Molecular ferroelectric with low-magnetic-field magnetoelectricity at room temperature.

Magnetoelectric materials, which encompass coupled magnetic and electric polarizabilities within a single phase, hold great promises for magnetic controlled electronic components or electric-field controlled spintronics. However, the realization of ideal magnetoelectric materials remains tough due to the inborn competion between ferroelectricity and magnetism in both levels of symmetry and electronic structure. Herein, we introduce a methodology for constructing single phase paramagnetic ferroelectric molecule [TMCM][FeCl4], which shows low-magnetic-field magnetoelectricity at room temperature. By applying a low magnetic field (≤1 kOe), the halogen Cl‧‧‧Cl distance and the volume of [FeCl4]- anions could be manipulated. This structural change causes a characteristic magnetostriction hysteresis, resulting in a substantial deformation of ~10-4 along the a-axis under an in-plane magnetic field of 2 kOe. The magnetostrictive effect is further qualitatively simulated by density functional theory calculations. Furthermore, this mechanical deformation significantly dampens the ferroelectric polarization by directly influencing the overall dipole configuration. As a result, it induces a remarkable α31 component (~89 mV Oe-1 cm-1) of the magnetoelectric tensor. And the magnetoelectric coupling, characterized by the change of polarization, reaches ~12% under 40 kOe magnetic field. Our results exemplify a design methodology that enables the creation of room-temperature magnetoelectrics by leveraging the potent effects of magnetostriction.

Alantolactone attenuates high-fat diet-induced inflammation and oxidative stress in non-alcoholic fatty liver disease.

BACKGROUND: Nonalcoholic fatty liver disease (NAFLD) is a chronic disease with an increasing incidence, which can further develop into liver fibrosis and hepatocellular carcinoma at the end stage. Alantolactone (Ala), a sesquiterpene lactone isolated from Asteraceae, has shown anti-inflammatory effects in different models. However, the therapeutic effect of Ala on NAFLD is not clear. METHODS: C57BL/6 mice were fed a high-fat diet (HFD) to induce NAFLD. After 16 weeks, Ala was administered by gavage to observe its effect on NAFLD. RNA sequencing of liver tissues was performed to investigate the mechanism. In vitro, mouse cell line AML-12 was pretreated with Ala to resist palmitic acid (PA)-induced inflammation, oxidative stress and fibrosis. RESULTS: Ala significantly inhibited inflammation, fibrosis and oxidative stress in HFD-induced mice, as well as PA-induced AML-12 cells. Mechanistic studies showed that the effect of Ala was related to the induction of Nrf2 and the inhibition of NF-κB. Taken together, these findings suggested that Ala exerted a liver protective effect on NAFLD by blocking inflammation and oxidative stress. CONCLUSIONS: The study found that Ala exerted a liver protective effect on NAFLD by blocking inflammation and oxidative stress, suggesting that Ala is an effective therapy for NAFLD.

Endothelial deubiquinatase YOD1 mediates Ang II-induced vascular endothelial-mesenchymal transition and remodeling by regulating ß-catenin.

Hypertension is a prominent contributor to vascular injury. Deubiquinatase has been implicated in the regulation of hypertension-induced vascular injury. In the present study we investigated the specific role of deubiquinatase YOD1 in hypertension-induced vascular injury. Vascular endothelial endothelial-mesenchymal transition (EndMT) was induced in male WT and YOD1-/- mice by administration of Ang II (1 µg/kg per minute) via osmotic pump for four weeks. We showed a significantly increased expression of YOD1 in mouse vascular endothelial cells upon Ang II stimulation. Knockout of YOD1 resulted in a notable reduction in EndMT in vascular endothelial cells of Ang II-treated mouse; a similar result was observed in Ang II-treated human umbilical vein endothelial cells (HUVECs). We then conducted LC-MS/MS and co-immunoprecipitation (Co-IP) analyses to verify the binding between YOD1 and EndMT-related proteins, and found that YOD1 directly bound to ß-catenin in HUVECs via its ovarian tumor-associated protease (OTU) domain, and histidine at 262 performing deubiquitination to maintain ß-catenin protein stability by removing the K48 ubiquitin chain from ß-catenin and preventing its proteasome degradation, thereby promoting EndMT of vascular endothelial cells. Oral administration of ß-catenin inhibitor MSAB (20 mg/kg, every other day for four weeks) eliminated the protective effect of YOD1 deletion on vascular endothelial injury. In conclusion, we demonstrate a new YOD1-ß-catenin axis in regulating Ang II-induced vascular endothelial injury and reveal YOD1 as a deubiquitinating enzyme for ß-catenin, suggesting that targeting YOD1 holds promise as a potential therapeutic strategy for treating ß-catenin-mediated vascular diseases.

Electroenzymatic tandem catalysis for the conversion of nitrate into ammonia.

A porous silver nanostructure-supported ionic liquid-modified chloroperoxidase nanohybrid was successfully used in electroenzymatic tandem catalysis to achieve an efficient, mild, and stable approach for the conversion of nitrate into ammonia.

A dendritic porous copper foam-carbonic anhydrase biohybrid for carbon dioxide electroreduction.

Carbonic anhydrase (CA) is bound to a dendritic porous copper foam (3D-Cu) via electrostatic interaction to form a biohybrid (CA/3D-Cu), which exhibits high selectivity and Faraday efficiency in the electroreduction of carbon dioxide (CO2) to formic acid (selectivity of 98.7%, Faraday efficiency of 82.1%) due to the large specific surface area of the 3D-Cu and the ultra-high CO2 hydration capacity of CA.

Extracellular and intracellular effects of bioactive glass nanoparticles on osteogenic differentiation of bone marrow mesenchymal stem cells and bone regeneration in zebrafish osteoporosis model.

Bioactive glass nanoparticles (BGNs) are well-recognized multifunctional biomaterials for bone tissue regeneration due to their capability to stimulate various cellular processes through released biologically active ions. Understanding the correlation between BGN composition and cellular responses is key to developing clinically usable BGN-based medical devices. This study investigated the influence of CaO content of binary SiO2-CaO BGNs (CaO ranging from 0 to 10 mol%) on osteogenic differentiation of rat bone marrow mesenchymal stem cells (rBMSCs) and in vivo bone regeneration in zebrafish osteoporosis model. The results showed that BGNs could promote osteogenic differentiation of rBMSCs by indirectly releasing active ions or directly interacting with rBMSCs by internalization. In both situations, BGNs of a higher CaO content could promote the osteogenic differentiation of rBMSCs to a greater extent. The internalized BGNs could activate the transcription factors RUNX2 and OSX, leading to the expression of osteogenesis-related genes. The results in the zebrafish osteoporosis model indicated that the presence of BGNs of higher CaO contents could enhance bone regeneration and rescue dexamethasone-induced osteoporosis to a greater extent. These findings demonstrate that BGNs can stimulate osteogenic differentiation of rBMSCs by releasing active ions or internalization. A higher CaO content facilitates osteogenesis and bone regeneration of zebrafish as well as relieving dexamethasone-induced osteoporosis. The zebrafish osteoporosis model can be a potent tool for evaluating the in vivo bone regeneration effects of bioactive materials. STATEMENT OF SIGNIFICANCE: Bioactive glass nanoparticles (BGNs) are increasingly used as fillers of nanocomposites or as delivery platforms of active ions to regenerate bone tissue. Various studies have shown that BGNs can enhance osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs) by releasing active ions. However, the correlation between BGN composition and cellular responses and in vivo bone regeneration effect has still not been well investigated. Establishment of a suitable in vivo animal model for investigating this correlation is also challenging. The present study reports the influence of CaO content in binary SiO2-CaO BGNs on osteogenic differentiation of BMSCs extracellularly and intracellularly. This study also demonstrates the suitability of zebrafish osteoporosis model to investigate in vivo bone regeneration effect of BGNs.

Electroenzymatic cascade reaction on a biohybrid boosts the chiral epoxidation reaction.

The chiral epoxidation of styrene and its derivatives is an important transformation that has attracted considerable scientific interest in the chemical industry. Herein, we integrate enzymatic catalysis and electrocatalysis to propose a new route for the chiral epoxidation of styrene and its derivatives. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (ILEMB) was loaded onto cobalt nitrogen-doped carbon nanotubes (CoN@CNT) to form a biohybrid (CPO-ILEMB/CoN@CNT). H2O2 species were generated in situ through a two-electron oxygen reduction reaction (2e-ORR) at CoN@CNT to initiate the following enzymatic epoxidation of styrene by CPO. CoN@CNT had high electroactivity for the ORR to produce H2O2 at a more positive potential, prohibiting the conversion of FeIII to FeII in the heme of CPO to maintain enzymatic activity. Meanwhile, CoN@CNT could serve as an ideal carrier for the immobilization of CPO-ILEMB. Hence, the coimmobilization of CPO-ILEMB and CoN@CNT could facilitate the diffusion of intermediate H2O2, which achieved 17 times higher efficiency than the equivalent amounts of free CPO-ILEMB in bulk solution for styrene epoxidation. Notably, an enhancement (∼45%) of chiral selectivity for the epoxidation of styrene was achieved.

Visible-Light-Driven Semiconductor-Metal Transition in Electron Gas at the (100) Surface of KTaO3.

Two-dimensional electron gas (2DEG) at the (100) KTaO3(KTO) surface and interfaces has attracted extensive interest because of its abundant physical properties. Here, light illumination-induced semiconductor-metal transition in the 2DEG at the KTO surface was investigated. 2DEG was formed at the surface of KTO by argon ion bombardment. The 2DEG prepared with a shorter bombardment time (300 s) exhibits semiconducting behavior in the range of 20~300 K in the dark. However, it shows a different resistance behavior, namely, a metallic state above ~55 K and a semiconducting state below ~55 K when exposed to visible light (405 nm) with a giant conductivity increase of about eight orders of magnitude at 20 K. The suppression of the semiconducting behavior is found to be more pronounced with increasing light power. After removing the illumination, the resistance cannot recover quickly, exhibiting persistent photoconductivity. More interestingly, the photoresponse of the 2DEG below 50 K was almost independent of the laser wavelength, although the photon energy is lower than the band gap of KTO. The present results provide experimental support for tuning oxide 2DEG by photoexcitation, suggesting promising applications of KTO-based 2DEG in future electronic and optoelectronic devices.

The chloroperoxidase immobilized on porous carbon nanobowls for the detection of trichloroacetic acid by electroenzymatic synergistic catalysis.

Trichloroacetic acid (TCA), as a by-product of chlorination disinfection, is a highly carcinogenic chemical. Due to the widespread use of chlorination disinfection, it is critical to detect TCA in drinking water to decrease the incidence of disease. In this work, we developed an efficient TCA biosensor via electroenzymatic synergistic catalysis. The porous carbon nanobowls (PCNB) are prepared and wrapped by an amyloid like proteins formed by phase-transitioned lysozyme (PTL-PCNB), then, chloroperoxidase (CPO) is abounding to PTL-PCNB owing to its strong adhesion. The ionic liquid of 1-ethyl-3-methylimidazolium bromide (ILEMB) is co-immobilized on PTL-PCNB to from CPO-ILEMB@PTL-PCNB nanocomposite to assist the direct electron transfer (DET) of CPO. The PCNB plays two roles here. In addition, to increasing the conductivity, it serves as an ideal support for holding CPO; The CPO-ILEMB@PTL-PCNB nanocomposite modified electrode presents high efficiency for sensing TCA. Through electroenzymatic synergistic catalysis, a wide detection range of 33 µmol L-1 to 98 mmol L-1 can be achieved with a low detection limit of 5.9 µmol L-1, and high stability, selectivity as well as reproducibility, which ensures its potential practical applicability. This work provides a new platform for the electro-enzyme synergistic catalysis in one pot.

Synergistic catalysis and detection of hydrogen peroxide based on a 3D-dimensional molybdenum disulfide interspersed carbon nanotubes nanonetwork immobilized chloroperoxidase biosensor.

Enzyme-based electrochemical biosensors are promising for a wide range of applications due to their unique specificity and high sensitivity. In this work, we present a novel enzyme bioelectrode for the sensing of hydrogen peroxide (H2O2). The molybdenum disulfide nanoflowers (MoS2) is self-assembled on carboxylated carbon nanotubes (CNT) to form a three-dimensional conductive network (3D-CNT@MoS2), which is modified with 1-ethyl-3-methylimidazolium bromide (ILEMB), and followed by anchoring chloroperoxidase (CPO) onto the nanocomposite (3D-CNT@MoS2/ILEMB) through covalent binding to form a bioconjugate (3D-CNT@MoS2/ILEMB/CPO). The ILEMB modified 3D-CNT@MoS2/ILEMB has good hydrophilicity and conductivity, which not only provides a suitable microenvironment for the immobilization of CPO but also facilitates the direct electron transfer (DET) of CPO at the electrode. The 3D-CNT@MoS2/ILEMB/CPO bioconjugate modified electrode has a high catalytic efficiency for H2O2. Through electroenzymatic synergistic catalysis for H2O2 detection by 3D-CNT@MoS2/ILEMB/CPO-GCE, a wide detection range of 0.2 µmol·L-1 to 997 µmol·L-1 and a low detection limit of 0.097 µmolï½¥L-1 with high sensitivity of 1050 µA·mmol·L-1·cm-2 were achieved. Additionally, the 3D-CNT@MoS2/ILEMB/CPO-GCE displayed exceptional stability, selectivity, and reproducibility. Furthermore, 3D-CNT@MoS2/ILEMB/CPO-GCE is suitable for sensing of H2O2 in human urine s with good recovery, suggesting its potential application for the detection of H2O2 in biomedical field.

Observation of Electric Hysteresis, Polarization Oscillation, and Pyroelectricity in Nonferroelectric p-n Heterojunctions.

The switchable electric polarization is usually achieved in ferroelectric materials with noncentrosymmetric structures, which opens exciting opportunities for information storage and neuromorphic computing. In another polar system of p-n junction, there exists the electric polarization at the interface due to the Fermi level misalignment. However, the resultant built-in electric field is unavailable to manipulate, thus attracting less attention for memory devices. Here, we report the interfacial polarization hysteresis (IPH) in the vertical sidewall van der Waals heterojunctions of black phosphorus and quasi-two-dimensional electron gas on SrTiO_{3}. A nonvolatile switching of electric polarization can be achieved by reconstructing the space charge region (SCR) with long-lifetime nonequilibrium carriers. The resulting electric-field controllable IPH is experimentally verified by electric hysteresis, polarization oscillation, and pyroelectric effect. Further studies confirm the transition temperature of 340 K, beyond which the IPH vanishes. The second transition is revealed with the temperature dropping below 230 K, corresponding to the sharp improvement of IPH and the freezing of SCR reconstruction. This work offers new possibilities for exploring the memory phenomena in nonferroelectric p-n heterojunctions.

Reasonable Accommodation and Disparate Impact: Clean Shave Policy Discrimination in Today's Workplace.

This article examines Bey v. City of New York - a recent Second Circuit case where four Black firefights suffering from Pseudofolliculitis Barbae (a skin condition causing irritation when shaving which mostly affects Black men) challenged the New York City Fire Department's Clean Shave Policy - with an intersectional approach utilizing legal theories of racial, disability, and religious discrimination.

Occurrence and risk assessment of PAHs from athletic fields under typical rainfall events.

Six polycyclic aromatic hydrocarbons (PAHs) including naphthalene (Nap), fluorene (Flu), phenanthrene (Phe), fluoranthene (Fla), pyrene (Pyr), and chrysene (Chr) were detected in runoff from five athletic fields during three rainfall events. The event mean concentration (EMC) of ∑6PAHs ranged from 3.96 to 23.23 µg/L, which was much higher than the EMC in urban traffic area runoff. Except for Nap, the PAH concentrations followed in the order of artificial turf > badminton court > basketball court > plastic runway > optennis court. The surface characteristics of the athletic fields, such as the composition of materials and roughness, played an essential role in the release of PAHs. ∑6PAHs concentration during the 2nd rainfall event (July 22nd) was the highest among the three rainfall events, indicating that high rainfall intensity facilitated the PAHs release. PAHs during three rainfall events showed little first flush effect except for the artificial turf during the 2nd (22nd July) and 3rd (29th July) rainfall events. The first flush effect could be affected by rainfall characters, PAH properties, and surface characteristics of athletic fields. Ecological risk assessment showed that PAHs in runoff corresponded to moderate-to-high risk, while health risk assessment showed that PAHs could pose a potential carcinogenic danger to human health via dermal contact.

Structure of the green heme isolated from allylbenzene-modified chloroperoxidase: A novel heme architecture implicating the mechanisms of CPO inactivation and epoxidation.

The chemical identification of the modified heme (the green heme) during chloroperoxidase catalyzed epoxidation of allylbenzene remains unestablished due to its high instability within the protein matrix, the absence of paramagnetically shifted signals, and the difficulty in obtaining crystals of the modified enzyme. We have established the unambiguous structure of the modified prosthetic heme group, which was extracted from the protein matrix using 2D NMR spectroscopy and LC-MS spectrometry. The modified heme was isolated as a µ-oxo dimer that can be quantitatively converted to the corresponding monomer. The depolymerized green heme displayed characteristic NMR signatures of iron porphyrin complexes, but no Nuclear Overhauser Effect was observable to assist in signal assignment. An alternative strategy was applied by removing the iron center of the green heme, resulting in a stable demetallated green porphyrin species. Complete assignment of all the NMR resonances in the demetallated green heme allowed us to establish the molecular architecture of the modified species as a novel N-alkylated heme. Decisive space correlations between the propyl protons of allylbenzene and the γ meso proton coupled with clear dipolar connectivities between the propyl-2H of the substrate and the ß proton in the side chain of the propionic acid at carbon-6 of the porphyrin ring, clearly indicate that allylbenzene was covalently attached to the nitrogen atom of the pyrrole ring III of the prosthetic heme. In this study, the mechanism of green CPO formation and its relation to CPO catalyzed chiral transformations are also discussed. It is concluded that the double-phenyl clamp formed by two phenylalanine residues at the distal heme pocket plays a critical role in fine-tuning substrate orientation that determines the outcome of CPO catalyzed epoxidation of substituted styrenes.

Robust Cost Volume Generation Method for Dense Stereo Matching in Endoscopic Scenarios.

Stereo matching in binocular endoscopic scenarios is difficult due to the radiometric distortion caused by restricted light conditions. Traditional matching algorithms suffer from poor performance in challenging areas, while deep learning ones are limited by their generalizability and complexity. We introduce a non-deep learning cost volume generation method whose performance is close to a deep learning algorithm, but with far less computation. To deal with the radiometric distortion problem, the initial cost volume is constructed using two radiometric invariant cost metrics, the histogram of gradient angle and amplitude descriptors. Then we propose a new cross-scale propagation framework to improve the matching reliability in small homogenous regions without increasing the running time. The experimental results on the Middlebury Version 3 Benchmark show that the performance of the combination of our method and Local-Expansion, an optimization algorithm, ranks top among non-deep learning algorithms. Other quantitative experimental results on a surgical endoscopic dataset and our binocular endoscope show that the accuracy of the proposed algorithm is at the millimeter level which is comparable to the accuracy of deep learning algorithms. In addition, our method is 65 times faster than its deep learning counterpart in terms of cost volume generation.

IRF4 as a novel target involved in malignant transformation of oral submucous fibrosis into oral squamous cell carcinoma.

Oral squamous cell carcinoma (OSCC) in the context of oral submucous fibrosis (OSF) has a high incidence owing to undefined pathogenesis. Identifying key genes and exploring the underlying molecular mechanisms involved in the conversion of OSF into OSCC are in urgent need. Differentially expressed genes (DEGs) between OSCC and OSF were dug from GEO databases and a total of 170 DEGs were acquired. Functional association of DEGs were analyzed by GO and KEGG. Protein-protein interactions (PPIs) analysis was carried out and candidate biomarkers were identified by Gene co-expression analysis and Cox analyses. Hub genes were confirmed by qRT-PCR in tissues and cell lines, of which we found that IRF4 mRNA was successively up-regulated from Normal to OSF and then to OSCC and associated with immune infiltrating levels. In addition, Immunohistochemical (IHC) and Immunofluorescence (IF) assays were conducted to validate the consistent upregulation of IRF4 and the oncogene role of IRF4 in OSF and OSCC at translation level. IRF4 may be indicative biomarker in transformation of OSF into OSCC. High IRF4 expression contribute to increased immune infiltration of OSCC and may provide a novel diagnostic marker for OSCC patients translated from OSF.

Monodispersed Pt Sites Supported on NiFe-LDH from Synchronous Anchoring and Reduction for High Efficiency Overall Water Splitting.

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for PtII . Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm-2 for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm-2 for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm-2 , which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.

Recent Progress in Strain Engineering on Van der Waals 2D Materials: Tunable Electrical, Electrochemical, Magnetic, and Optical Properties.

Strain engineering is a promising way to tune the electrical, electrochemical, magnetic, and optical properties of 2D materials, with the potential to achieve high-performance 2D-material-based devices ultimately. This review discusses the experimental and theoretical results from recent advances in the strain engineering of 2D materials. Some novel methods to induce strain are summarized and then the tunable electrical and optical/optoelectronic properties of 2D materials via strain engineering are highlighted, including particularly the previously less-discussed strain tuning of superconducting, magnetic, and electrochemical properties. Also, future perspectives of strain engineering are given for its potential applications in functional devices. The state of the survey presents the ever-increasing advantages and popularity of strain engineering for tuning properties of 2D materials. Suggestions and insights for further research and applications in optical, electronic, and spintronic devices are provided.

Modulating Hydrogen Adsorption via Charge Transfer at the Semiconductor-Metal Heterointerface for Highly Efficient Hydrogen Evolution Catalysis.

Designing and synthesizing highly efficient and stable electrocatalysts for hydrogen evolution reaction (HER) is important for realizing the hydrogen economy. Tuning the electronic structure of the electrocatalysts is essential to achieve optimal HER activity, and interfacial engineering is an effective strategy to induce electron transfer in a heterostructure interface to optimize HER kinetics. In this study, ultrafine RhP2 /Rh nanoparticles are synthesized with a well-defined semiconductor-metal heterointerface embedded in N,P co-doped graphene (RhP2 /Rh@NPG) via a one-step pyrolysis. RhP2 /Rh@NPG exhibits outstanding HER performances under all pH conditions. Electrochemical characterization and first principles density functional theory calculations reveal that the RhP2 /Rh heterointerface induces electron transfer from metallic Rh to semiconductive RhP2 , which increases the electron density on the Rh atoms in RhP2 and weakens the hydrogen adsorption on RhP2 , thereby accelerating the HER kinetics. Moreover, the interfacial electron transfer activates the dual-site synergistic effect of Rh and P of RhP2 in neutral and alkaline environments, thereby promoting reorganization of interfacial water molecules for faster HER kinetics.