ABSTRACT
The surface photochemical activity of goethite, which occurs widely in surface soils and sediments, plays a crucial role in the environmental transformation of various pollutants and natural organic matter. This study systemically investigated the mechanism of different types of surface hydroxyl groups on goethite in generating reactive oxygen species (ROSs) and Fe(III) reduction under sunlight irradiation. Surface hydroxyl groups were found to induce photoreductive dissolution of Fe(III) at the goethite-water interface to produce Fe2+(aq), while promoting the production of ROSs. Substitution of the surface hydroxyl groups on goethite by fluoride significantly inhibited the photochemical activity of goethite, demonstrating their important role in photochemical activation of goethite. The results showed that the surface hydroxyl groups (especially the terminating hydroxyl groups, ≡FeOH) led to the formation of Fe(III)-hydroxyl complexes via ligand-metal charge transfer on the goethite surface upon photoexcitation, facilitating the production of Fe2+(aq) and â¢OH. The bridging hydroxyl groups (≡Fe2OH) were shown to mainly catalyze the production of H2O2, leading to the subsequent light-driven Fenton reaction to produce â¢OH. These findings provide important insights into the activation of molecular oxygen on the goethite surface driven by sunlight in the environment, and the corresponding degradation of anthropogenic and natural organic compounds caused by the generated ROSs.
Subject(s)
Reactive Oxygen Species , Reactive Oxygen Species/chemistry , Oxidation-Reduction , Ferric Compounds/chemistry , Iron Compounds/chemistry , Iron/chemistry , Minerals/chemistry , Hydroxyl Radical/chemistry , Photochemical ProcessesABSTRACT
Immune checkpoint inhibitor (ICI) therapy, which targets programmed cell death protein 1, has demonstrated enhanced survival outcomes in numerous patients with cancer. Historically, individuals with autoimmune diseases have been excluded from clinical trials involving cancer immunotherapies due to concerns about the potential worsening of their underlying autoimmune conditions. In the present case report, a patient with non-small cell lung cancer and bullous pemphigoid (BP) who underwent treatment with the ICI pembrolizumab is described. In this specific clinical case, no severe exacerbation of the underlying autoimmune disease was observed. Contrarily, the patient not only tolerated pembrolizumab well but also experienced amelioration of the BP lesions after the treatment. This case challenges the conventional exclusion criteria for ICI therapy in patients with autoimmune diseases, suggesting the potential safety and efficacy of such treatments in this specific population. However, further investigations and larger-scale studies are warranted to validate these findings and provide a more comprehensive understanding of the implications of ICI therapy in patients with autoimmune comorbidities.
ABSTRACT
Rechargeable aqueous batteries adopting Fe-based materials are attracting widespread attention by virtue of high-safety and low-cost. However, the present Fe-based anodes suffer from low electronic/ionic conductivity and unsatisfactory comprehensive performance, which greatly restrict their practicability. Concerning the principle of physical chemistry, fabricating electrodes that could simultaneously achieve ideal thermodynamics and fast kinetics is a promising issue. Herein, hierarchical Fe3O4@Fe foam electrode with enhanced interface/grain boundary engineering is fabricated through an in situ self-regulated strategy. The electrode achieves ultrahigh areal capacity of 31.45 mA h cm-2 (50 mA cm-2), good scale application potential (742.54 mA h for 25 cm2 electrode), satisfied antifluctuation capability, and excellent cycling stability. In/ex situ characterizations further validate the desired thermodynamic and kinetic properties of the electrode endowed with accurate interface regulation, which accounts for salient electrochemical reversibility in a two-stage phase transition and slight energy loss. This work offers a suitable strategy in designing high-performance Fe-based electrodes with comprehensive inherent characteristics for high-safety large-scale energy storage.
ABSTRACT
Lithium-sulfur (Li-S) batteries represent the most promising next-generation energy storage systems because of their high theoretical specific capacity and energy density. However, the severe shuttle effect and volume expansion of sulfur cathodes have impeded their commercial viability. Hence, accelerating the conversion of lithium polysulfides (LiPSs) is crucial for achieving efficient Li-S batteries. In this study, we employ a straightforward electrostatic self-assembly method to coat ultra-thin MXene nanosheets onto a S@MnO2 core-shell structure, resulting in a highly conductive three-dimensional network. This unique structure not only suppresses the diffusion of LiPSs but also accelerates electron and ion transfer, ensuring a rapid and efficient conversion of LiPSs. The CV curves of symmetrical cells and the Li2S deposition curves demonstrate a significant improvement in the catalytic performance of batteries with S@MnO2@MXene. The capacity of Li-S batteries achieved an impressive 842 mAh/g at the current density of 1C, with a minimal capacity decay of only 0.84 mAh/g per cycle within 500 cycles. Additionally, increasing the sulfur loading mass to 5.88 mg cm-2 resulted in an areal capacity of 6.33 mAh cm-2, demonstrating practical application potential.
ABSTRACT
Sophora alopecuroides has important uses in medicine, wind breaking, and sand fixation. The CHY-zinc-finger and RING-finger (CHYR) proteins are crucial for plant growth, development, and environmental adaptation; however, genetic data regarding the CHYR family remain scarce. We aimed to investigate the CHYR gene family in S. alopecuroides and its response to abiotic stress, and identified 18 new SaCHYR genes from S. alopecuroides whole-genome data, categorized into 3 subclasses through a phylogenetic analysis. Gene structure, protein domains, and conserved motifs analyses revealed an exon-intron structure and conserved domain similarities. A chromosome localization analysis showed distribution across 12 chromosomes. A promoter analysis revealed abiotic stress-, light-, and hormone-responsive elements. An RNA-sequencing expression pattern analysis revealed positive responses of SaCHYR genes to salt, alkali, and drought stress. SaCHYR4 overexpression considerably enhanced alkali and drought tolerance in Arabidopsis thaliana. These findings shed light on SaCHYR's function and the resistance mechanisms of S. alopecuroides, presenting new genetic resources for crop resistance breeding.
Subject(s)
Gene Expression Regulation, Plant , Multigene Family , Phylogeny , Plant Proteins , Sophora , Stress, Physiological , Stress, Physiological/genetics , Plant Proteins/genetics , Plant Proteins/metabolism , Sophora/genetics , Arabidopsis/genetics , Genome, Plant , Droughts , Chromosomes, Plant/geneticsABSTRACT
Organic small molecules are proven to be capable of passivating the bulk/interfacial defects in inorganic perovskite solar cells. Considering the burdensome situation to screen the functional small molecules, we employ a modified machine learning (ML) strategy to guide screening suitable small molecules toward efficient solar cells through three modified ML algorithms to construct the prediction model: (i) random forest algorithm (RF), (ii) support vector machine algorithm (SVR), and (iii) XGBoost. Among them, the XGBoost algorithm displays a better overall predictive performance, whereby the R2 index reaches 0.939. Accordingly, eight small molecules are selected to modify the interface of perovskite films, and both the theoretical and experimental results certify that the difluorobenzylamine with additional fluorine atoms has a better interface modification effect among the small molecules containing functional groups, e.g., the benzene ring and amino group. The high accuracy of the modified machine learning model enables us to simplify the small-molecule screening process and form an important step for ongoing developments in perovskite solar cells and other optoelectronic devices.
ABSTRACT
Sluggish kinetics and severe structural instability of manganese-based cathode materials for rechargeable aqueous zinc-ion batteries (ZIBs) lead to low-rate capacity and poor cyclability, which hinder their practical applications. Pillaring manganese dioxide (MnO2) by pre-intercalation is an effective strategy to solve the above problems. However, increasing the pre-intercalation content to realize stable cycling of high capacity at large current densities is still challenging. Here, high-rate aqueous Zn2+ storage is realized by a high-capacity K+-pillared multi-nanochannel MnO2 cathode with 1 K per 4 Mn (δ-K0.25MnO2). The high content of the K+ pillar, in conjunction with the three-dimensional confinement effect and size effect, promotes the stability and electron transport of multi-nanochannel layered MnO2 in the ion insertion/removal process during cycling, accelerating and accommodating more Zn2+ diffusion. Multi-perspective in/ex-situ characterizations conclude that the energy storage mechanism is the Zn2+/H+ ions co-intercalating and phase transformation process. More specifically, the δ-K0.25MnO2 nanospheres cathode delivers an ultrahigh reversible capacity of 297 mAh g-1 at 1 A g-1 for 500 cycles, showing over 96 % utilization of the theoretical capacity of δ-MnO2. Even at 3 A g-1, it also delivered a 63 % utilization and 64 % capacity retention after 1000 cycles. This study introduces a highly efficient cathode material based on manganese oxide and a comprehensive analysis of its structural dynamics. These findings have the potential to improve energy storage capabilities in ZIBs significantly.
ABSTRACT
Amidst these growing sustainability concerns, producing NH4 + via electrochemical NO3 - reduction reaction (NO3RR) emerges as a promising alternative to the conventional Haber-Bosch process. In a pioneering approach, this study introduces Ru incorporation into Co3O4 lattices at the nanoscale and further couples it with electroreduction conditioning (ERC) treatment as a strategy to enhance metal oxide reducibility and induce oxygen vacancies, advancing NH4 + production from NO3RR. Here, supported by a suite of ex situ and in situ characterization measurements, the findings reveal that Ru enrichment promotes Co species reduction and oxygen vacancy formation. Further, as evidenced by the theoretical calculations, Ru integration lowers the energy barrier for oxygen vacancy formation, thereby facilitating a more energy-efficient NO3RR-to-NH4 + pathway. Optimal catalytic activity is realized with a Ru loading of 10 at.% (named 10Ru/Co3O4), achieving a high NH4 + production rate (98 nmol s-1 cm-2), selectivity (97.5%) and current density (≈100 mA cm-2) at -1.0 V vs RHE. The findings not only provide insights into defect engineering via the incorporation of secondary sites but also lay the groundwork for innovative catalyst design aimed at improving NH4 + yield from NO3RR. This research contributes to the ongoing efforts to develop sustainable electrochemical processes for nitrogen cycle management.
ABSTRACT
The integration of graphene and metal-organic frameworks (MOFs) has numerous implications across various domains, but fabricating such assemblies is often complicated and time-consuming. Herein, a one-step preparation of graphene-MOF assembly is presented by directly impregnating vertical graphene (VG) arrays into the zeolitic imidazolate framework (ZIF) precursors under ambient conditions. This approach can effectively assemble multiple ZIFs, including ZIF-7, ZIF-8, and ZIF-67, resulting in their uniform dispersion on the VG with adjustable sizes and shapes. Hydrogen defects on the VG surface are critical in inducing such high-efficiency ZIF assembly, acting as the reactive sites to interact with the ZIF precursors and facilitate their crystallisation. The versatility of VG-ZIF-67 assembly is further demonstrated by exploring the process of MOF amorphization. Surprisingly, this process leads to an amorphous thin-film coating formed on VG (named VG-IL-amZIF-67), which preserves the short-range molecular bonds of crystalline ZIF-67 while sacrificing the long-range order. Such a unique film-on-graphene architecture maintains the essential characteristics and functionalities of ZIF-67 within a disordered arrangement, making it well-suited for electrocatalysis. In electrochemical oxygen reduction, VG-IL-amZIF-67 exhibits exceptional activity, selectivity, and stability to produce H2O2 in acid media.
ABSTRACT
This paper presents a high-performance MEMS accelerometer with a DC/AC electrostatic stiffness tuning capability based on double-sided parallel plates (DSPPs). DC and AC electrostatic tuning enable the adjustment of the effective stiffness and the calibration of the geometric offset of the proof mass, respectively. A dynamical model of the proposed accelerometer was developed considering both DC/AC electrostatic tuning and the temperature effect. Based on the dynamical model, a self-centering closed loop is proposed for pulling the reference position of the force-to-rebalance (FTR) to the geometric center of DSPP. The self-centering accelerometer operates at the optimal reference position by eliminating the temperature drift of the readout circuit and nulling the net electrostatic tuning forces. The stiffness closed-loop is also incorporated to prevent the pull-in instability of the tuned low-stiffness accelerometer under a dramatic temperature variation. Real-time adjustments of the reference position and the DC tuning voltage are utilized to compensate for the residue temperature drift of the proposed accelerometer. As a result, a novel controlling approach composed of a self-centering closed loop, stiffness-closed loop, and temperature drift compensation is achieved for the accelerometer, realizing a temperature drift coefficient (TDC) of approximately 7 µg/°C and an Allan bias instability of less than 1 µg.
ABSTRACT
Chitosan exhibits a wide source, non-toxic and biodegradable, and is the optimal functional raw material for preparing food packaging materials. However, the pure chitosan film has some disadvantages such as limited antibacterial activity and weak mechanical properties. In this study, sulfobetaines modified chitosan (CS-SBMA) was synthesized by grafting copolymerized betaine methacrylate sulfonate onto the chain of chitosan to improve the anti-bacterial adhesion and antibacterial properties of chitosan, aiming to develop antibacterial and anti-bacterial adhesion films based on CS-SBMA and polyvinyl alcohol (PVA) by the casting method. The structure of CS-SBMA was characterized by 1H NMR and FTIR. The appropriate proportion of CS-SBMA/PVA was determined to be 1/1 and 1/2, by characterizing the composite films with FTIR, XRD, SEM, mechanical, optical, and water resistance behaviors. In addition, CS-SBMA/PVA films showed excellent antibacterial, anti-bacterial adhesion and biofilm control function. The colonies number of E. coli and S. aureus on the surface of CS-SBMA/PVA 1/1 film decreased 94.15 % and 94.27 %, respectively, and 92.93 % of S. aureus and 94.87 % of E. coli colonies were inactivated within 60 min contact. These results indicate that CS-SBMA/PVA film exhibits potential antibacterial and anti-bacterial adhesion properties, which is suitable for food packaging materials.
Subject(s)
Betaine/analogs & derivatives , Chitosan , Chitosan/chemistry , Polyvinyl Alcohol/chemistry , Staphylococcus aureus , Escherichia coli , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Food Packaging/methodsABSTRACT
Chronic obstructive pulmonary disease (COPD) is a clinical syndrome characterized by persistent and irreversible airflow limitation and chronic respiratory symptoms. It has a wide spectrum of complications, and sleep disorders, as part of it, are common in severe cases, especially in elderly patients. Long-term lack of sleep may lead to the aggravation of the original disease, reducing patients' quality of life. Benzodiazepines are mainly used for symptomatic treatment of COPD combined with sleep disorders. However, such drugs have the side effect of respiratory central inhibition and could probably aggravate hypoxia symptoms. Auricular acupuncture is a special method of treating physical and psychosomatic dysfunctions by stimulating specific points in the ear. This article explains the specific methods of clinical operation of auricular acupuncture in detail, including assessment of patient eligibility, medical devices used, acupuncture points, course of treatment, post-treatment care, responses to emergencies, etc. The Pittsburgh sleep quality index (PSQI) and chronic obstructive pulmonary disease assessment scale (CAT) were used as the observational index of this method. So far, clinical reports have proved that auricular acupuncture has a definite curative effect in the treatment of COPD combined with sleep disorders, and its advantages of simple operation, few adverse reactions are worthy of further study and promotion, which provide a reference for the clinical treatment of such diseases.
Subject(s)
Acupuncture, Ear , Pulmonary Disease, Chronic Obstructive , Sleep Wake Disorders , Humans , Medicine, Chinese Traditional , Quality of Life , Pulmonary Disease, Chronic Obstructive/complications , Pulmonary Disease, Chronic Obstructive/therapy , Sleep Wake Disorders/etiology , Sleep Wake Disorders/therapyABSTRACT
Tuberculosis (TB), as a respiratory infectious disease, has damaged public health globally for decades, and mainland China has always been an area with high incidence of TB. Since the outbreak of COVID-19, it has seriously occupied medical resources and affected medical treatment of TB patients. Therefore, the authenticity and reliability of TB data during this period have also been questioned by many researchers. In response to this situation, this paper excludes the data from 2019 to the present, and collects the data of TB incidence in mainland China and the data of 11 influencing factors from 2014 to 2018. Using spatial autocorrelation methods and multiscale geographically weighted regression (MGWR) model to study the temporal and spatial distribution of TB incidence in mainland China and the influence of selected influencing factors on TB incidence. The experimental results show that the distribution of TB patients in mainland China shows spatial aggregation and spatial heterogeneity during this period. And the R2 and the adjusted R2 of MGWR model are 0.932 and 0.910, which are significantly better than OLS model (0.466, 0.429) and GWR model (0.836, 0.797). The fitting accuracy indicators MAE, MSE and MAPE of MGWR model reached 5.802075, 110.865107 and 0.088215 respectively, which also show that the overall fitting effect is significantly better than OLS model (19.987574, 869.181549, 0.314281) and GWR model (10.508819, 267.176741, 0.169292). Therefore, this model is based on real and reliable TB data, which provides decision-making references for the prevention and control of TB in mainland China and other countries.
Subject(s)
COVID-19 , Tuberculosis , Humans , Spatial Regression , Reproducibility of Results , COVID-19/epidemiology , Tuberculosis/epidemiology , China/epidemiologyABSTRACT
Food digestion requires the cooperation of different digestive organs. The differentiation of digestive organs is crucial for larvae to start feeding. Therefore, during digestive organogenesis, cell identity and the tissue morphogenesis must be tightly coordinated but how this is accomplished is poorly understood. Here, we demonstrate that WD repeat domain 5 (Wdr5)-mediated H3K4 tri-methylation (H3K4me3) coordinately regulates cell differentiation, proliferation and apoptosis in zebrafish organogenesis of three major digestive organs including intestine, liver, and exocrine pancreas. During zebrafish digestive organogenesis, some of cells in these organ primordia usually undergo differentiation without apoptotic activity and gradually reduce their proliferation capacity. In contrast, cells in the three digestive organs of wdr5-/- mutant embryos retain progenitor-like status with high proliferation rates, and undergo apoptosis. Wdr5 is a core member of COMPASS complex to implement H3K4me3 and its expression is enriched in digestive organs from 2 days post-fertilization (dpf). Further analysis reveals that lack of differentiation gene expression is due to significant decreases of H3K4me3 around the transcriptional start sites of these genes; this histone modification also reduces the proliferation capacity in differentiated cells by increasing the expression of apc to promote the degradation of ß-Catenin; in addition, H3K4me3 promotes the expression of anti-apoptotic genes such as xiap-like, which modulates p53 activity to guarantee differentiated cell survival. Thus, our findings have discovered a common molecular mechanism for cell fate determination in different digestive organs during organogenesis, and also provided insights to understand mechanistic basis of human diseases in these digestive organs.
ABSTRACT
Genetic compensation responses (GCRs) can be induced by deleterious mutations in living organisms in order to maintain genetic robustness. One type of GCRs, homology-dependent GCR (HDGCR), involves transcriptional activation of one or more homologous genes related to the mutated gene. In zebrafish, ~80% of the genetic mutants produced by gene editing technology failed to show obvious phenotypes. The HDGCR has been proposed to be one of the main reasons for this phenomenon. It is triggered by mutant mRNA bearing a premature termination codon and has been suggested to depend on components of both the nonsense mRNA-mediated degradation (NMD) pathway and the complex of proteins associated with Set1 (COMPASS). However, exactly which specific NMD factor is required for HDGCR remains disputed. Here, zebrafish leg1 deleterious mutants are adopted as a model to distinguish the role of the NMD factors Upf1 and Upf3a in HDGCR. Four single mutant lines and three double mutant lines were produced. The RNA-seq data from 71 samples and the ULI-NChIP-seq data from 8 samples were then analyzed to study the HDGCR in leg1 mutants. Our results provide strong evidence that Upf3a, but not Upf1, is essential for the HDGCR induced by nonsense mutations in leg1 genes where H3K4me3 enrichment appears not to be a prerequisite. We also show that Upf3a is responsible for correcting the expression of hundreds of genes that would otherwise be dysregulated in the leg1 deleterious mutant.
ABSTRACT
Ni-rich layered ternary cathodes (i.e., LiNixCoyMzO2, M = Mn or Al, x + y + z = 1 and x ≥ 0.8) are promising candidates for the power supply of portable electronic devices and electric vehicles. However, the relatively high content of Ni4+ in the charged state shortens their lifespan due to inevitable capacity and voltage deteriorations during cycling. Therefore, the dilemma between high output energy and long cycle life needs to be addressed to facilitate more widespread commercialization of Ni-rich cathodes in modern lithium-ion batteries (LIBs). This work presents a facile surface modification approach with defect-rich strontium titanate (SrTiO3-x) coating on a typical Ni-rich cathode: LiNi0.8Co0.15Al0.05O2 (NCA). The defect-rich SrTiO3-x-modified NCA exhibits enhanced electrochemical performance compared to its pristine counterpart. In particular, the optimized sample delivers a high discharge capacity of â¼170 mA h/g after 200 cycles under 1C with capacity retention over 81.1%. The postmortem analysis provides new insight into the improved electrochemical properties which are ascribed to the SrTiO3-x coating layer. This layer appears to not only alleviate the internal resistance growth, from uncontrollable cathode-electrolyte interface evolution, but also acts as a lithium diffusion channel during prolonged cycling. Therefore, this work offers a feasible strategy to improve the electrochemical performance of layered cathodes with high nickel content for next-generation LIBs.
ABSTRACT
Hydrotalcite, first found in natural ores, has important applications in supercapacitors. NiCoAl-LDH, as a hydrotalcite-like compound with good crystallinity, is commonly synthesized by a hydrothermal method. Al3+ plays an important role in the crystallization of hydrotalcite and can provide stable trivalent cations, which is conducive to the formation of hydrotalcite. However, aluminum and its hydroxides are unstable in a strong alkaline electrolyte; therefore, a secondary alkali treatment is proposed in this work to produce cation vacancies. The hydrophilicity of the NiCoAl-OH surface with cation vacancy has been greatly improved, which is conducive to the wetting and infiltration of electrolyte in water-based supercapacitors. At the same time, cation vacancies generate a large number of defects as active sites for energy storage. As a result, the specific capacity of the NiCoAl-OH electrode after 10,000 cycles can be maintained at 94.1%, which is much better than the NiCoAl-LDH material of 74%.
ABSTRACT
Single-atom catalysts (SACs) have shown potential for achieving an efficient electrochemical CO2 reduction reaction (CO2RR) despite challenges in their synthesis. Here, Ag2S/Ag nanowires provide initial anchoring sites for Cu SACs (Cu/Ag2S/Ag), then Cu/Ag(S) was synthesized by an electrochemical treatment resulting in complete sulfur removal, i.e., Cu SACs on a defective Ag surface. The CO2RR Faradaic efficiency (FECO2RR) of Cu/Ag(S) reaches 93.0% at a CO2RR partial current density (jCO2RR) of 2.9 mA/cm2 under -1.0 V vs RHE, which outperforms sulfur-removed Ag2S/Ag without Cu SACs (Ag(S), 78.5% FECO2RR with 1.8 mA/cm2jCO2RR). At -1.4 V vs RHE, both FECO2RR and jCO2RR over Cu/Ag(S) reached 78.6% and 6.1 mA/cm2, which tripled those over Ag(S), respectively. As revealed by in situ and ex situ characterizations together with theoretical calculations, the interacted Cu SACs and their neighboring defective Ag surface increase microstrain and downshift the d-band center of Cu/Ag(S), thus lowering the energy barrier by â¼0.5 eV for *CO formation, which accounts for the improved CO2RR activity and selectivity toward related products such as CO and C2+ products.
ABSTRACT
Photonic integrated circuits (PICs) based on gallium nitride (GaN) platforms have been widely explored for various applications at C-band (1530â nmâ¼1565â nm) and visible light wavelength range. However, for O-band (1260â nmâ¼1360â nm) commonly used in short reach/cost sensitive markets, GaN-based PICs still have not been fully investigated. In this article, a microring resonator with an intrinsic Q-factor of â¼2.67 × 104 and an extinction ratio (ER) of 35.1â dB at 1319.9â nm and 1332.1â nm, is monolithically integrated with a transverse electric-polarized focusing grating coupler and a ridge waveguide on a GaN-on-sapphire platform. This shows a great potential to further exploit the optical properties of GaN materials and integrate GaN-based PICs with the mature GaN active electronic and optoelectronic devices to form a greater platform of optoelectronic-electronic integrated circuits (OEICs) for data-center and telecom applications.