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The long-period stacking ordered phases (LPSOs) in Mg−Ni−Y system have been attracting great interest as effective strengthening components because of their unique structural characteristics and deformation mechanism. However, the phase relationships in LPSOs are complicated and unclear, which restricts the design of advanced magnesium-based alloys. The aim of the present work is to experimentally determine the phase equilibria relationships focusing on LPSOs and establish the thermodynamic description for Mg−Ni−Y system. Four types of LPSOs, that is, 14H, 12R, 18R and 10H, are confirmed through equilibrated alloys and high-resolution transmission electron microscopy (HR-TEM). The formation enthalpies of LPSOs (14H, 12R, 18R and 10H) are calculated based on density functional theories (DFT) calculations. A new ternary compound, termed as τ phase, is observed for the first time which is likely to be the distorted structure of 12R as determined from the TEM image which shows a 12-layer closed packing plane distance of 3.252 nm and a shear angle of 83.2° between (0002) and (10 1 ¯ 0) planes. Based on the determined phase equilibria relationship, the Mg−Ni−Y system is assessed and a self-consistent description is obtained where the LPSOs are modeled as the stoichiometric compounds. The comparison between the calculation result and experimental data suggests the accuracy of the present thermodynamic database in the Mg-rich corner.

Optical absorbers with multiple absorption channels are required in integrated optical circuits and have always been a challenge in visible and near-infrared (NIR) region. This paper proposes a perfect plasmonic absorber (PPA) that consists of a closed loop and a linked intersection in a unit cell for sensitive biosensing applications. We elucidate the physical nature of finite element method simulations through the absorptance spectrum, electric field intensity, magnetic flux density, and surface charge distribution. The designed PPA achieves triple channels, and the recorded dual-band absorptance reaches 99.64 and 99.00% nm, respectively. Besides, the sensitivity can get 1000.00 and 650 nm/RIU for mode 1 and mode 2, respectively. Our design has a strong electric and magnetic field coupling arising from the mutual inductance and the capacitive coupling in the proposed plasmonic system. Therefore, the designed structure can serve as a promising option for biosensors and other optical devices. Here, we illustrated two examples, i.e., detecting cancerous cells and diabetes cells.

Background Trimethylamine N-oxide (TMAO) is a microbiota-derived metabolite, which is linked to vascular inflammation and atherosclerosis in cardiovascular (CV) diseases. But its effect in infectious diseases remains unclear. We conducted a single-center prospective study to investigate association of TMAO with in-hospital mortality in septic patients admitted to an intensive care unit (ICU). Methods Totally 95 septic, mechanically ventilated patients were enrolled. Blood samples were obtained within 24 h after ICU admission, and plasma TMAO concentrations were determined. Septic patients were grouped into tertiles according to TMAO concentration. The primary outcome was in-hospital death, which further classified as CV and non-CV death. Besides, we also compared the TMAO concentrations of septic patients with 129 non-septic patients who were admitted for elective coronary angiography (CAG). Results Septic patients had significantly lower plasma TMAO levels than did subjects admitted for CAG (1.0 vs. 3.0 μmol/L, p p = 0.014). However, TMAO concentration was no longer an independent predictor for non-CV death after adjustment for disease severity and nutritional status. Conclusion Plasma TMAO concentration was inversely associated with non-CV death among extremely ill septic patients, which could be characterized as TMAO paradox. For septic patients, the impact of malnutrition reflected by circulating TMAO levels was greater than its pro-inflammatory nature.

We have fabricated a new perylene bisimide (PBI) folda-dimer (BPBI-CB-1) by tethering two PBI moieties to the ortho-carbon positions of a carborane unit. The synthesized compound adopted distinct c...

The effect of Ce on the structure of MoVNbCeO multi-metal oxide catalysts and the performance of ethane selective oxidation was investigated. These multi-metal oxide catalysts with superior oxidizability exhibit high catalytic activity, and vanadium acts as the active center for ethane oxidation reaction. The improved catalytic activity is related to the increased V5+ content on the catalyst surface, which results from the enhanced transformation of the electrons between V and Ce. Moreover, Ce effectively promotes oxygen adsorption, activation, and mobility. And the presence of Ce can also prevent MoO3 formation and stabilize the Mo5O14-like structure. In addition, the catalyst with a moderate amount of Ce exhibits outstanding catalytic performance. Especially, the MVN-Ce catalyst with a Ce/V ratio of 0.1 exhibits the best performance: the total selectivity of the catalyst toward C2H4 and CH3COOH is the highest (72%) at the ethane conversion of 31%. Therefore, MoVNbCeO multi-metal oxides are promising candidates for selective oxidation.

Electrochemistry and X-ray absorption spectroscopy (XAS) of MnO2/reduced graphene oxide (RGO) were made to evaluate capacitive performance and electronic structure as a supercapacitor. MnO2 was deposited on the surface of RGO by a spontaneous redox reaction. At low current density (1 A g−1), the specific capacitance of MnO2/RGO (MRGO) greatly increased with increasing growth time from 281 to 462 F g−1. Electrochemical results show that the specific capacitance of RGO and MRGO arises from the combined contributions of electrochemical double-layer capacitance (EDLC) and pseudo-capacitance. To gain insights into the charge storage mechanism of RGO and MRGO, it was characterized using ex-situ soft XAS techniques at Mn L-edge and C, O K-edges in the charging/discharging process. The ex-situ soft XAS results provide evidence that the contribution of RGO to specific capacitance involves an oxygen-functionality-related contribution of pseudocapacitance and EDLC. In addition, the specific capacitance of MRGO reveals pseudocapacitive contributions from the redox processes that involve the Mn(III)/Mn(IV) redox reaction in MnO2. This work utilizes electrochemical and ex-situ XAS techniques to elucidate charge storage mechanism for supercapacitor applications.

BACKGROUND/AIM The clinical significance of frailty status on treatment outcome in patients with esophageal cancer (EC) has been seldom explored. This study aimed to evaluate the impact of pretreatment frailty on treatment-related toxicity and survival outcome in patients with EC undergoing concurrent chemoradiotherapy (CCRT). PATIENTS AND METHODS Patients aged ≥20 years and with newly diagnosed locally advanced EC receiving neoadjuvant radiotherapy and concurrent chemotherapy with weekly administration of carboplatin and paclitaxel for 5 weeks were prospectively enrolled. A pretreatment frailty assessment was performed within 7 days before CCRT initiation. The primary endpoint was treatment-related toxicity and complications of CCRT while the secondary endpoint was overall survival. RESULTS A total of 87 patients were enrolled, 41 (47%) and 46 (53%) of whom were allocated in the frail and fit group, respectively. Frail patients had a significantly higher incidence of having at least one severe hematological adverse event (63.4% vs. 19.6%, p

Molybdenum silicides (Mo–Si) have attracted great interest owing to their good electrical conductivity, ultra-high melting point and well oxidation resistance. In this work, the controllable syntheses of Mo5Si3 and Mo3Si powders by silicothermic reduction of MoS2 in the presence of lime are studied for the first time. The internal mixture composed of MoS2 and Si is wrapped by sufficient CaO. After the reaction is finished, the synthesized molybdenum silicides can be easily separated from the desulfurization layer by peeling off the desulfurization product. The results show that Mo3Si and Mo5Si3 can be prepared at 1500 °C for the samples with the MoS2:Si molar ratio of 1:1.7 and 1:2.33, respectively. In addition, the results show that both SiS2 and SiS can be formed during the heating process. The thermodynamic analysis about the disproportionation reaction of SiS indicates that the existence of SiS2 depends on the partial pressure of SiS (PSiS) and temperature. Moreover, it is demonstrated that SiS2 is preferentially formed under low temperature conditions. As the temperature rises, it is much easier for SiS2 to react with Si to form SiS. Additionally, this work experimentally proves for the first time that SiS gas can directly reduce MoS2 to form MoSi2 and SiS2. Subsequently, the recovery of S in the desulfurization product was studied. S in MoS2 was first captured by CaO in the form of CaS (accompanied by Ca2SiO4 and Si). In order to solve this CaS containing desulfurization product which is detrimental to the environment, CaS in the desulfurization product is react with Fe2O3 and C to form FeS. This work provides new insights into the closed-loop capture and recovery of S in the process of extracting metals or metal compounds from sulfide ores.

The effect of copper oxide doping (0.05–1 wt%) on the densification, microstructure evolution and mechanical characteristics of alumina toughened zirconia (ATZ: 80 wt% Y-TZP + 20 wt% Al2O3) ceramic composites was investigated. Green samples were pressureless sintered using a short hold time of 12 min at temperatures varying from 1250 °C to 1500 °C. The incorporation of up to 0.2 wt% copper oxide was beneficial in promoting densification at low sintering temperature and improving the mechanical properties of ATZ without affecting the tetragonal phase stability. It was found that 0.2 wt% copper oxide addition was most efficacious, and the samples could attain a relative density of approximately 92% at 1250 °C, approximately 97% dense at 1350 °C and above 99% dense at 1450–1500 °C. This approach was also accompanied by an improvement in the Vickers hardness (12.7 GPa) and fracture toughness (6.94 MPam1/2) when consolidated at 1450 °C/12 min. In comparison, the undoped composite exhibited relative densities of approximately 80% at 1250 °C, 87% at 1350 °C and approximately 97%–98% at 1450 °C-1500 °C. However, the study also found that higher dopant levels (0.5 wt% and 1 wt%) was not beneficial because the tetragonal zirconia phase was disrupted upon cooling from sintering, resulting in the monoclinic phase formation. In addition, low densification and poor mechanical properties were obtained.

Efficient bifunctional OER/ORR catalysts are crucial for the further development of zinc-air battery. From a sustainable point of view, it is important that electrocatalysts are efficient, low cost, and composed of abundant resources instead of scarce metals. Due to their good conductivity, low cost, and strong durability, carbon-based materials are considered a promising alternative in the field of commercial zinc-air battery catalysts. Herein, we briefly introduce the zinc-air battery and then summarize recent progress in the development of carbon-based bifunctional catalysts by defect engineering, heteroatom doping and metal doping. Finally, we discuss the main challenges and prospects for the future development of carbon-based bifunctional oxygen catalysts.

SrFeO3-δ perovskite material is considered as a potential substitute for Ni-based fuel electrodes, while the problem of Sr segregation limits the development of material. Herein, different high-valence elements Ti4+, Nb5+and Mo6+ are gradient doped into La0.5Sr0.5FeO3-δ (LSF) to solve Sr segregation and study the influence mechanism for high valence elements. After the LSF is doped by high-valence elements, the reduction stability and CO2 tolerance are found to be obviously improved in a CO2:CO = 1:1 atm. Under the premise of stability, lower-valence element doping requires less Fe4+ reduction and lattice oxygen to match the charge, therefore, La0.5Sr0.5Fe0.9Ti0.1O3-δ (LSFTi5591) possesses more oxygen vacancies than La0.5Sr0.5Fe0.9Nb0.1O3-δ (LSFNb5591) and La0.5Sr0.5Fe0.9Mo0.1O3-δ(LSFMo5591). Since Ti ions possess a weaker binding force with O ions, LSFTi5591 more easily loses lattice oxygen and generates oxygen vacancies under high-temperature and reduction conditions, which results in stronger CO2 adsorption. Using LSCF-GDC as the oxygen electrode of electrolytic cells, the LSFTi5591 cell (1.35 A cm−2) exhibits higher electrochemical performance than LSFNb5591 (1.18 A cm−2) and LSFMo5591 (1.04 A cm−2) cells due to stronger CO2 adsorption and dissociation in the medium-frequency resistance range.

Biological redox signaling plays an important role in many diseases. Redox signaling involves reductive and oxidative mechanisms. Oxidative stress occurs when reductive mechanism overwhelms oxidative challenges. Cellular oxidative stress occurs when reactive oxygen/nitrogen species (RO/NS) exceed the cellular reductive/antioxidant capacity. Endogenously produced RO/NS from mitochondrial metabolic citric-acid-cycle coupled with electron-transport-chain or exogenous stimuli trigger cellular signaling events leading to homeostatic response or pathological damage. Recent evidence suggests that RO/NS also modulate epigenetic machinery driving gene expression. RO/NS affect DNA methylation/demethylation, histone acetylation/deacetylation or histone methylation/demethylation. Many health beneficial phytochemicals possess redox capability that counteract RO/NS either by directly scavenging the radicals or via inductive mechanism of cellular defense antioxidant/reductive enzymes. Amazingly, these phytochemicals also possess epigenetic modifying ability. This review summarizes the latest advances on the interactions between redox signaling, mitochondrial metabolism, epigenetics and redox active phytochemicals and the future challenges of integrating these events in human health.

Targeted therapies against human epidermal growth factor receptor 2 (HER2) are associated with increased interstitial lung disease (ILD). Trastuzumab, lapatinib, pertuzumab, and trastuzumab emtansine have markedly extended HER2 breast cancer survival but current knowledge on how these HER2-targeted agents induce interstitial lung disease is still poorly defined due to limited cases in the literature. Physicians mostly managed this complication by dose interruption, dose de-escalation, or discontinuation with success. In 2019, the FDA had granted accelerated approval on trastuzumab deruxtecan (T-Dxd) in HER2 breast cancer in the late line setting. Severe ILD incidence rate was over ten percent and led to fatal outcomes in 2.2% of patients in the T-Dxd trial. Searching for biomarkers to detect ILD incidence before it becomes clinically fulminant or for treatment response monitoring is of high clinical value. A Case of life-threatening trastuzumab-induced ILD was encountered in our facility. The ILD was confirmed to be antineutrophil cytoplasmic antibody (ANCA) pulmonary capillaritis. The biomarker of neutrophil extracellular traps (NETs), serum MPO-DNA complex, showed a good correlation with the clinical severity. Soon after B cell depleting agent rituximab usage, the serum MPO-DNA outperformed ANCA autoantibody and maintained its correlation with clinical severity. In addition to the trastuzumab-induced ILD case, a prospective cohort in our facility also confirmed the usefulness of MPO-DNA in monitoring vasculitis activity. We postulated that upfront testing with biomarkers of vasculitis during HER2 targeted treatment with high ILD incidence may be beneficial in the future., Graphical abstract Interaction Between Anti-HER2 Antibody and ANCA-Associated Vasculitis and Neutrophil In lung tissues, only bronchial epithelial cells express human epidermal growth factor 2 (HER2) protein in the cell surfaces. Once trastuzumab binds to the HER2 protein, trastuzumab acts as a stimulus to activate neutrophils to express autoantigen, including leukocyte proteinase 3 (PR3) and myeloperoxidase (MPO). The neutrophils could also directly release PR3 and MPO with cell-free DNA and histone through exocytosis to form a neutrophil extracellular trap (NETs). NETs containing PR3 and MPO could further trigger autoreactive B cells to produce ANCA antibodies, resulting in more neutrophil activation and alveolar-capillary endothelial as well as alveolar epithelial damage, although alveolar epithelial cells do not express HER2. A two-step mechanism explains how all previously reported cases that we identified manifests late with a median time of onset two months after the first trastuzumab exposure.Image 1, Highlights • Drug-induced Interstitial lung disease (DIILD) induced by HER2-targeted therapies, is a well-known adverse drug reaction, but the mechanism is ill-defined and no effective strategy for monitoring and prevention were reported. • We report a Case of trastuzumab-related interstitial lung disease induced by anti-neutrophil cytoplasmic antibody, which was never reported in previous literature. • As neutrophils dominate the inflammatory infiltrate in vasculitis, serum MPO-DNA, a biomarker of neutrophil activity, was performed in this Case and within a prospective vasculitis cohort in our facility and showed promising clinical severity correlation. • Monitoring with vasculitis-related autoantibodies and serum MPO-DNA may be helpful in future HER2-targeted agents since high rates of DIILD were reported due to this group of HER2-targeted agents.

BACKGROUNDS Alveolar bone and cementum share many biological and developmental similarities. The mineralizing effect of calcitriol has been previously reported. Yet, its cementoinductivity has not been confirmed. This study evaluated the potential cementoinductivity effect of calcitriol and enamel matrix derivative (EMD) on human periodontal ligament-ligament derived cells (hPDCs). METHODS Human PDCs obtained from extracted third molars or premolars were cultured with calcitriol, or EMD. Cementogenic gene expression was examined using RT-qPCR. Expression analysis also included cementoblast-specific markers, Cementum Protein 1 (CEMP1), cementum attachment protein (CAP), and recently reported cementoblast-enriched genes, secreted frizzled related protein 1 (SFRP1), and Dickkopf-related protein 1 (DKK1). Mineralization capacities were evaluated by alkaline phosphatase (ALP) activity, Alizarin Red and Von Kossa staining followed by scanning electron microscope imaging and element mapping. RESULTS Among tested conditions, 10 nM calcitriol enhanced most cementogenic gene expression, Trans-forming growth factor-β1 (TGF-β1), bone morphogenetic proteins (BMP-2 and BMP-4), Core-binding factor subunit alpha-1/Runt-related transcription factor 2 (Cbfa1/RUNX2), Type I collagen (Col-1), Alkaline phosphatase (ALP), Bone sialoprotein (BSP), osteopontin (OPN/SPP1), osteocalcin (OCN), CEMP1 and CAP, and Wnt signaling negative modulators, SFRP1 and DKK1, along with highest ALP activity and mineralization formation in hPDCs. However, only moderate CEMP-1 protein was observed. In contrast, EMD stimulated stronger CEMP-1 and CAP protein, but presented weaker mineralization capacity, hinting at the possibility that strong stimulation of mineralization might dominate cemetogenic specific factors and vice versa. CONCLUSION Calcitriol demonstrated not only great osteoinductivity, but also the potential to induce cementogenic gene expression by initiating hPDC differentiation and promoting mineralization. Compared to calcitriol, EMD promoted cementoinductivity in hPDCs at a later time point via highly expressed CEMP1 and CAP protein, but with less mineralization. Thus, calcitriol and EMD could provide differential enhancement of cementoinduction and mineralization, likely acting at various differentiation stages. This article is protected by copyright. All rights reserved.

Basic thermal properties and mechanical properties are critical parameters for the structural magnesium alloys. Solute atoms and second phases can improve mechanical properties, but are deteriorating the heat dissipation performance. Through experimental determination of alloys, it is found that REMg12 phases have fewer negative impacts on thermal diffusivities than τ1 phases. With the same intermetallic compound, the solute atom Zn have more negative influences on thermal diffusivities of Mg–Zn–La/Ce alloys than the content of second phases. In order to quantitatively evaluate thermal conductivities and further design Mg alloys with both high strength and high thermal conductivity, a calculated method is provided to describe the thermal diffusivity of alloys as a function of alloy composition and phase constitution. A set of parameters for expression of thermal diffusivity of Mg–Zn–La/Ce alloys were obtained through assessing the experimental data. The thermal conductivities of Mg–Zn–La/Ce system were predicted and agreed well with experimental values with calculation error of 1.6% and standard error of ±3.0 W/(m•K). The calculation method considering thermal diffusivity resistivity improves the calculation accuracy and would be physically significant.

Perlite is one of the major constituents of the radioactive thermal insulation waste (RTIW) originating from nuclear power plants and, for proper waste management, a significant reduction in its volume is required prior to disposal. In this work, the volume reduction of perlite is studied by high-temperature treatment method with using K2CO3 as a flux. The perlite is ground with 0–30 wt% K2CO3, and differential thermal analysis/thermogravimetric analysis is used to monitor the glass transition temperature (Tg) and weight loss. The Tg varied between ~772.2 and 837.1 °C with the minima at ~643.5 °C with the addition of ~10 wt% K2CO3. It is observed that compared to the pure perlite the volume reduction ratio (VRR) increases with the addition of K2CO3. The VRR of 11.20 is observed with 5 wt% K2CO3 at 700 °C, as compared to VRR of 5.56 without K2CO3 at 700 °C. The X-ray photoelectron spectroscopy and scanning electron microscopy are used to characterize perlite samples heat-treated without/with 5 wt% K2CO3 at 700 °C. Moreover, the atomic absorption spectroscopy indicates that the proposed heat-treatment procedure is able to completely retain the radionuclides present in the perlite RTIW.

In this work, we, for the first time, observed the remarkable thermoelectric properties of a few high-quality PtSe2 layered films fabricated by a post selenization of Pt thin films. An excellent po...

PtNi octahedra were utilized as the counter electrodes (CEs) of N719-dye based DSSCs and well characterized via high-resolution transmission electron microscopy, powder x-ray pattern scan, and on-axis transmission Kikuchi Diffraction technique, rendering the crystallographic orientation of individual particle. The photovoltaic results show that the power conversion efficiency (PCE) of devices with different CEs is in the following sequence: Pt thin film Pt5Ni5 octahedra > Pt7Ni3 octahedra > Pt thin film. This study provides fundamental understanding of the exposed surface of PtNi octahedra, for which the coverage of {1 1 1} facets plays a key role in the tri-iodide reduction and thereby leads to the increase of device PCE with significant decrease of the Pt component in CEs.

An all-vanadium redox flow battery (VRFB) system, with multiple stacks, is typically used for large-scale electrical energy storage applications. In a VRFB system, pumps deliver positive and negati...

In this paper, we present a copper(I)-catalyzed nitrile-addition/N-arylation ring-closure cascade for the synthesis of 5,11-dihydro-6H-indolo[3,2-c]quinolin-6-ones from 2-(2-bromophenyl)-N-(2-cyanophenyl)acetamides. Using CuBr and t-BuONa in dimethylformamide (DMF) as the optimal reaction conditions, the cascade reaction gave the target products, in high yields, with a good substrate scope. Application of the cascade reaction was demonstrated on the concise total syntheses of alkaloid isocryptolepine. Further optimization of the products from the cascade reaction led to 3-chloro-5,12-bis[2-(dimethylamino)ethyl]-5,12-dihydro-6H-[1,3]dioxolo[4',5':5,6]indolo[3,2-c]quinolin-6-one (2k), which exhibited the characteristic DNA topoisomerase-I inhibitory mechanism of action with potent in vitro anticancer activity. Compound 2k actively inhibited ARC-111- and SN-38-resistant HCT-116 cells and showed in vivo activity in mice bearing human HCT-116 and SJCRH30 xenografts. The interaction of 2k with the Top-DNA cleavable complex was revealed by docking simulations to guide the future optimization of 5,11-dihydro-6H-indolo[3,2-c]quinolin-6-ones as topoisomerase-I inhibitors.

The availability of natural calcium derived from biowaste materials is an inexpensive alternative to commercial calcium reagents used to produce calcium phosphate bioceramics. This approach is more ecofriendly, cost effective and sustainable owing to its abundant availability. In this study, zinc-substituted hydroxyapatite (ZnHA-Es) was synthesised using calcium precursor derived from eggshells through precipitation method. Zn concentration was varied from 1 mol% to 5 mol% during the synthesis, and the derived powders were calcined at 700 °C in air atmosphere. XRD analysis revealed that ZnHA-Es powders were highly crystalline and comprised biphasic mixtures of HA as the major phase and β-tricalcium phosphate as the minor phase. FTIR examination indicated that all ZnHA-Es samples had a similar structure to pure HA as evidenced by the presence of frequency bands corresponding to phosphate, carbonate and hydroxyl functional groups. The disappearance of vibrational bands of carbonate groups became more apparent with increased Zn concentration. Microstructure analysis revealed that the derived nanostructured particles were spherical (approximately 40–100 nm in diameter) regardless of Zn substitution.

This study successfully developed a semiconductor metal oxide-based ammonia gas sensor that was powered by an Ultraviolet–Visible-near-IR optical light source. However, optical fibre gas sensors using single metal oxide nanomaterial are limited. To address this situation, a h-MoO3 nanorod was grown on a tapered region of optical fibre glass using a simple chemical bath deposition to form a unique sensing element. An additional annealing treatment was then performed to modify the oxidation state of h-MoO3. The property changes of the samples were characterised using different techniques, such as FESEM, TEM, XRD, XPS, TGA and UV–Vis. Overall, the annealing treatment improved the sensitivity performance, response and recovery time of the sensor towards NH3. h-MoO3 that was annealed at 150 °C in air showed stable room temperature absorbance responses of 0.05, 0.18, 0.22, 0.28 and 0.35, a fast response time of 210 s towards 500 ppm of NH3 and strong stability and repeatability. The optical NH3 gas-sensing behaviour was significantly correlated with the non-stoichiometric Mo5+ content. The chemisorbed oxygen species and physiosorbed NH3 altered the refractive index and its absorption coefficient on the nanorod, which manipulated the optical signal and acts as a sensing mechanism. These results verify that a chemical bath deposition growth of the h-MoO3 nanorod exhibits a promising optical sensing characteristic, which paves a path for emerging gas-sensing technology.

Background: 4,4′-isopropylidenediphenol (BPA) hydrogenated to 2,2-bis(4-hydroxycyclohexyl) propane (HBPA) is a simple way to reduce its toxicity and environmental impact. In addition, the higher trans/trans HBPA moiety in polymer will has better mechanical properties. Therefore, how to prepare trans/trans HBPA via hydrogenation is an important issue. Method: One-dimensional nickel-palladium catalyst was successfully synthesized via reduction by an external magnetic field. The high ratio of trans/trans HBPA was characterized by FTIR, GC/MS, and NMR, respectively. The adsorption behavior of BPA and its half-hydrogenated intermediates was studied by Material Studio software. Significant findings: The pd nanoparticles immobilized on the magnetization of 1-D Ni catalyst with high amount of Ni(111) plane is the novelty of this research. The conversion of BPA was high to 100% and the ratio of trans/trans HBPA was over than 75% at 180 °C and 70 kgf/cm2 in isopropanol medium. The trans/trans ratio of HBPA was slightly increasing as increasing hydrogen pressure and decreasing reaction temperature. Reaction intermediate was selected with the aid of molecular simulation. Moreover, the reaction path of BPA hydrogenated by one-dimensional nickel-palladium catalyst was proposed that BPA was firstly hydrogenated to tetrahydro intermediate and followed roll-over mechanism to obtain trans/trans HBPA product.

We demonstrate the fabrication of a flexible and conductive bioelectrode via the electrodeposition of IrO2 nanoparticles on a metalized polypropylene micromembrane (PPMM). The metalized PPMM is prepared by carrying out conformal electroless deposition of Au on individual polypropylene (PP) fibers of PPMM using both polydopamine and polyvinyl alcohol as the surface–modifying agents to improve the hydrophilicity of PPMM. Images from scanning and transmission electron microscopes, as well as analysis from energy dispersive X–ray spectrometer and X–ray photoelectron spectroscopy confirm the successful formation of IrO2 nanoparticles on individual PP fibers of metalized PPMM. For bio–stimulating purpose, the IrO2–coated PPMM reveals an impressive charge–storage–capacity of 54.6 mC/cm2 in cyclic voltammetry, In addition, under a symmetric bi–phasic current pulse, its charge–injection–capacity reaches 466 μC/cm2. Since the entire constituents for the IrO2–coated PPMM are bio−compatible, we envision its potential use as a bioelectrode in implantable biomedical devices.

Background The virion secretion mechanism of human hepatitis B virus (HBV) remains to be investigated. In our current study, we characterized a reverse transcriptase mutant, which changed from the YMDD motif to YMHA. We noted that this mutant YMHA secreted no virions in the medium. Because of the overlapping open reading frame (ORF) between the polymerase and the envelope genes, the lack of virion secretion is likely due to corresponding concurrent mutations in a small loop of the envelope protein (HBsAg, HBV surface antigen). In literature, small loop mutations are thought to affect virion secretion of hepatitis delta virus (HDV), but not HBV. Methods Here, we revisited the relationship between the small loop and virion secretion by site-directed mutagenesis and native agarose gel electrophoresis. Results A proline substitution at residue 196 or 198 in the small loop blocked both HBV genome-containing and genome-free virion secretion, but not the secretion of 22-nm HBsAg subviral particles. Surprisingly, a leucine substitution at residue 196 enhanced genome-containing virion secretion. It is also intriguing that a proline-197, sandwiched by residue 196 and 198, exhibited no apparent defect in secreted virions, with or without containing an HBV genome. By complementation assay, we demonstrated that the wild type small envelope protein alone is sufficient to rescue the virion secretion defect of a small loop mutant M198P. Conclusions The effect of the small loop mutation of HBV small envelope protein on virion secretion is position-dependent. It warrants further investigation how the small loop of HBsAg plays a subtle role in HBV morphogenesis and secretion of virions with or without containing an HBV genome.

Metal phosphides have shown great potential for potassium-ion batteries because of their high theoretical specific capacity. Nevertheless, most of the metal phosphide anodes are plagued by rapid capacity decay (caused by the large volume changes during the discharge/charge process), which would restrict their further practical application. Herein, a chemically bonded CuP2/C composite was prepared by a facile high-energy ball milling method. A potassium bis(trifluoromethanesulfonyl)imide (KFSI)-based electrolyte was adopted instead of a conventional KPF6-based electrolyte for the CuP2/C composite anode. Benefiting from the synergistic effects of the formation of strong P–O–C chemical bonds and the KFSI-based electrolyte, the CuP2/C composite anode exhibited high reversible capacity (451.4 mAh g−1 at 50 mA g−1), excellent rate performance (123.5 mAh g−1 at 1000 mA g−1), and superior cycling stability (300 mAh g−1 after 100 cycles). This work paves the way for the development of high-performance CuP2 anode for potassium-ion batteries.

Key points Intentional ingestion of agricultural organophosphorus insecticides is a significant public health issue in rural Asia, causing thousands of deaths annually. Survivors may develop a severe myasthenic syndrome or paralysis, associated with increased plasma levels of cyclohexanol, an insecticide solvent metabolite. Analysis of synaptic transmission at neuromuscular junctions in isolated mouse skeletal muscle, using isometric tension recording and microelectrode recording of endplate voltages and currents, showed that cyclohexanol reduced postsynaptic sensitivity to acetylcholine neurotransmitter (reduced quantal size) while simultaneously enhancing evoked transmitter release (increased quantal content). Patch recording from transfected cell lines, together with molecular modelling, indicated that cyclohexanol causes selective, allosteric antagonism of postsynaptic nicotinic acetylcholine receptor and block of presynaptic K+ -channel function. The data provide insight into the cellular and molecular mechanisms of neuromuscular weakness following intentional ingestion of agricultural organophosphorus insecticides. Our findings also extend understanding of the effects of alcohols on synaptic transmission and homeostatic synaptic function. Abstract Intentional ingestion of agricultural organophosphorus insecticides is a significant public health issue in rural Asia, causing thousands of deaths annually. Some survivors develop a severe, acute or delayed myasthenic syndrome. In animal models, similar myasthenia has been associated with increasing plasma concentration of one insecticide solvent metabolite, cyclohexanol. We investigated possible mechanisms using voltage and current recordings from mouse neuromuscular junctions (NMJs) and transfected human cell lines. Cyclohexanol (10-25 mM) reduced EPP amplitudes by 10-40% and enhanced depression during repetitive (2-20 Hz) stimulation by up to 60%. EPP decay was prolonged more than two fold. MEPPs were attenuated by more than 50%. Cyclohexanol inhibited whole-cell currents recorded from CN21 cells expressing human postjunctional acetylcholine receptors (hnAChR) with an IC50 of 3.74 mM. Cyclohexanol (10-20 mM) also caused prolonged episodes of reduced-current, multi-channel bursting in outside-out patch recordings from hnAChR expressed in transfected HEK293T cells, reducing charge transfer by more than 50%. Molecular modelling indicated cyclohexanol binding (-6kcal.mol-1 ) to a previously-identified alcohol binding site on nicotinic AChR α-subunits. Cyclohexanol also increased quantal content of evoked transmitter release by ∼50%. In perineurial recordings, cyclohexanol selectively inhibited pre-synaptic K+ -currents. Modelling indicated cyclohexanol binding (-3.8 kcal.mole-1 ) to voltage-sensitive K+ -channels at the same site as tetraethylammonium (TEA). TEA (10 mM) blocked K+ -channels more effectively than cyclohexanol but EPPs were more prolonged in 20 mM cyclohexanol. The results explain the pattern of neuromuscular dysfunction following ingestion of organophosphorus insecticides containing cyclohexanol precursors and suggest that cyclohexanol may facilitate investigation of mechanisms regulating synaptic strength at NMJs. Graphical Abstract: Cyclohexanol, the principal metabolite of a common agricultural insecticide solvent cyclohexanone, acts both presynaptically and postsynaptically to impair neuromuscular transmission. [1] Cyclohexanol binds to sites in the pore of voltage-sensitive K-channels that also bind the K+ -channel blocker tetraethylammonium (TEA), with the effect of reducing presynaptic motor nerve terminal K+ -currents and increasing quantal content of evoked transmitter release. [2] Simultaneously, cyclohexanol binds allosterically to an alcohol binding site on postsynaptic nicotinic acetylcholine receptors, altering ligand-gating characteristics and reducing charge transfer. The combined, overall effects of [1] and [2] result in reduced amplitude, prolonged depolarization and enhanced synaptic depression of endplate potentials (EPPs), weakening tetanic tension responses and causing fade in twitch responses to low frequency nerve stimulation. These effects mimic myasthenia or paralysis that occur in self-harming individuals who have swallowed significant quantities of organophosphorus insecticide, a significant public health issue in rural Asia. The present findings therefore provide an explanation for these clinical signs; and indicate potential utility of cyclohexanol in further study of mechanisms of neuromuscular synaptic homeostasis. This article is protected by copyright. All rights reserved.

Alzheimer's disease (AD) has become highly relevant in aging societies, yet the fundamental molecular basis for AD is still poorly understood. New tools to study the undergoing structural conformation changes of amyloid beta (Aβ) peptides, the pathogenic hallmark of AD, could play a crucial role in the understanding of the underlying mechanisms of misfolding and cytotoxicity of this peptide. It has been recently reported that Zn2+ interacts with Aβ and changes its aggregation pathway away from less harmful fibrillar forms to more toxic species. Here, we present a versatile platform based on a set of sub-10 nm nanogap electrodes for the manipulation and sensing of biomolecules in the physiological condition at a low copy number, where molecules are trapped via dielectrophoresis (DEP) across the nanogap, which also serves as a surface-enhanced Raman spectroscopy hotspot. In this study, we demonstrate that our electrode nanogap platform can be used to study the structural difference between Aβ40 and ZnAβ40 peptides at different aggregation stages in the physiologically relevant concentration and in solution phase. The Raman spectroscopic signatures of the DEP-captured neuropeptides prove the device to be attractive as a label-free bioanalytical tool.

Triple negative breast cancer (TNBC) is one of the leading causes of cancer death in the world and lacks an effective targeted therapy. G-protein-coupled receptor 161 (GPR161) has been demonstrated to perform the functional regulations on TNBC progression and might be a potential new target for TNBC therapy. This study showed the effects of bisdemethoxycurcumin (BDMC) on GPR161 regulation, indicating that BDMC effectively inhibited GPR161 expression and downregulated GPR161-driven signaling. BDMC showed the potent inhibitory effects on TNBC proliferation through suppressing GPR161-mediated mammalian target of rapamycin (mTOR)/70 kDa ribosomal protein S6 kinase (p70S6K) activation. Besides, in this study, we discover the mechanism of GPR161-driven TNBC metastasis, linking to GPR161-mediated twist-related protein 1 (Twist1)/matrix metallopeptidase 9 (MMP9) contributing to the epithelial-mesenchymal transition (EMT). BDMC effectively repressed GPR161-mediated TNBC metastasis via inhibiting Twist1/MMP9-induced EMT. The three-dimensional invasion assay also showed that BDMC significantly inhibited TNBC invasion. The combination treatment of BDMC and rapamycin enhanced the inhibition of TNBC proliferation and metastasis through increasing the blockage of mTOR activation. Furthermore, this study also observed that BDMC activated the caspase 3/9 signaling pathway to induce TNBC apoptosis. Therefore, BDMC could be applicable to anticancer therapy, especially targeting on the GPR161-driven cancer type.

Pacemaker cells can be differentiated from stem cells or transdifferentiated from quiescent mature cardiac cells via genetic manipulation. Here we show that the exposure of rat quiescent ventricular cardiomyocytes to a silk-fibroin hydrogel activates the direct conversion of the quiescent cardiomyocytes to pacemaker cardiomyocytes by inducing the ectopic expression of the vascular endothelial cell-adhesion glycoprotein cadherin. The silk-fibroin-induced pacemaker cells exhibited functional and morphological features of genuine sinoatrial-node cardiomyocytes in vitro, and pacemaker cells generated via the injection of silk fibroin in the left ventricles of rats functioned as a surrogate in situ sinoatrial node. Biomaterials with suitable surface structure, mechanics and biochemistry could facilitate the scalable production of biological pacemakers for human use. A silk-fibroin hydrogel converts rat quiescent ventricular cardiomyocytes into pacemaker cardiomyocytes by inducing the ectopic expression of the vascular endothelial cell-adhesion glycoprotein cadherin.

Air pollution is typically at its lowest in Taiwan during summer. The mean concentrations of PM10, PM2.5, and daytime ozone (08:00–17:00 LST) during summer (June–August) over central Taiwan were 35–40 µg m−3, 18–22 µg m−3, and 30–42 ppb, respectively, between 2004 and 2019. Sampling analysis revealed that the contribution of organic carbon (OC) to PM2.5 could have exceeded 30 % in urban and inland mountain sites during July in 2017 and 2018. Frequent episodes of air quality deterioration occur over the western plains of Taiwan when an easterly typhoon circulation interacts with the complex topographic structure of the island. We explored an episode of air quality deterioration that was associated with a typhoon between 15 and 17 July 2018 using the Weather Research Forecasting with Chemistry (WRF-Chem) model. The results indicated that the continual formation of low-pressure systems or typhoons in the area between Taiwan and Luzon island in the Philippines provided a strong easterly ambient flow, which lasted for an extended period between 15 and 17 July. The interaction between the easterly flow and Taiwan's Central Mountain Range (CMR) resulted in stable weather conditions and weak wind speed in western Taiwan during the study period. Numerical modeling also indicated that a lee side vortex easily formed, and the wind direction could have changed from southwesterly to northwesterly over central Taiwan because of the interaction between the typhoon circulation and the CMR. The northwesterly wind coupled with a sea breeze was conducive to the transport of air pollutants from the coastal upstream industrial and urban areas to the inland area. The dynamic process for the wind direction changed given a reasonable explanation for why the observed SO42- became the major contributor to PM2.5 during the episode. SO42- contribution proportions (%) to PM2.5 at the coastal, urban, and mountain sites were 9.4 µg m−3 (30.5 %), 12.1 µg m−3 (29.9 %), and 11.6 µg m−3 (29.7 %), respectively. Moreover, the variation of the boundary layer height had a strong effect on the concentration level of both PM2.5 and ozone. The lee vortex and land–sea breeze, as well as the boundary layer development, were the key mechanisms in air pollutant accumulation and transport. As typhoons frequently occur around Taiwan during summer and fall, their effect on the island's air quality merits further research attention.

Introducing therapeutic ions into pulp capping materials has been considered a new approach for enhancing regeneration of dental tissues. However, no studies have been reported on its dentinogenic effects on human dental pulp cells (HDPCs). This study was designed to investigate the effects of magnesium (Mg2+) on cell attachment efficiency, proliferation, differentiation, and mineralization of HDPCs. HDPCs were cultured with 0.5 mM, 1 mM, 2 mM, 4 mM, and 8 mM concentrations of supplemental Mg2+ and 0 mM (control). Cell attachment was measured at 4, 8, 12, 16, and 20 hours. Cell proliferation rate was evaluated at 3, 7, 10, 14, and 21 days. Crystal violet staining was used to determine cell attachment and proliferation rate. Alkaline phosphatase (ALP) activity was assessed using the fluorometric assay at 7, 10, and 14 days. Mineralization of cultures was measured by Alizarin red staining. Statistical analysis was done using multiway analysis of variance (multiway ANOVA) with Wilks’ lambda test. Higher cell attachment was shown with 0.5 mM and 1 mM at 16 hours compared to control (P<0.0001). Cells with 0.5 mM and 1 mM supplemental Mg2+ showed significantly higher proliferation rates than control at 7, 10, 14, and 21 days (P<0.0001). However, cell proliferation rates decreased significantly with 4 mM and 8 mM supplemental Mg2+ at 14 and 21 days (P<0.0001). Significantly higher levels of ALP activity and mineralization were observed in 0.5 mM, 1 mM, and 2 mM supplemental Mg2+ at 10 and 14 days (P<0.0001). However, 8 mM supplemental Mg2+ showed lower ALP activity compared to control at 14 days (P<0.0001), while 4 mM and 8 mM supplemental Mg2+showed less mineralization compared to control (P<0.0001). The study indicated that the optimal (0.5–2 mM) supplemental Mg2+ concentrations significantly upregulated HDPCs by enhancing cell attachment, proliferation rate, ALP activity, and mineralization. Magnesium-containing biomaterials could be considered for a future novel dental pulp-capping additive in regenerative endodontics.

Organic semiconducting polymers exhibited promising photocatalytic behavior for hydrogen (H2) evolution, especially when prepared in the form of polymer dots (Pdots). However, the Pdot structures were formed using common nonconjugated amphiphilic polymers, which have a negative effect on charge transfer between photocatalysts and reactants and are unable to participate in the photocatalytic reaction. This study presents a new strategy for constructing binary Pdot photocatalysts by replacing the nonconjugated amphiphilic polymer typically employed in the preparation of polymer nanoparticles (Pdots) with a low-molecular-weight conjugated polyelectrolyte. The as-prepared polyelectrolyte/hydrophobic polymer-based binary Pdots truly enhance the electron transfer between the Pt cocatalyst and the polymer photocatalyst with good water dispersibility. Moreover, unlike the nonconjugated amphiphilic polymer, the photophysics and mechanism of this photocatalytic system through time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements confirmed the Forster resonance energy transfer (FRET) between the polyelectrolyte as a donor and the hydrophobic polymer as an acceptor. As a result, the designated binary Pdot photocatalysts significantly enhanced the hydrogen evolution rate (HER) of 43 900 μmol g-1 h-1 (63.5 μmol h-1, at 420 nm) for PTTPA/PFTBTA Pdots under visible-light irradiation.

Integrating multiple photosensitive properties into an “all-in-one” photosensitizer (PS) shows great promise for the treatment of cancers owing to synergistic effect among them. However, the development of such PSs, especially those that need a single laser source, remains a challenge. Herein, we report an orchestration of electron donors and acceptors in a propeller-like pentad, PBI-4Cz, where four carbazole (Cz) units are covalently linked to the ortho-positions of the perylene bisimide (PBI) core. Strong intramolecular donor-acceptor interaction significantly quenches the luminescence and largely extends the absorption spectra to near-infrared region. Excited-state dynamics investigated via femto- and nano-second transient absorption spectroscopy revealed exclusive charge separation of the PBI-4Cz within initial 0.5 ps when photoexcited regardless of which intermediate is involved. Energy dissipation of the resulting charge-separated state (PBI•−-4Cz•−) is subjected to the toggle between intersystem-crossing toward excited triplet states and charge recombination toward ground states. Relative importance of the two pathways can be tuned by micro-environmental polarity, which endows PBI-4Cz remarkable performances of singlet-oxygen generation (>90.0%) in toluene and photothermal conversion (∼28.6%) in DMSO. Harnessing intrinsic photostability and excited-state processes of heavy-atom-free PBI derivatives not only holds a promise for multifunctional phototheranostics, but also provides a prototype for designing high-performance PSs with tunable photoconversion pathways.

In this work, the suppression of hydrogen diffusion in top-gate InGaZnO thin film transistors (TFTs) was observed. Under positive-bias temperature stress, the threshold voltage in short-channel devices was negatively shifted; this shift was attributed to hydrogen diffusion. To inhibit hydrogen migration, low-temperature high-pressure (LTHP) fluorine treatment was subsequently utilized. Under supercritical fluid states, fluorine, the most electronegative species of all elements, acted as a reactant and reduced mobile hydrogen. It was confirmed that the treatment benefited the characteristic properties of InGaZnO TFTs with varied channel lengths, especially in devices with short channels. The reliability of devices under stress improved through the LTHP treatment; the effects of suppression of hydrogen diffusion were illustrated by the energy band and capacitance–voltage curves of devices. Energy-dispersive X-ray spectroscopy of the specimen treated with LTHP indicated the presence of fluorine, which ensured the contribution of the treatment. Thus, LTHP treatment enables the realization of small-sized high-performance top-gate InGaZnO TFTs.

Sodium-ion batteries (SIBs) have attracted much scientific interest for use in large-scale energy storage systems because sodium is cheaper than lithium. However, the large radius of Na+ and barriers to Na+ transport result in sluggish kinetics and complicated structural distortion, leading to unsatisfactory rate capability and poor cycling stability. It therefore is essential to develop an electrode with enhanced kinetics and a stable structure during cycling to improve SIB performance. Among the various layered oxide cathodes, those with a spinel-like structure could play an important role in boosting electron transport because of their excellent intrinsic conductivity, including by coordinating with Na+ insertion/extraction. Moreover, thanks to the inherent high stability of the spinel-like phase, it could function as a stabilizer for host cathode structures. This review summarizes recent advances in spinel engineering on layered oxide cathodes to boost Na+ transport kinetics and provide structural stability to achieve high-performance SIBs, focusing particularly on post-spinel structures, layered oxide integrated spinel-like structures, and spinel transition. The insights proposed in this review will be useful for guiding rational structural engineering and design to drive the development of new materials and chemistries in Na-based electrode materials.

The ability to coat scaffolds and wound dressings with therapeutic short interfering RNA (siRNA) holds much potential for applications in wound healing, cancer treatment, and regenerative medicine. Layer-by-layer (LbL) technology is an effective method to formulate polyelectrolyte thin films for local delivery of siRNA; however, the formation and efficacy of LbL coatings as drug delivery systems are highly contingent on the assembly conditions. Here, we investigate the effects of LbL assembly parameters on film composition and consequent siRNA-mediated gene knockdown efficiency in vitro. Films comprising poly(β-amino ester) (PBAE) and siRNA were built on polyglactin 910 (Vicryl) sutures consisting of poly(10% L-lactide, 90% glycolide). A fractional factorial design was employed, varying the following LbL assembly conditions: pH, ionic strength, PBAE concentration, and siRNA concentration. Effects of these parameters on PBAE loading, siRNA loading, their respective weight ratios, and in vitro siRNA-mediated knockdown were elucidated. The parameter effects were leveraged to create a rationally designed set of solution conditions that was predicted to give effective siRNA-mediated knockdown, but not included in any of the original experimental conditions. This level of knockdown with our rationally designed loading conditions (47%) is comparable to previous formulations from our lab while being simpler in construction and requiring fewer film layers, which could save time and cost in manufacturing. This study highlights the importance of LbL solution conditions in the preparation of surface-mediated siRNA delivery systems and presents an adaptable methodology for extending these electrostatically-assembled coatings to the delivery of other therapeutic nucleic acids. Statement of significance Short interfering RNA (siRNA) therapeutics are powerful tools to silence aberrant gene expression in the diseased state; however, the clinical utility of these therapies relies on effective controlled delivery approaches. Electrostatic self-assembly through the layer-by-layer (LbL) process enables direct siRNA release from surfaces, but this method is highly dependent upon the specific solution conditions used. Here, we use a fractional factorial design to illustrate how these assembly conditions impact composition of siRNA-eluting LbL thin films. We then elucidate how these properties mediate in vitro transfection efficacy. Ultimately, this work presents a significant step towards understanding how optimization of assembly conditions for surface-mediated LbL delivery can promote transfection efficacy while reducing the processing and material required.

Background A considerable amount of azo dye wastewater is generated from textile industry every day, which jeopardizes human health and environment. To treat azo dye-containing wastewater in visible-light environment, a perovskite YFeO3/carbon fiber (CF) electrode was developed. Methods A sol-gel process combined with calcination was adopted to synthesize YFeO3 catalysts, and the composite electrode was fabricated using a facile dip-coating method. Significant findings The YFeO3 powder that was calcined at 700 °C consisted of mixed hexagonal and orthorhombic phases with crystallite sizes of 15–30 nm. The particles tended to aggregate, forming a porous structure, and they exhibited a photocatalytic degradation capability for Reactive Black 5 (RB5) dyes. Notably, the YFeO3/CF composite electrode enabled significant photoelectrocatalytic activity over RB5 under visible light irradiation, with a removal efficiency of 99% in a 60 min treatment. In addition, the composite electrode demonstrated its high stability during the repeated treatments. The synergetic effect of photo- and electrocatalysis accounted for breaking the N=N bonds, as well as the benzene and naphthalene structures of RB5, resulting in a favorable pollutant degradation. Moreover, the photoelectrocatalytic treatment system kinetics followed a pseudo-first-order rate equation, corresponding to a single-molecule reaction. The improved photoelectrocatalytic activity of the composite electrode can be attributed to the reduced surface and charge transfer resistances during the photoelectrocatalysis process.