Atomic site-specific reactivity induced by the lattice distortion has garnered increasing research interest for advancing the heterogeneous catalytic conversions, owing to strain-field-tunable electronic structure of the distorted active sites. Here, we prepare the catalysts with reactive center of ferromagnetically nanoparticulate cobalt that is fully exposed by the Co(111) lattice plane with increasing strain. Such sites can boost peracetic acid (PAA) utilization under a mild magnetic field (MF, maximum 500 mT) to produce a bulk of reactive species with high ratio 93.1% R-O• for sulfamethoxazole abatement and thus attain high-effective greener decontamination for water remediations. Spin‒polarized density functional theory and experimental results collectively confirm strain-induced spin modulation at Co(111) step A sites as a critical reactivity determinant. This work integrates MF into PAA utilization and thus provides a perspective on improving the atomic economies of developing ferromagnetic nanoparticulated metal sites into water remediation in low-energy utilization route.
In this paper, CdS nanopaticles were first prepared by a simple hydrothermal method, and then CoS2 nanosheet was grown in situ on CdS, thereby successfully constructing CdS/CoS2 binary heterojunction photocatalyst. The prepared CdS/CoS2-15 % nano-heterojunction exhibited the highest hydrogen yield in photocatalytic water decomposition (45.89 mmol h- 1 g- 1), which was 112 times higher than that of single CdS. The high photocatalytic activity and relatively high stability of the CdS/CoS2-15 % nano heterojunction could be mainly attributed to the loading of the co-catalyst CoS2. Density functional theory (DFT) calculations show that CoS2 has properties similar to metals, and the Fermi level of CoS2 are lower than that of CdS. The sheet-like CoS2 and its higher binding energy provide favorable conditions for the adsorption of hydrogen ions, and its metallic like properties and lower Fermi level help CoS2 effectively obtain photo generated electrons from CdS, which effectively promotes the production of hydrogen gas. This study provides a useful idea for the development of cost-effective co-catalysts to assist other semiconductor materials in improving the hydrogen production efficiency of visible-light-driven photolysis of water.
The electrocatalytic two-electron oxygen reduction reaction (2e ^− ORR) for the synthesis of hydrogen peroxide (H _2 O _2 ) is an efficient, green, and sustainable technology. However, due to the scaling relationship of the adsorption energy of reaction intermediates, there has long been a trade-off between the activity and selectivity of catalysts, unfavorable in realizing the Sustainable Development Goals. This work comprehensively studies the feasibility of achieving efficient 2e ^− ORR using pyridine nitrogen-coordinated p -block metal-based single-atom catalyst (SAC) (P@N _x ) through density functional theory (DFT) calculations, analyzing its thermodynamic stability, catalytic activity, and H _2 O _2 selectivity. The results show that P@N _x can partially break the scaling relationship between Δ G _*OOH and Δ G _*O through the transformation of adsorption configurations and the relaxation deformation of the metal–nitrogen (M–N) bonds in the substrate. By regulating the degree of charge transfer, the Δ G _*OOH can be tuned into the optimal range for 2e ^− ORR activity, while maintaining the selectivity descriptor ΔΔ G at a low level, thereby enabling a synergistic enhancement in both activity and selectivity. Furthermore, we combine multivariate correlation analysis and multiple linear regression to construct a comprehensive descriptor ϕ based on material property parameters, which quantitatively elucidates the influence weight of material properties on Δ G _*OOH . Our work not only screens out P@N _x catalysts with promising application potential but also offers key theoretical insights for the rational design of high-performance p -block metal-based SACs for H _2 O _2 electrosynthesis. It is thereby expected to advance the development of green, sustainable electrochemical synthesis technology and beyond.
Graphitic carbon nitride (g-C3N4) is confronted with the issue of poor utilization of photogenerated charge carriers, thereby leading to limited performance of photocatalytic hydrogen (H2) production, which restricts its potential application. Herein, the electron transport material SnO2/BaSO4 was synthesized to integrate with g-C3N4 for addressing the above problem. Various characterizations were conducted to investigate the g-C3N4-SnO2/BaSO4 photocatalyst, and it demonstrated that photogenerated electrons from g-C3N4 expeditiously migrate to SnO2/BaSO4 nanoparticles, which markedly hindered photogenerated carriers’ recombination. Subsequently, the g-C3N4-SnO2/BaSO4 photocatalyst demonstrated promoted photocatalytic H2 production at a rate of 14.2 μmol h−1 under visible-light illumination, which was 2.5 times higher than that of pristine g-C3N4.
The development of excellent photocatalysts for hydrogen production from water photolysis is a feasible strategy to realize efficient solar energy conversion and solve the energy crisis. The homogeneously dispersed CdS nanoparticles were in-situ grown on coral like carbon nitride (ag-C3N4) by a simple hydrothermal method. Compared with pure ag-C3N4, the prepared ag-C3N4/CdS exhibited excellent hydrogen evolution efficiency under visible light. The photocatalytic hydrogen production rate of ag-C3N4/CdS-17 % was 20.25 mmol h- 1 g- 1, which was about 18.1 times that of pure ag-C3N4. And ag-C3N4/CdS-17 % still maintained high stability after 16 consecutive hours of testing. The experimental results demonstrated that there were two key factors that contributed to the excellent photocatalytic performance of this binary heterojunction. Firstly, the coral like agC3N4 provided a good and sufficient dispersion site for CdS nanoparticles, making the CdS grains 15 times smaller than pure CdS. Secondly, an internal electric field from CdS to ag-C3N4 was formed between CdS and agC3N4, which promoted the charge transfer on the ag-C3N4/CdS binary heterostructure with the Z-scheme, changed the hole and electron transfer paths of ag-C3N4 and CdS, reduced the recombination rate of photogenerated electrons and holes, and thus improved the photocatalytic performance of ag-C3N4/CdS. Therefore, constructing Z-scheme heterojunction might provide an effective method to improve photocatalytic performance of binary heterojunctions.
Electrosynthesis of hydrogen peroxide (H2O2) via the oxygen reduction reaction (ORR) offers a sustainable alternative for the traditional anthraquinone method. p-block metals exhibit unique electronic structures and tunable surface properties, showing great potential in 2e- ORR. However, a systematic review focusing on recent progress in p-block metal-based electrocatalysts for H2O2 synthesis is lacking. To fill the gap, this work first shows a marked increase in p-block metal research over the past decade by bibliometric analysis of over 300 publications. Research on 2e- ORR has surged since 2019, while research on 2e‒ water oxidation reaction (WOR) has declined. Strategies for the synthesis and optimization of various p-block metal-based catalysts are discussed in detail. Based on a synthesis of DFT calculations in the literature, the reaction mechanisms of p-block metal catalysis proceeding are summarized via a 2e- pathway. Finally, considering the merits and limitations of different metals, this review outlines the primary challenges and future directions in this area, emphasizing the importance of improving catalyst stability, deepening mechanistic understanding, and developing cost-effective synthesis methods. It also offers novel perspectives on the engineering of p-block metal-based catalysts and promotes the development of sustainable H2O2 electrosynthesis technologies.
Photocatalysis technology can efficiently produce hydrogen, which is essential for the sustainable development of clean energy. Herein, molybdenum sulfide/carbon nanotubes/ cadmium sulfide (MoS2/CNTs/CdS) ternary composites are designed as catalysts to obtain an efficient photocatalytic hydrogen production system. In particular, the in-situ growth of CdS on the surface of MoS2/CNTs improves the dispersion of CdS nanoparticles, reduces the size of CdS particles, and increases the active site of photocatalytic reaction. A built-in electric field is formed between the interface between CdS and MoS2, which causes photogenerated electrons in conduction band (CB) of CdS and photogenerated holes in valence band (VB) of MoS2 to move in Z-type conduction mechanism. The excellent charge -conducting ability of CNTs reduces the recombination of photogenerated electrons and holes in CdS, further improving the hydrogen production efficiency and the stability of photocatalytic performance. Experiments showed that MoS2/CNTs/CdS (15%) have the highest hydrogen production rate (101.18 mmol h-1 g-1), which was 253 times higher than that of pure CdS. This study is expected to provide new ideas for the design and preparation of ternary hybrid photocatalysts for hydrogen production by photolysis of water.(c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
The ternary nanocomposites of CNTs/CdS/MoS2 was synthesized by a simple two-step hydrothermal method and characterized accordingly. In situ growth of CdS on the surface of CNTs decreased the size of CdS particles and increased its dispersibility. Moreover, CdS took advantage of the good conductivity of CNTs to accelerate the conduction of photogenerated holes and reduced the recombination efficiency of charge carriers. MoS2 grew in situ on the surface of CdS, and the interface between them formed a close contact heterostructure. The built-in electric field formed at the interface between the two forced the photogenerated electrons of CdS and the holes of MoS2 to recombine here. This property not only changed the path of photogenerated electrons and holes, but also made the surface of MoS2 becoming the active center of reduction reaction. The hybrid structure of CNTs/CdS/ MoS2 in-situ composite significantly improved the photocatalytic performance. When CNTs/CdS/MoS2 was used as photocatalyst, the degradation rate of tetracycline was 96.7% under 100 min of visible irradiation, and the data was still above 95% after 5 cycles indicate. This indicated that the ternary complex has good photocatalytic performance and stability. The successful preparation of CNTs/CdS/MoS2 provides an economically feasible approach for the degradation of tetracycline.
Triangular silver nanoplates exhibit excellent optical and catalytic properties in many fields, such as catalysts, sensors and bio-medicine. In this paper, triangular nanoplates were generated just in the presence of sodium citrate through a light-induced ripening process, which were converted from spherical silver nanoparticles by reducing silver nitrate with sodium borohydride. By using UV–Vis spectroscopy, particle size analyzer, transmission electron microscopy (TEM) and Ag+ concentration analysis, the effects of precursors during the preparation of triangular nanoplates were systematically investigated and the optimal experimental conditions were determined. Based on density functional theory (DFT), the adsorption energies of citrate ion, malate ion and tartronate ion on Ag (1 1 1), (1 1 0) and (1 0 0) were calculated. In addition, theoretical calculations coupled with experimental observations showed that citrate ion as capping agent could more preferentially bind to Ag (1 1 1) and thus blocked Ag (1 1 1) while only allowing extensive growth along the lateral direction. This well explains sodium citrate is an efficient agent in preparing triangular silver nanoplates.
A novel nano-heterojunction photocatalysts of CdS/MoS2 with appropriate interfacial contact was successfully obtained by the facile two-step hydrothermal synthesis. The MoS2 ultrathin layer was well combined with CdS nanosheets and formed the interaction, which facilitated the transfer and separation of charges. The CdS/MoS2 15 wt% possessed much higher H2 evolution photocatalytic performance (35.24 mmol h-1 g-1), exhibiting an 85.95 times enhancement as compared to that of pure CdS (0.41 mmol h-1 g-1). Moreover, the photochemical stability of CdS/MoS2 heterojunctions was excellent, which showed no significant decrease in activity after four cycles of experiments. The finding provides a novel method to integrate the structure of MoS2 with CdS, which exhibits great potential in solar energy conversion. (c) 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Mitochondria are important organelles that present extensively in cells, serving diverse functions. In addition to controlling cell energy production and metabolism, mitochondria are also involved in various biological processes, including anti-infection, apoptosis, and autophagy. Harmful stimuli from external environment or those generated by the cells themselves can damage mitochondria and cause mitochondrial stress response, during which the mitochondrial matrix containing mitochondrial DNA (mtDNA) can leak into the cytoplasm. Cytoplasmic mtDNA, acting as a damage-associated molecular pattern (DAMP), can activate a panel of DNA sensors and elicit innate immune response in organisms. Cyclic GMP-AMP synthase (cGAS), a key intracellular DNA sensor, can catalyze the conversion of GTP and ATP to cyclic GMP-AMP (2'3'-cGAMP), which serves as second messenger to bind and activate stimulator of interferon gene (STING), an endoplasmic adaptor protein. Beyond its critical roles in anti-microbial immunity, cGAS-STING pathway also serves important functions in many pathological and physiological processes such as autoimmunity, tumor and senescence. In this review, we focus on how the mtDNA released during mitochonrial stress response activates the cGAS-STING innate immune signaling pathway and the associated diseases, in order to help promote basic research about the role of mitochondria in innate immunity and provide new strategies for developing mitochondria-targeting drugs.
Stroke is the second most common cause of death after cancer worldwide and a major cause of acquired disability in adults. Overwhelming majority of strokes are caused by cerebral ischemia and are classified as ischemic stroke. Microglia are the resident immune cells and play dual roles in response to ischemia injury in the central nervous system (CNS). On the one hand, microglia may contribute to tissue function recovery process by promoting inflammation resolution, cellular debris clearance, nerve regeneration and synapse remodeling. On the other hand, excessive activation of microglia aggravates nerve damage after ischemic injury. Here, we briefly describe the mechanism of microglia activation after stroke, and comprehensively review the dual role of microglia in neurodegeneration and regeneration after stroke. In-depth exploration of the cytotoxic and protective mechanisms of microglia will provide new targets and new strategies for stroke treatment.
识别病毒核酸可触发宿主针对病毒的固有免疫反应.维甲酸诱导基因Ⅰ(retinoic acid-inducible geneⅠ,RIG-Ⅰ)和黑色素瘤分化相关基因5 (melanoma differentiation-associated gene 5,MDA5)存在于多种类型细胞中,参与识别入侵细胞质的病毒RNA,诱导下游抗病毒效应分子产生,在细胞抗病毒免疫反应中发挥重要作用.RIG-Ⅰ或MDA5与病毒RNA结合进而被激活的过程在时空上受到精密复杂的调控.近年来研究发现,辅助受体在RIG-Ⅰ和MDA5激活的过程中发挥重要辅助功能.文章概述了目前已知的RIG-Ⅰ和MDA5辅助受体研究进展,重点阐述了其在所介导的抗病毒信号通路中的调控机制和作用.这有助于深刻理解RIG-Ⅰ和MDA5所介导的抗病毒信号通路,并为相关疾病的治疗提供新策略.
IFN刺激基因15(interferon-stimulated gene 15,ISG15)编码的蛋白ISG15是最早被发现的一种类泛素蛋白,在生物体内以单体和复合体形式存在.和泛素一样,ISG15的单体和其共价修饰的蛋白参与并调节了复杂的生物学过程.在病毒、细菌感染以及肿瘤发生过程中,ISG15单体和底物蛋白的共价修饰水平均出现不同程度改变,这表明ISG15在固有免疫的调控中发挥重要作用.越来越多的研究表明ISG15和其共价修饰系统已成为疾病预防和治疗的重要靶点.文章介绍了ISG15的发现、结构特点以及其共价修饰系统,并阐述了近年来ISG15在抗病毒、抗菌和肿瘤发生过程中的重要作用.
Four kinds of ZnS@MoS2nanocomposite photocatalysts were successfully preparedviaa facile hydrothermal method.
Stimulator of interferon genes (STING) is critical for cytosolic DNA-triggered innate immunity. STING is modified by several types of polyubiquitin chains. Here, we report that the deubiquitinase CYLD sustains STING signaling by stabilizing the STING protein. CYLD deficiency promoted the K48-linked polyubiquitination and degradation of STING, attenuating the induction of IRF3-responsive genes after HSV-1 infection or the transfection of DNA ligands. Additionally, CYLD knockout mice were more susceptible to HSV-1 infection than their wild-type (WT) littermates. Mechanistically, STING translocated from the ER to the Golgi upon HSV-1 stimulation; CYLD partially accumulated with STING and interacted selectively with K48-linked polyubiquitin chains on STING, specifically removing the K48-linked polyubiquitin chains from STING and ultimately boosting the innate antiviral response. Our study reveals that CYLD is a novel checkpoint in the cGAS-STING signaling pathway and sheds new light on the dynamic regulation of STING activity by ubiquitination.
Induction time of silver colloids primary nucleation was determined by UV-Vis spectra,silver colloids were synthesized by a reaction of silver nitrate and sodium citrate.The effects of temperature and supersaturation(S) on induction time were considered.The results show that induction time decreases with increasing supersaturation and temperature.According to the classical theory of homogeneous nucleation,the primary nucleation of reaction was a homogeneous nucleation when S ≥ 4×108.Interfacial tensions between solid and liquid were estimated at different temperatures and compared with an empirical correlation for calculation of interfacial tension.The estimated values of the interfacial tension are lower than the values predicted by the empirical correlation.In this paper,the concentration of silver ion in the process of nucleation was also determined by UV-Vis spectra and it validates the method for measuring induction time by monitoring the adsorption of the colloids.
In the paper the Origin 8.0 software for data processing was introduced briefly.Meantime,the applications of Origin 8.0 in the experiments of physical chemistry were discussed.Data processing can be performed by linear regression,nonlinear fitting and other methods in Origin 8.0.The results obtained were reliable and the efficiency of data processing could be improved.
The spectrophotometric method for determination of azithromycin based on the color reaction of sulfuric acid and azithromycin was optimized and all variables reaction conditions such as sulfuric acid concentration,heating time,temperature were carefully studied.The result showed the maximum absorbance at 482nm is linear to concentration of azithromycin with A=0.0172C(mg·L-1)+0.0504 in the range of 11.26—45.03mg·L-1.The average recovery was 99.1%(n=9).This optimized method is simple,sensitive,accurate,and suitable for the rapid determination of azithromycin.
文章主要论述了药学类物理化学双语多媒体课件的设计理念,完成的物理化学课件在教学过程中广泛使用,得到了学生及同行的好评.