cancer, neuro-regulatory, antidiabetic, and antioxidant activity. AIMS: The purpose of this study is to examine the potential of hair growth promotion and/or hair loss prevention by L. indica extract. PATIENTS/METHODS: The effects of L. indica on hair growth have been studied in human hair follicle dermal papillary (hHFDP) cells and follicular organ culture ex vivo by cell proliferation assay, PCR, western blot analysis, and reporter gene activity assay. Moreover, a clinical trial was conducted in healthy volunteers. RESULTS: Lagerstroemia indica significantly promoted the proliferation of hHFDP cells, which was associated with increased expression of TCF/LEF, VEGF, and Gli1 mRNA, and inhibition of STAT6 and Smad2 mRNA. Treatment with L. indica also increased the TCF/LEF reporter gene activity but downregulated the SBE- and STAT6-luciferase activities. The expression of total ß-catenin, CDK4, and CDK2 were elevated, while that of STAT6 and SMAD2/3 was suppressed upon treatment with L. indica. In human hair follicles organ culture, L. indica significantly inhibited hair follicular degeneration. The clinical trial showed a statistically significant rise in total hair count in test group (n = 24) after 24 weeks of applying the hair tonic enriched with L. indica (141.46 ± 21.27 number/cm2 , p < 0.05). CONCLUSION: We suggest that L. indica extract prevents hair loss as well as stimulate hair growth by regulating the Wnt-ß-catenin, JAK3-STAT6, and TGF-ß1-Smad signaling pathways, and may be further developed as a novel functional cosmetic for preventing hair loss.

A 3D Hierarchical Host with Enhanced Sodiophilicity Enabling Anode-Free Sodium-Metal Batteries.

Sodium-metal batteries (SMBs) are considered as a compliment to lithium-metal batteries for next-generation high-energy batteries because of their low cost and the abundance of sodium (Na). Herein, a 3D nanostructured porous carbon particle containing carbon-shell-coated Fe nanoparticles (PC-CFe) is employed as a highly reversible Na-metal host. PC-CFe has a unique 3D hierarchy based on sub-micrometer-sized carbon particles, ordered open channels, and evenly distributed carbon-coated Fe nanoparticles (CFe) on the surface. PC-CFe achieves high reversibility of Na plating/stripping processes over 500 cycles with a Coulombic efficiency of 99.6% at 10 mA cm-2 with 10 mAh cm-2 in Na//Cu asymmetric cells, as well as over 14 400 cycles at 60 mA cm-2 in Na//Na symmetric cells. Density functional theory calculations reveal that the superior cycling performance of PC-CFe stems from the stronger adsorption of Na on the surface of the CFe, providing initial nucleation sites more favorable to Na deposition. Moreover, the full cell with a PC-CFe host without Na metal and a high-loading Na3 V2 (PO4 )3 cathode (10 mg cm-2 ) maintains a high capacity of 103 mAh g-1 at 1 mA cm-2 even after 100 cycles, demonstrating the operation of anode-free SMBs.

First-Principles-Based Machine-Learning Molecular Dynamics for Crystalline Polymers with van der Waals Interactions.

Machine-learning (ML) techniques have drawn an ever-increasing focus as they enable high-throughput screening and multiscale prediction of material properties. Especially, ML force fields (FFs) of quantum mechanical accuracy are expected to play a central role for the purpose. The construction of ML-FFs for polymers is, however, still in its infancy due to the formidable configurational space of its composing atoms. Here, we demonstrate the effective development of ML-FFs using kernel functions and a Gaussian process for an organic polymer, polytetrafluoroethylene (PTFE), with a data set acquired by first-principles calculations and ab initio molecular dynamics (AIMD) simulations. Even though the training data set is sampled only with short PTFE chains, structures of longer chains optimized by our ML-FF show an excellent consistency with density functional theory calculations. Furthermore, when integrated with molecular dynamics simulations, the ML-FF successfully describes various physical properties of a PTFE bundle, such as a density, melting temperature, coefficient of thermal expansion, and Young's modulus.

Multiscale Modeling of Agglomerated Ceria Nanoparticles: Interface Stability and Oxygen Vacancy Formation.

The interface formation and its effect on redox processes in agglomerated ceria nanoparticles (NPs) have been investigated using a multiscale simulation approach with standard density functional theory (DFT), the self-consistent-charge density functional tight binding (SCC-DFTB) method, and a DFT-parameterized reactive force-field (ReaxFF). In particular, we have modeled Ce40O80 NP pairs, using SCC-DFTB and DFT, and longer chains and networks formed by Ce40O80 or Ce132O264 NPs, using ReaxFF molecular dynamics simulations. We find that the most stable {111}/{111} interface structure is coherent whereas the stable {100}/{100} structures can be either coherent or incoherent. The formation of {111}/{111} interfaces is found to have only a very small effect on the oxygen vacancy formation energy, E vac. The opposite holds true for {100}/{100} interfaces, which exhibit significantly lower E vac values than the bare surfaces, despite the fact that the interface formation eliminates reactive {100} facets. Our results pave the way for an increased understanding of ceria NP agglomeration.

Delamination-Free Multifunctional Separator for Long-Term Stability of Lithium-Ion Batteries.

Next-generation lithium-ion batteries (LIBs) that satisfy the requirements for an electric vehicle energy source should demonstrate high reliability and safety for long-term high-energy-density operation. This inevitably calls for a novel approach to advance major components such as the separator. Herein, a separator is designed and fabricated via application of multilayer functional coating on both sides of a polyethylene separator. The multilayer-coated separator (MCS) has a porous structure that does not interfere with lithium ion diffusion and exhibits superior heat resistance, high electrolyte uptake, and persistent adhesion with the electrode. More importantly, it enables high capacity retention and reduced impedance build up during cycling when used in a coin or pouch cell. These imply its promising application in energy sources requiring long-term stability. Fabrication of the MCS without the use of organic solvents is not only environmentally beneficial but also effective at cost reduction. This approach paves the way for the separator, which has long been considered an inactive major component of LIBs, to become an active contributor to the energy density toward achieving longer cycle stability.

Clinical efficacy of herbal extract cream on the skin hydration, elasticity, thickness, and dermis density for aged skin: A randomized controlled double-blind study.

BACKGROUND: Traditional medicine herbal prescriptions used for the treatment of skin disease have been developed into cosmetics. Sang-Hyul-Yun-Boo-Em (SHYBE) is a mixed herbal formula prescribed for patients with yin or blood deficiency patterns of skin disease. A previous study reported that SHYBE exercises anti-allergic and anti-inflammatory effects. To date, no study has reported the efficacy of cosmetics containing the SHYBE extract. AIMS: To observe the efficacy of SHYBE extract cream on hydration, elasticity, thickness, and dermis density in aged skin. METHODS: This was a double-blind randomized placebo-controlled parallel-group trial. The trial consisted of an 8-week topical application of the test or placebo products with two visits at 4-week intervals. A total of 46 healthy Korean females, aged 40-59, were enrolled in this study. Objective skin assessments for hydration, elasticity, thickness and dermis density, self-assessment, and safety assessment were conducted. RESULTS: Sang-Hyul-Yun-Boo-Em extract cream improved skin hydration, elasticity, and dermal density in Asian middle-aged females compared with placebo cream, which excluded SHYBE extract and contained other cosmetic materials. CONCLUSIONS: Sang-Hyul-Yun-Boo-Em extract cream showed anti-aging properties in middle-aged women. It could be recommended for aging skin with dryness, and loss of elasticity and density.

Real-time Humidity Sensor Based on Microwave Resonator Coupled with PEDOT:PSS Conducting Polymer Film.

A real-time humidity sensor based on a microwave resonator coupled with a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) conducting polymer (CP) film is proposed in this paper. The resonator is patterned on a printed circuit board and is excited by electromagnetic field coupling. To enhance the sensitivity of the sensor, the CP film is located in the area with the strongest electric field in the resonator. To investigate the performance, the proposed sensor is placed alongside a reference sensor in a humidity chamber, and humidity is injected at room temperature. The experimental results indicate that the electrical properties of the resonator with the CP film, such as the transmission coefficient (S 21) and resonance frequency, change with the relative humidity (RH). Specifically, as the RH changes from 5% to 80%, S 21 and the resonance frequency change simultaneously. Moreover, the proposed sensor exhibits great repeatability in the middle of the sensing range, which is from 40% to 60% RH. Consequently, our resonator coupled with the CP film can be used as a real-time humidity-sensing device in the microwave range, where various radio-frequency devices are in use.

Insecticidal activity of the metalloprotease AprA occurs through suppression of host cellular and humoral immunity.

The biochemical characterization of virulence factors from entomopathogenic bacteria is important to understand entomopathogen-insect molecular interactions. Pseudomonas entomophila is a typical entomopathogenic bacterium that harbors virulence factors against several insects. However, the molecular actions of these factors against host innate immune responses are not clearly elucidated. In this study, we observed that bean bugs (Riptortus pedestris) that were injected with P. entomophila were highly susceptible to this bacterium. To determine how P. entomophila counteracts the host innate immunity to survive within the insect, we purified a highly enriched protein with potential host insect-killing activity from the culture supernatant of P. entomophila. Then, a 45-kDa protein was purified to homogeneity and identified as AprA which is an alkaline zinc metalloprotease of the genus Pseudomonas by liquid chromatography mass spectrometry (LC-MS). Purified AprA showed a pronounced killing effect against host insects and suppressed both host cellular and humoral innate immunity. Furthermore, to show that AprA is an important insecticidal protein of P. entomophila, we used an aprA-deficient P. entomophila mutant strain (ΔaprA). When ΔaprA mutant cells were injected to host insects, this mutant exhibited extremely attenuated virulence. In addition, the cytotoxicity against host hemocytes and the antimicrobial peptide-degrading ability of the ΔaprA mutant were greatly decreased. These findings suggest that AprA functions as an important insecticidal protein of P. entomophila via suppression of host cellular and humoral innate immune responses.

PhaR, a Negative Regulator of PhaP, Modulates the Colonization of a Burkholderia Gut Symbiont in the Midgut of the Host Insect, Riptortus pedestris.

Five genes encoding PhaP family proteins and one phaR gene have been identified in the genome of Burkholderia symbiont strain RPE75. PhaP proteins function as the surface proteins of polyhydroxyalkanoate (PHA) granules, and the PhaR protein acts as a negative regulator of PhaP biosynthesis. Recently, we characterized one phaP gene to understand the molecular cross talk between Riptortus insects and Burkholderia gut symbionts. In this study, we constructed four other phaP gene-depleted mutants (ΔphaP1, ΔphaP2, ΔphaP3, and ΔphaP4 mutants), one phaR gene-depleted mutant, and a phaR-complemented mutant (ΔphaR/phaR mutant). To address the biological roles of four phaP family genes and the phaR gene during insect-gut symbiont interaction, these Burkholderia mutants were fed to the second-instar nymphs, and colonization ability and fitness parameters were examined. In vitro, the ΔphaP3 and ΔphaR mutants cannot make a PHA granule normally in a stressful environment. Furthermore, the ΔphaR mutation decreased the colonization ability in the host midgut and negatively affected the host insect's fitness compared with wild-type Burkholderia-infected insects. However, other phaP family gene-depleted mutants colonized well in the midgut of the fifth-instar nymph insects. However, in the case of females, the colonization rate of the ΔphaP3 mutant was decreased and the host's fitness parameters were decreased compared with the wild-type-infected host, suggesting that the environment of the female midgut may be more hostile than that of the male midgut. These results demonstrate that PhaR plays an important role in the biosynthesis of PHA granules and that it is significantly related to the colonization of the Burkholderia gut symbiont in the host insects' midgut.IMPORTANCE Bacterial polyhydroxyalkanoate (PHA) biosynthesis is a complex process requiring several enzymes. The biological roles of PHA granule synthesis enzymes and the surface proteins of PHA granules during host-gut symbiont interactions are not fully understood. Here, we report the effects on colonization ability in the host midguts and the fitness of host insects after feeding Burkholderia mutant cells (four phaP-depleted mutants and one phaR-depleted mutant) to the host insects. Analyses of both synthesized PHA granule amounts and CFU numbers suggest that the phaR gene is closely related to synthesis of the PHA granule and the colonization of the Burkholderia gut symbiont in the host insect's midgut. Like our previous report, this study also supports the idea that the environment of the host midgut may not be favorable to symbiotic Burkholderia cells and that PHA granules may be required to adapt in the host midgut.

Functionalization effect on a Pt/carbon nanotube composite catalyst: a first-principles study.

Chemical interactions between Pt and both pristine and defective carbon nanotubes (CNTs) that were functionalized with various surface functional groups, including atomic oxygen (-O), atomic nitrogen (-N), hydroxyl (-OH) and amine (-NH2) groups, were investigated through first-principles calculations. Our calculations suggest that the oxygen or nitrogen of the surface functional group can promote better structural stability of a Pt/CNT complex in terms of the binding energy enhancement between Pt and CNTs. Enhanced binding of the Pt/CNT complex would improve the long-term durability of the complex and thus enhance the catalytic activity of Pt catalysts supported on CNTs. Among the functional groups investigated, atomic nitrogen resulted in the most consistent increase in the Pt binding energies on pristine or defective CNTs. Moreover, atomic nitrogen decoration on the surface of CNTs rather than substitution into the CNTs appears to be more desirable. A d-band centre analysis and H2 adsorption calculations also revealed that the catalytic activity of Pt can be improved via efficient functionalization of the CNT support.

Flexible Non-Constrained RF Wrist Pulse Detection Sensor Based on Array Resonators.

This paper presents the development of a non-contact, nonintrusive wrist pulse sensor based on the near-field variation of an array resonator. A compact resonator and its array were designed and fabricated on flexible substrate. The reflection coefficient of the resonator can vary as a function of the distance between the resonator and the walls of the major arteries, and the corresponding variation is utilized to obtain heart rate information at the wrist. To detect very weak pulse signals from the main arteries, a sensitivity enhancement technique was devised using a radio frequency (RF) array resonator. The sensor system was implemented with an RF switch to combine or select appropriate signals from the resonator element and was tested using the 2.4 GHz ISM band. The results demonstrated the sensor system's excellent performance in both sequential and simultaneous detection schemes. The measurement results showed that a heartbeat pulse can be detected from both radial and ulnar arteries via the array resonators. Considering the high sensitivity and characteristics, the proposed detection system can be utilized as a wearable, long-term health monitoring device.

Heart Rate Detection During Sleep Using a Flexible RF Resonator and Injection-Locked PLL Sensor.

Novel nonintrusive technologies for wrist pulse detection have been developed and proposed as systems for sleep monitoring using three types of radio frequency (RF) sensors. The three types of RF sensors for heart rate measurement on wrist are a flexible RF single resonator, array resonators, and an injection-locked PLL resonator sensor. To verify the performance of the new RF systems, we compared heart rates between presleep time and postsleep onset time. Heart rates of ten subjects were measured using the RF systems during sleep. All three RF devices detected heart rates at 0.2 to 1 mm distance from the skin of the wrist over clothes made of cotton fabric. The wrist pulse signals of a flexible RF single resonator were consistent with the signals obtained by a portable piezoelectric transducer as a reference. Then, we confirmed that the heart rate after sleep onset time significantly decreased compared to before sleep. In conclusion, the RF system can be utilized as a noncontact nonintrusive method for measuring heart rates during sleep.

Noncontact proximity vital sign sensor based on PLL for sensitivity enhancement.

In this paper, a noncontact proximity vital sign sensor, using a phase locked loop (PLL) incorporated with voltage controlled oscillator (VCO) built-in planar type circular resonator, is proposed to enhance sensitivity in severe environments. The planar type circular resonator acts as a series feedback element of the VCO as well as a near-field receiving antenna. The frequency deviation of the VCO related to the body proximity effect ranges from 0.07 MHz/mm to 1.8 MHz/mm (6.8 mV/mm to 205 mV/mm in sensitivity) up to a distance of 50 mm, while the amount of VCO drift is about 21 MHz in the condition of 60 (°)C temperature range and discrete component tolerance of ± 5%. Total frequency variation occurs in the capture range of the PLL which is 60 MHz. Thus, its loop control voltage converts the amount of frequency deviation into a difference of direct current (DC) voltage, which is utilized to extract vital signs regardless of the ambient temperature. The experimental results reveal that the proposed sensor placed 50 mm away from a subject can reliably detect respiration and heartbeat signals without the ambiguity of harmonic signals caused by respiration signal at an operating frequency of 2.4 GHz.

A molecular dynamics simulation study on the initial stage of Si(001) oxidation under biaxial strain.

We have studied the very early stage of the room temperature oxidation of the externally-strained Si(001) surface using molecular dynamics simulation. It was found that the different treatment history of the sample under the same strain resulted in the difference in the number density of dimer. The as-prepared samples of different treatment history with 12.15% strain were used to investigate the initial oxidation behavior of Si(001). 500 times of independent deposition of single oxygen molecule onto the random position of clean Si(001) surface was simulated. Oxidation behavior was statistically analyzed for various dimer density of the surface which is dependent on strain-treatment history. Oxygen uptake and penetration depth profile showed an important role of dimers on the surface oxidation behavior.