Cascaded orbital-oriented hybridization of intermetallic Pd3Pb boosts electrocatalysis of Li-O2 battery.

Catalysts with a refined electronic structure are highly desirable for promoting the oxygen evolution reaction (OER) kinetics and reduce the charge overpotentials for lithium-oxygen (Li-O2) batteries. However, bridging the orbital interactions inside the catalyst with external orbital coupling between catalysts and intermediates for reinforcing OER catalytic activities remains a grand challenge. Herein, we report a cascaded orbital-oriented hybridization, namely alloying hybridization in intermetallic Pd3Pb followed by intermolecular orbital hybridization between low-energy Pd atom and reaction intermediates, for greatly enhancing the OER electrocatalytic activity in Li-O2 battery. The oriented orbital hybridization in two axes between Pb and Pd first lowers the d band energy level of Pd atoms in the intermetallic Pd3Pb; during the charging process, the low-lying 4dxz/yz and 4dz2 orbital of the Pd further hybridizes with 2π* and 5σ orbitals of lithium superoxide (LiO2) (key reaction intermediate), eventually leading to lower energy levels of antibonding and, thus, weakened orbital interaction toward LiO2. As a consequence, the cascaded orbital-oriented hybridization in intermetallic Pd3Pb considerably decreases the activation energy and accelerates the OER kinetics. The Pd3Pb-based Li-O2 batteries exhibit a low OER overpotential of 0.45 V and superior cycle stability of 175 cycles at a fixed capacity of 1,000 mAh g-1, which is among the best in the reported catalysts. The present work opens up a way for designing sophisticated Li-O2 batteries at the orbital level.

Up-regulation of BTN3A1 on CD14+ cells promotes Vγ9Vδ2 T cell activation in psoriasis.

Vγ9Vδ2 T cells play an important role in the development and progression of psoriasis vulgaris (PV), but how they promote skin inflammation and the molecular mechanisms underlying Vγ9Vδ2 T cell dysfunction are poorly understood. Here, we show that circulating Vγ9Vδ2 T cells are decreased and exhibit enhanced proliferation and increased production of IFN-γ and TNF-α in PV patients. Monocytes from PV patients express higher levels of the phosphoantigen sensor butyrophilin 3A1 (BTN3A1) than monocytes from healthy controls. Blockade of BTN3A1 suppresses Vγ9Vδ2 T cell activation and abolishes the difference in Vγ9Vδ2 T cell activation between PV patients and healthy controls. The CD14+ cells in PV skin lesions highly express BTN3A1 and juxtapose to Vδ2 T cells. In addition, IFN-γ induces the up-regulation of BTN3A1 on monocytes. Collectively, our results demonstrate a crucial role of BTN3A1 on monocytes in regulating Vγ9Vδ2 T cell activation and highlight BTN3A1 as a potential therapeutic target for psoriasis.

Carbon-Extraction-Induced Biaxial Strain Tuning of Carbon-Intercalated Iridium Metallene for Hydrogen Evolution Catalysis.

Metallene materials with atomic thicknesses are receiving increasing attention in electrocatalysis due to ultrahigh surface areas and distinctive surface strain. However, the continuous strain regulation of metallene remains a grand challenge. Herein, taking advantage of autocatalytic reduction of Cu2+ on biaxially strained, carbon-intercalated Ir metallene, we achieve control over the carbon extraction kinetics, enabling fine regulation of carbon intercalation concentration and continuous tuning of (111) in-plane (-2.0%-2.6%) and interplanar (3.5%-8.8%) strains over unprecedentedly wide ranges. Electrocatalysis measurements reveal the strain-dependent activity toward hydrogen evolution reaction (HER), where weakly strained Ir metallene (w-Ir metallene) with the smallest lattice constant presents the highest mass activity of 2.89 A mg-1Ir at -0.02 V vs reversible hydrogen electrode (RHE). Theoretical calculations validated the pivotal role of lattice compression in optimizing H binding on carbon-intercalated Ir metallene surfaces by downshifting the d-band center, further highlighting the significance of strain engineering for boosted electrocatalysis.

Mitochondrial DNA Stress-Mediated Health Risk to Dibutyl Phthalate Contamination on Zebrafish (Danio rerio) at Early Life Stage.

Plastics contaminations are found globally and fit the exposure profile of the planetary boundary threat. The plasticizer of dibutyl phthalate (DBP) leaching has occurred and poses a great threat to human health and the ecosystem for decades, and its toxic mechanism needs further comprehensive elucidation. In this study, environmentally relevant levels of DBP were used for exposure, and the developmental process, oxidative stress, mitochondrial ultrastructure and function, mitochondrial DNA (mtDNA) instability and release, and mtDNA-cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING) signaling pathway with inflammatory responses were measured in zebrafish at early life stage. Results showed that DBP exposure caused developmental impairments of heart rate, hatching rate, body length, and mortality in zebrafish embryo. Additionally, the elevated oxidative stress damaged mitochondrial ultrastructure and function and induced oxidative damage to the mtDNA with mutations and instability of replication, transcription, and DNA methylation. The stressed mtDNA leaked into the cytosol and activated the cGAS-STING signaling pathway and inflammation, which were ameliorated by co-treatment with DBP and mitochondrial reactive oxygen species (ROS) scavenger, inhibitors of cGAS or STING. Furthermore, the larval results suggest that DBP-induced mitochondrial toxicity of energy disorder and inflammation were involved in the developmental defects of impaired swimming capability. These results enhance the interpretation of mtDNA stress-mediated health risk to environmental contaminants and contribute to the scrutiny of mitochondrial toxicants.

Assessment of the migration characteristics and source-oriented health risks of heavy metals in the soil and groundwater of a legacy contaminated by the chlor-alkali industry in central China.

The chlor-alkali industry (CAI) is crucial for global chemical production; however, its operation has led to widespread heavy metal (HM) contamination at numerous sites, which has not been thoroughly investigated. This study analysed 122 soil and groundwater samples from a typical CAI site in Kaifeng, China. Our aim was to assess the ecological and health risks, identify the sources, and examine the migration characteristics of HMs at this site using Monte Carlo simulation, absolute principal component score-multiple linear regression (APCS-MLR), and the potential environmental risk index (Ei). Our findings revealed that the exceedance rates for Cd, Pb, Hg, and Ni were 71.96%, 45.79%, 49.59%, and 65.42%, respectively. Mercury (Hg) displayed the greatest coefficient of variation across all the soil layers, indicating a significant anthropogenic influence. Cd and Hg were identified as having high and extremely high potential environmental risk levels, respectively. The spatial distributions of the improved Nemerow index (INI), total ecological risk (Ri), and HM content varied considerably, with the most contaminated areas typically associated with the storage of raw and auxiliary materials. Surface aggregation and significant vertical transport were noted for HMs; As and Ni showed substantial accumulation in subsoil layers, severely contaminating the groundwater. Self-organizing maps categorized the samples into two different groups, showing strong positive correlations between Cd, Pb, and Hg. The APCS-MLR model suggested that industrial emissions were the main contributors, accounting for 60.3% of the total HM input. Elevated hazard quotient values for Hg posed significant noncarcinogenic risks, whereas acceptable levels of carcinogenic risk were observed for both adults (96.60%) and children (97.83%). This study significantly enhances historical CAI pollution data and offers valuable insights into ongoing environmental and health challenges.

Low-Electronegativity Mn-Contraction of PtMn Nanodendrites Boosts Oxygen Reduction Durability.

Platinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well-known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low-electronegativity Mn-contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg-1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well-known high-electronegativity Ni-based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals' dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite-based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm-2 at a low Pt loading and high-performance retention over 50 h operations at 0.6 V in H2 -O2 hydrogen fuel cells.

Conversion of THz refractive index variation to detectable voltage change realized by a graphene-based Brewster angle device.

The Brewster effect has been previously reported as an essential mechanism for terahertz (THz) wave sensing application. However, generally in a sensing application, a complex rotation apparatus is required for detecting the slight change in Brewster angle. Here, we propose a graphene-based Brewster angle device operating at a specific terahertz frequency capable of sensing the refractive index at a fixed incident angle. In other words, our sensing device could avoid the impact of Brewster angle shift and eliminate the need for high-precision rotating equipment, which is usually required in traditional sensing applications. The conversion from the refractive index to a Volt-level detectable voltage roots from the tunability of graphene's Fermi level in the external electrical field. A linear correlation between the output voltage and the background refractive index is observed and theocratically analyzed. Furthermore, we present the improvement of our device in terms of sensing range and sensitivity by adjusting the permittivity of the dielectric substrate. As a demonstration of our proposed device, a detection range of 1.1-2.4 and a sensitivity of 20.06 V/RIU for refractive index is achieved on a high-resistance silicon substrate operating at 0.3 THz.

High sensitivity graphene based health sensor with self-warning function.

In order to reduce the damage to people's health from diseases that attack the respiratory system such as COVID-19, asthma, and pneumonia, it is desired that patients' breathing can be monitored and alerted in real-time. The emergence of wearable health detection sensing devices has provided a relatively good response to this problem. However, there are still problems such as complex structure and poor performance. This paper introduces a laser-induced graphene (LIG) device that is attached to PDMS. The LIG is produced by laser irradiation of Nomex and subsequently transferred and attached to the PDMS. After being tested, it has demonstrated high sensitivity, stable tensile performance, good acoustic performance, excellent thermal stability, and other favorable properties. Notably, its gauge factor (GF) value can reach 721.67, which is quite impressive. Additionally, it is capable of emitting an alarm sound with an SPL close to 60 dB when receiving signals within the range of 5-20 kHz. The device realizes mechanical sensing and acoustic functions in one chip, and has a high application value in applications that need to combine sensing and early warning.

Longitudinal relationships between grip strength, subjective memory complaints and cognitive function among middle-aged and older adults in China.

BACKGROUND: Subjective memory complaints are considered an early sign of cognitive decline. Recent evidence shows that grip strength is an important predictor of cognitive function. However, few studies have compared whether one condition is uniquely associated with cognitive function when another condition is controlled for. AIMS: To explore the longitudinal associations of cognitive function with subjective memory complaints and grip strength in middle-aged and older adults, with a particular focus on whether one condition is uniquely associated with cognitive function when another condition is considered. METHODS: A total of 3,877 middle-aged and older adults (aged 45-92 years) from the China Health and Retirement Longitudinal Study reported on their demographic and health status and completed measures of grip strength and subjective memory complaints, as well as a series of cognitive tests, every two years between 2011 and 2015. Generalized estimating equation models were used to assess the relationships between grip strength, subjective memory complaints, and cognitive function. RESULTS: Grip strength was longitudinally associated with cognitive function (ß = 0.021, 95% confidence interval [CI]: 0.011, 0.030, P < 0.001) independent of subjective memory complaints. In contrast, changes in the subjective memory complaints were not related to cognitive function over time (ß = 0.107, 95% CI: - 0.025, 0.238, P = 0.112). Only at baseline subjective memory complaints were associated with poorer cognitive function (ß = - 1.142, 95% CI: - 1.309, - 0.975, P < 0.001). CONCLUSIONS: Grip strength might be a more important clinical correlate of cognitive function decline over time than subjective memory complaints. DISCUSSION: Regular assessment and close monitoring of grip strength might help identify individuals who might be at high risk for cognitive impairment.

Valorisation of food waste for valuable by-products generation with economic assessment.

This study assessed the techno-economic feasibility of a biorefinery for valuable by-products (mainly hydrogen, ethanol and fertilizer) generation from food waste. The plant was designed to be built in Zhejiang province (China) with a processing capacity of 100 t food waste per day. It was found that the total capital investment (TCI) and annual operation cost (AOC) of the plant were US$ 7625549 and US$ 2432290.7 year-1, respectively. After the tax, US$ 3141867.6 year-1 of net profit could be reached. The payback period (PBP) was 3.5 years at a 7% discount rate. The internal rate of return (IRR) and return on investment (ROI) were 45.54% and 43.88%, respectively. Shutdown condition could happen with the feed of food waste less than 7.84 t day-1 (2587.2 t year-1) for the plant. This work was beneficial for attracting interests and even investment for valuable by-products generation from food waste in large scale.

Research Progress and Forensic Application of Human Vascular Finite Element Modeling and Biomechanics.

The finite element method (FEM) is a mathematical method for obtaining approximate solutions to a wide variety of engineering problems. With the development of computer technology, it is gradually applied to the study of biomechanics of human body. The application of the combination of FEM and biomechanics in exploring the relationship between vascular injury and disease, and pathological mechanisms will be a technological innovation for traditional forensic medicine. This paper reviews the construction and development of human vascular FEM modeling, and its research progress on the vascular biomechanics. This paper also looks to the application prospects of FEM modeling in forensic pathology.

A General Synthetic Method for High-Entropy Alloy Subnanometer Ribbons.

High-entropy alloys (HEAs) are attracting intensive attention due to their broad compositional tunability and interesting catalytic properties. However, precisely shaping the HEAs into suprathin low-dimensional nanostructures for achieving diverse applications remains an enormous challenge owing to their intrinsic thermodynamic instability. Herein we propose a new and general low-temperature method for incorporating up to eight metallic elements into one single-phase subnanometer ribbon to achieve the thinnest HEA metal materials in the world. We experimentally demonstrate that synthetic processes for suprathin HEA subnanometer ribbons (SNRs) include (1) different metal atom nucleation via galvanic exchange reaction between different metal precursors and Ag nanowire template, (2) co-reduction of different metal precursors on nanowire template, and (3) the removal of the inner Ag core. Density functional theory (DFT) calculations reveal that the crystallization and stabilization of HEA SNRs strongly depend on the "highly dynamic" Ag from the template, and the crystallization levels of HEA subnanometer ribbons are closely correlated with the concentration of Pt and Pd. We demonstrate that the present synthetic method enables the flexible control of components and concentrations in HEAs SNRs for achieving a library of HEA SNRs and also superior electrocatalytic properties. The well-designed HEA SNRs show great improvement in catalyzing the oxygen reduction reaction of fuel cells and also high discharge capacity, low charge overpotential, and excellent durability for Li-O2 batteries. DFT calculations reveal the superior electrochemical performances are attributed to the strong reduction capability from high-concentration reductive elements in HEAs, while the other elements guarantee the site-to-site efficient electron transfer.

Enhancing the efficiency of graphene-based THz modulator by optimizing the Brewster angle.

The gate-controllable electronical property of graphene provides a possibility of active tuning property for THz modulator. However, the common modulation technology which only depends on voltage cannot solve the problem of power consumption limitation in communication applications. Here, we demonstrated a Brewster angle-controlled graphene-based THz modulator, which could achieve a relatively high modulation depth with low voltage. First, we explored the complex relationships among the Brewster angles, reflection coefficients and the conductivities of graphene. Then, we further investigated the optimal incident angle selection based on the unusual reflection effect which occurs at Brewster angle. Finally, an improved scheme by dynamically adjusting the incident angle was proposed in this paper. It would make it possible that the modulator could achieve a modulation depth of more than 90% with a Fermi level as low as 0.2eV at any specific frequency in the range of 0.4THz-2.2THz. This research will help to realize a THz modulator with high-performance and ultra-low-power in quantities of applications, such as sensing and communication.

Theoretical analysis of the absorption of CO2 and CO on pristine and Al-doped C3B.

CO2 and CO, the by-products of fossil fuels; one of them is a major cause of global warming and the other endangers the nervous and cardiovascular systems of humans. Therefore, real-time monitoring towards those harmful gases is of practical significance. Nano-structured materials have attracted the attention of scholars for their enormous potential for harmful gas detection. In this work, the adsorption and sensing behavior of C3B and Al-doped C3B monolayers for these two typical hazardous gases were investigated theoretically. The most stable doping model was obtained, and the adsorption process for CO and CO2 was simulated based on this model. The adsorption system shows that the gas molecules are all deformed and that the charge transfer and adsorption energy are significantly increased. Moreover, the adsorption mechanism was investigated by analyzing the electronic behavior of the adsorbent, and the physical adsorption between the hazardous gas and the adsorbent was more favorable for desorption. The good adsorption performance and sensing mechanism suggest that the CO/CO2 sensor prepared using Al-C3B has great potential for application. Our work may provide some guidance for the application of toxic gas monitoring and adsorption.

Cesium Lead Bromide Perovskite-Based Lithium-Oxygen Batteries.

The main challenge for lithium-oxygen (Li-O2) batteries is their sluggish oxygen evolution reaction (OER) kinetics and high charge overpotentials caused by the poorly conductive discharge products of lithium peroxide (Li2O2). In this contribution, the cesium lead bromide perovskite (CsPbBr3) nanocrystals were first employed as a high-performance cathode for Li-O2 batteries. The battery with a CsPbBr3 cathode can exhibit the lowest charge overpotential of 0.5 V and the best cycling performance of 400 cycles among all the reported perovskite-based Li-O2 cells, which represents a new benchmark. Most importantly, the density functional theory (DFT) calculations further prove that the rate limitation step during OER processes is the decomposition of LiO2 to form O2 and Li+, and the weak adsorption strength between CsPbBr3 surfaces and LiO2 results in a low charge overpotential for the CsPbBr3-based Li-O2 battery. This work first demonstrates the good potential of CsPbBr3 for application in metal-air batteries.

Periplaneta americana extract ameliorates dextran sulfate sodium-induced ulcerative colitis via immunoregulatory and PI3K/AKT/NF-κB signaling pathways.

Ulcerative colitis (UC) is a chronic inflammatory bowel disease (IBD) with a low cure rate. Periplaneta americana is a traditional American Cockroach and reportedly has potential therapeutic roles for UC treatment; however, its mechanisms remain unclear. To address this, we investigated the therapeutic effects and underlying molecular mechanisms of Ento-A, a Periplaneta americana extract, in a dextran sulfate sodium (DSS)-induced chronic and recurrent UC mouse model. Ento-A treatment decreased pro-inflammatory cytokine secretion, disease activity index (DAI), colon mucosa damage index (CMDI), histopathological scores (HS), and increased colon length. Additionally, Ento-A effectively increased interleukin-4 (IL-4), and forkhead transcription factor protein 3 (Foxp3) expression levels, while it abated interferon-γ (IFN-γ) and IL-17 levels in spleen lymphocytes. Conversely, in mesenteric lymph nodes, IL-4 and Foxp3 expression were decreased, while IFN-γ and IL-17 expression was increased. Furthermore, Ento-A blocked p-PI3K, p-AKT,*and p-NF-κB activation. In conclusion, Ento-A improved UC symptoms and exerted therapeutic effects by regulating immune responses and inhibiting PI3K/AKT/NF-κB signaling.

Engineering eg Orbital Occupancy of Pt with Au Alloying Enables Reversible Li-O2 Batteries.

Constructing well-designed catalysts to accelerate OER catalytic activity and alleviate the charge overpotential is prevailing for achieving sophisticated Li-O2 batteries. Herein, we report a concept for engineering the eg occupancy of Pt with M alloying (M=Au, Ru) to tune the charge overpotentials for achieving high-performance Li-O2 batteries. The X-ray photoelectron spectroscopy results coupled with density functional theory (DFT) calculations reveal that the highly electronegative Au can capture more eg electrons from Pt, leading to less eg electrons of Pt in PtAu than that in PtRu. The lower eg occupancy of Pt atoms in PtAu alloys entails the upward shift of the Pt d band, which causes a strong binding strength towards the intermediates (LiO2 ), thereby decreasing the OER energy barrier. As a consequence, the Li-O2 battery with a PtAu cathode delivers a low charge overpotential of 0.36 V and superior cycle life of 220 cycles at a cutoff capacity of 1000 mAh g-1 , which is among the best in the reported noble metal-based cathodes.

One Nanometer PtIr Nanowires as High-Efficiency Bifunctional Catalysts for Electrosynthesis of Ethanol into High Value-Added Multicarbon Compound Coupled with Hydrogen Production.

The electrosynthesis of high-value-added multicarbon compounds coupled with hydrogen production is an efficient way to achieve carbon neutrality; however, the lack of effective bifunctional catalysts in electrosynthesis largely hinders its development. Herein, we report the first example on the highly efficient electrosynthesis of high-value-added 1,1-diethoxyethane (DEE) at the anode and high-purity hydrogen at the cathode using 1 nm PtIr nanowires (NWs) as the bifunctional catalysts. We demonstrate that the cell using 1 nm PtIr nanowires as the bifunctional catalysts can achieve a reported lowest voltage of 0.61 V to reach the current density of 10 mA cm-2, much lower than those of the Pt NWs (0.85 V) and commercial Pt/C (0.86 V), and also can have the highest Faraday efficiencies of 85% for DEE production and 94.0% for hydrogen evolution in all the reported electrosynthesis catalysts. The in situ infrared spectroscopy study reveals that PtIr NWs can facilitate the activation of O-H and C-H bonds in ethanol, which is important for the formation of acetaldehyde intermediate, and finally DEE. In addition, the cell using PtIr NWs as bifunctional catalysts exhibits excellent stability by showing almost no obvious decrease in the Faraday efficiency of the DEE production.

Characteristics of Visual Evoked Potential in Different Parts of Visual Impairment. / 不同部位损伤致视力障碍的视觉诱发电位特征.

OBJECTIVES: To study the quantitative and qualitative differences of visual evoked potential (VEP) in monocular visual impairment after different parts of visual pathway injury. METHODS: A total of 91 subjects with monocular visual impairment caused by trauma were selected and divided into intraocular refractive media-injury group (eyeball injury group for short), optic nerve injury group, central nervous system injury and intracranial combined injury group according to the injury cause and anatomical segment. Pattern Reversal visual evoked potential (PR-VEP) P100 peak time and amplitude, Flash visual evoked potential (F-VEP) P2 peak time and amplitude were recorded respectively. SPSS 26.0 software was used to analyze the differences of quantitative (peak time and amplitude) and qualitative indexes (spatial frequency sweep-VEP acuity threshold, and abnormal waveform category and frequency) of the four groups. RESULTS: Compared with healthy eyes, the PR-VEP P100 waveforms of the intraocular eyeball injury group and the F-VEP P2 waveforms of the optic nerve group showed significant differences in prolonged peak time and decreased amplitude in injured eyes (P<0.05). The PR-VEP amplitudes of healthy eyes were lower than those of injured eyes at multiple spatial frequencies in central nervous system injury group and intracranial combined injury group (P<0.05).The amplitude of PR-VEP in patients with visual impairment involving central injury was lower than that in patients with eye injury at multiple spatial frequencies. The frequency of VEP P waveforms reaching the threshold of the intraocular injury group and the optic nerve injury group were siginificantly different from the intracranial combined injury group, respectively(P<0.008 3), and the frequency of abnormal reduction of VEP amplitude of threshold were significantly different from the central nervous system injury group, respectively(P<0.008 3). CONCLUSIONS: VEP can distinguish central injury from peripheral injury, eyeball injury from nerve injury in peripheral injury, but cannot distinguish simple intracranial injury from complex injury, which provides basic data and basis for further research on the location of visual impairment injury.

Application of Immunohistochemistry and Special Staining Technique in Forensic Traumatic Pathology Identification. / å ç–«ç»„ç»‡åŒ–å­¦åŠç‰¹æ®ŠæŸ“è‰²æŠ€æœ¯åœ¨æ³•åŒ»æŸä¼¤ç— ç†å­¦é‰´å®šä¸­çš„åº”ç”¨.

In forensic traumatic pathology practice, immunohistochemistry and special staining technique play an important role in wound age estimation and complications of traumatic complication identification. They even play an important role in the identification of special cases, such as snakebites and insulin killings. This article reviews the application and value of immunohistochemistry and special staining techniques in forensic traumatic pathology based on the cases of forensic practice reported in literature.