Background Vascular hyporeactivity and leakage are key pathophysiologic features that produce multi-organ damage upon sepsis.We hypothesized that pericytes,a group of pluripotent cells that maintain vascular integrity...Background Vascular hyporeactivity and leakage are key pathophysiologic features that produce multi-organ damage upon sepsis.We hypothesized that pericytes,a group of pluripotent cells that maintain vascular integrity and tension,are protective against sepsis via regulating vascular reactivity and permeability.Methods We conducted a series of in vivo experiments using wild-type(WT),platelet-derived growth factor receptor-β(PDGFR-β)-Cre+mT/mG transgenic mice and Tie2-Cre+Cx43^(flox/flox)mice to examine the relative contribution of pericytes in sepsis,either induced by cecal ligation and puncture(CLP)or lipopolysaccharide(LPS)challenge.In a separate set of experiments with Sprague-Dawley(SD)rats,pericytes were depleted using CP-673451,a selective PDGFR-βinhibitor,at a dosage of 40 mg/(kg·d)for 7 consecutive days.Cultured pericytes,vascular endothelial cells(VECs)and vascular smooth muscle cells(VSMCs)were used for mechanistic investigations.The effects of pericytes and pericyte-derived microvesicles(PCMVs)and candidate miRNAs on vascular reactivity and barrier function were also examined.Results CLP and LPS induced severe injury/loss of pericytes,vascular hyporeactivity and leakage(P<0.05).Transplantation with exogenous pericytes protected vascular reactivity and barrier function via microvessel colonization(P<0.05).Cx43 knockout in either pericytes or VECs reduced pericyte colonization in microvessels(P<0.05).Additionally,PCMVs transferred miR-145 and miR-132 to VSMCs and VECs,respectively,exerting a protective effect on vascular reactivity and barrier function after sepsis(P<0.05).miR-145 primarily improved the contractile response of VSMCs by activating the sphingosine kinase 2(Sphk2)/sphingosine-1-phosphate receptor(S1PR)1/phosphorylation of myosin light chain 20 pathway,whereas miR-132 effectively improved the barrier function of VECs by activating the Sphk2/S1PR2/zonula occludens-1 and vascular endothelial-cadherin pathways.Conclusions Pericytes are protective against sepsis through regulating vascular reactivity and barrier function.Possible mechanisms include both direct colonization of microvasculature and secretion of PCMVs.展开更多
The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)...The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.展开更多
The sessile drop method was applied to the experimental investigation of the wetting and spreading behaviors of liquid Mg drops on pure Ni substrates.For comparison,the experiments were performed in two variants:(1)us...The sessile drop method was applied to the experimental investigation of the wetting and spreading behaviors of liquid Mg drops on pure Ni substrates.For comparison,the experiments were performed in two variants:(1)using the Capillary Purification(CP)procedure,which allows the non-contact heating and squeezing of a pure oxide-free Mg drop;(2)by classical Contact Heating(CH)procedure.The high-temperature tests were performed under isothermal conditions(CP:760℃for 30 s;CH:715℃for 300 s)using Ar+5 wt%H_(2) atmosphere.During the sessile drop tests,images of the Mg/Ni couples were recorded by CCD cameras(57 fps),which were then applied to calculate the contact angles of metal/substrate couples.Scanning and transmission electron microscopy analyses,both coupled with energy-dispersive X-ray spectroscopy,were used for detailed structural characterization of the solidified couples.It was found that an oxide-free Mg drop obtained by the CP procedure showed a wetting phenomenon on the Ni substrate(an average contact angleθ<90°in<1 s),followed by fast spreading and good wetting over the Ni substrate(θ_((CP))~20°in 5 s)to form a final contact angle ofθ_(f(CP))~18°.In contrast,a different wetting behavior was observed for the CH procedure,where the unavoidable primary oxide film on the Mg surface blocked the spreading of liquid Mg showing apparently non-wetting behavior after 300 s contact at the test temperature.However,in both cases,the deep craters formed in the Ni substrates under the Mg drops and significant change in the structure of initially pure Mg drops to Mg-Ni alloys suggest a strong dissolution of Ni in liquid Mg and apparent values of the final contact angles measured for the Mg/Ni system.展开更多
Following publication of the original article,the authors observed that both Fig.5 and Fig.4 depict the same image.Figure 5 was inaccurately referenced and displayed.The correct Fig.5 is copied below:The original arti...Following publication of the original article,the authors observed that both Fig.5 and Fig.4 depict the same image.Figure 5 was inaccurately referenced and displayed.The correct Fig.5 is copied below:The original article has been updated.展开更多
The aim of this study was to investigate the oxidation reactivity and behavior of exhaust particulate matter(PM)from diesel engines.PM samples from two diesel engines(1K,CY4102)with different emission levels were coll...The aim of this study was to investigate the oxidation reactivity and behavior of exhaust particulate matter(PM)from diesel engines.PM samples from two diesel engines(1K,CY4102)with different emission levels were collected by a thermophoretic system and a quartz filter.The oxidation reactivity,oxidation behaviors,and physicochemical properties of the PM samples were analyzed using thermogravimetric analysis(TGA),high-resolution transmission electron microscopy(HRTEM),Fourier-transform infrared spectrometry(FTIR),and Raman spectroscopy.The results showed that there was a great difference in the oxidation reactivity of soot particles emitted by the two different diesel engines.A qualitative analysis of the factors influencing oxidation reactivity showed that the nanostructure,degree of graphitization,and relative concentration of aliphatic C—H functional groups were the most important factors,whereas no significant correlation was found between the primary particle size and activation energy of the diesel soot.Based on the oxidation behavior analysis,the diesel soot particles exhibited both internal and surface oxidation modes during the oxidation process.Surface oxidation was dominant during the initial stage,and as oxidation progressed,the mode gradually changed to internal oxidation.Internal oxidation mode of soot particles from the 1K engine was significantly higher than that of CY4102.展开更多
The reactivity and stability of seventeen (17) imidazo [1,2-a]pyridine N-acylhydrazone derivatives were investigated using density functional theory at the B3LYP/6-31+ G (d, p) level. Analysis of the molecular electro...The reactivity and stability of seventeen (17) imidazo [1,2-a]pyridine N-acylhydrazone derivatives were investigated using density functional theory at the B3LYP/6-31+ G (d, p) level. Analysis of the molecular electrostatic potential (MEP) and determination of the dual descriptor revealed that in most cases, the nitrogen atoms of the 6-πelectron conjugation, the oxygen, and the sulfur atom are nucleophilic site. Chemical reactivity of the compounds was assessed through analysis of frontier molecular orbitals (HOMO and LUMO), energy gap (Δℰ), chemical hardness (η), and the softness (S). Consequently, the compound 9e exhibited the lowest reactivity, least electron donating, and the highest stability. This comprehensive study offers valuable insights into the chemical behavior of these derivatives, crucial for further exploration and potential applications.展开更多
Several works have been based on the study of thermal variations in biomass to derive more valuable products such as fuels capable of replacing oil in the event of a crisis or activated carbon used as an adsorbent mat...Several works have been based on the study of thermal variations in biomass to derive more valuable products such as fuels capable of replacing oil in the event of a crisis or activated carbon used as an adsorbent material, widely used in industry for the elimination of unwanted materials, both in liquid and gaseous environments. A study of thermal parameters such as: heating speed, retention time, drying temperature, carbonization temperature, particle size, was carried out with the aim of determining the characteristic factors of the carbonization of Polyethylene terephthalate (PET), sawdust (SC) and sawdust/polyethylene terephthalate (CPS) mixture. The results of the immediate analysis revealed a very low level of ash in PET (0.013%) compared to the level of ash in sawdust (2.9%), as well as a high level of fixed carbon (82.960%), which suggests the presence of mineral oxides and a significant carbon matrix unlike PET, which indicates a very significant organic matrix (essentially made up of organic matter) with the absence of mineral oxides. The study of thermal parameters showed the water loss from Sawdust (SC) and the Sawdust/Polyethylene terephthalate (CPS) mixture, an increase with temperature, unlike that of PET whose variation is essentially zero. Without heat treatment, sawdust alone contains approximately 7% water. The optimal drying temperature for this study is 110˚C for a stay of 24 hours. It appears that the largest mass losses for the PET samples are between 87.19% and 96.05%, followed by that of the mixture, between 47.33% and 64.37%. And the lowest are observed, those of sawdust (from 24.02% to 62.6%). However, here we can say that the influence of the mass is not great, given the slight difference between the losses by temperature. The results of the study of the influence of grain size showed that the differences are insignificant, even if we vary the diameter of the grains from simple to triple. To better minimize physical constraints such as the intragranular diffusibility of the volatile matter and the homogeneity of the temperature in the grains, 75 μm particles are found to be optimal for our study. It can be noted when studying the heating rate that the mass loss at the end of the reaction is approximately the same depending on each precursor material. However, it has been demonstrated that the heating rate strongly influences the nature of the reaction products both for volatile materials and for the solid residue as well as on the kinetic parameters of the chemical reaction. Furthermore, the variation in apparent density shows a decrease as a function of the increase in the residence time of the materials in the reactor. As the carbonization time increases, the apparent density decreases. We note, for the lignocellulosic material, that the apparent density stabilizes after 60 minutes.展开更多
Astrocytes are the most abundant type of glial cell in the central nervous system.Upon injury and inflammation,astrocytes become reactive and undergo morphological and functional changes.Depending on their phenotypic ...Astrocytes are the most abundant type of glial cell in the central nervous system.Upon injury and inflammation,astrocytes become reactive and undergo morphological and functional changes.Depending on their phenotypic classification as A1 or A2,reactive astrocytes contribute to both neurotoxic and neuroprotective responses,respectively.However,this binary classification does not fully capture the diversity of astrocyte responses observed across different diseases and injuries.Transcriptomic analysis has revealed that reactive astrocytes have a complex landscape of gene expression profiles,which emphasizes the heterogeneous nature of their reactivity.Astrocytes actively participate in regulating central nervous system inflammation by interacting with microglia and other cell types,releasing cytokines,and influencing the immune response.The phosphoinositide 3-kinase(PI3K)/protein kinase B(AKT)signaling pathway is a central player in astrocyte reactivity and impacts various aspects of astrocyte behavior,as evidenced by in silico,in vitro,and in vivo results.In astrocytes,inflammatory cues trigger a cascade of molecular events,where nuclear factor-κB serves as a central mediator of the pro-inflammatory responses.Here,we review the heterogeneity of reactive astrocytes and the molecular mechanisms underlying their activation.We highlight the involvement of various signaling pathways that regulate astrocyte reactivity,including the PI3K/AKT/mammalian target of rapamycin(mTOR),αvβ3 integrin/PI3K/AKT/connexin 43,and Notch/PI3K/AKT pathways.While targeting the inactivation of the PI3K/AKT cellular signaling pathway to control reactive astrocytes and prevent central nervous system damage,evidence suggests that activating this pathway could also yield beneficial outcomes.This dual function of the PI3K/AKT pathway underscores its complexity in astrocyte reactivity and brain function modulation.The review emphasizes the importance of employing astrocyte-exclusive models to understand their functions accurately and these models are essential for clarifying astrocyte behavior.The findings should then be validated using in vivo models to ensure real-life relevance.The review also highlights the significance of PI3K/AKT pathway modulation in preventing central nervous system damage,although further studies are required to fully comprehend its role due to varying factors such as different cell types,astrocyte responses to inflammation,and disease contexts.Specific strategies are clearly necessary to address these variables effectively.展开更多
BACKGROUND:Soft tissue damage induced by cobalt nanoparticles is currently the most noticeable complication in patients with artificial joint prostheses.Therefore,an effective therapeutic strategy is needed to limit t...BACKGROUND:Soft tissue damage induced by cobalt nanoparticles is currently the most noticeable complication in patients with artificial joint prostheses.Therefore,an effective therapeutic strategy is needed to limit the toxicity of cobalt nanoparticles.OBJECTIVE:To investigate the protective effect of a ferroptosis inhibitor on cobalt nanoparticles-induced cytotoxicity.METHODS:To evaluate the detoxification effect of ferroptosis inhibitor on mouse fibroblasts(Balb/3T3),Balb/3T3 cells were treated with cobalt nanoparticles and ferroptosis inhibitor for 24 hours.The cell viabilities were measured by cell viability assay.Based on the results of the cell viability assay,the concentrations of cobalt nanoparticles and deferiprone were determined.The experiment was divided into four groups:the cobalt nanoparticles group(400μmol/L cobalt nanoparticles),the cobalt nanoparticles+deferiprone group(400μmol/L cobalt nanoparticles and 25μmol/L deferiprone),the deferiprone group(25μmol/L deferiprone),and the control group.The expressions of glutathione peroxidase 4 and solute carrier family 7 member 11 protein were examined by western blot assay.RESULTS AND CONCLUSION:(1)The cell viability assay results showed that as the exposure time or the drug concentration increased,cell viability decreased further,indicating that the cytotoxic effect of cobalt nanoparticles was time-and dose-dependent.Additionally,after 24 hours of exposure,cobalt nanoparticles significantly reduced cell viability and glutathione levels compared with the control group(P<0.05).At the same time,compared with the control group,there was an increase in reactive oxygen species production,intracellular iron levels,and the expression of inflammatory cytokines such as tumor necrosis factorα,interleukin-1β,and interleukin-6.After the addition of deferiprone,compared with the cobalt nanoparticles group,cell viability significantly improved,and reactive oxygen species production,intracellular iron levels,and the expression of inflammatory cytokines(tumor necrosis factorα,interleukin-1β,and interleukin-6)significantly decreased(P<0.05).This demonstrated that deferiprone had a protective effect on cells exposed to cobalt nanoparticles.(2)Western blot assay results showed that cobalt nanoparticles reduced the expression of glutathione peroxidase 4 and solute carrier family 7 member 11 protein(P<0.05),while deferiprone inhibited this effect(P<0.05).(3)The above findings verify that cobalt nanoparticles are highly cytotoxic and ferroptosis inhibitor deferiprone has a detoxification effect on cytotoxicity induced by cobalt nanoparticles.Ferroptosis plays an important role in the process by which cobalt nanoparticles induce cytotoxicity.The inhibitory effect of ferroptosis inhibitors on the toxicity of cobalt nanoparticles may provide valuable insights for further research into the mechanisms of cobalt nanoparticle toxicity and potential detoxification strategies.展开更多
Microwave discharge plasma in liquid(MDPL)is a new type of water purification technology with a high mass transfer efficiency.It is a kind of low-temperature plasma technology.The reactive species produced by the disc...Microwave discharge plasma in liquid(MDPL)is a new type of water purification technology with a high mass transfer efficiency.It is a kind of low-temperature plasma technology.The reactive species produced by the discharge can efficiently act on the pollutants.To clarify the application prospects of MDPL in water treatment,the discharge performance,practical application,and pollutant degradation mechanism of MDPL were studied in this work.The effects of power,conductivity,pH,and Fe^(2+)concentration on the amount of reactive species produced by the discharge were explored.The most common and refractory perfluorinated compounds(perfluorooctanoic acid(PFOA)and perfluorooctane sulfonate(PFOS)in water environments are degraded by MDPL technology.The highest defluorination of PFOA was 98.8% and the highest defluorination of PFOS was 92.7%.The energy consumption efficiency of 50% defluorination(G_(50-F))of PFOA degraded by MDPL is 78.43 mg/kWh,PFOS is 42.19 mg/kWh.The results show that the MDPL technology is more efficient and cleaner for the degradation of perfluorinated compounds.Finally,the reaction path and pollutant degradation mechanisms of MDPL production were analyzed.The results showed that MDPL technology can produce a variety of reactive species and has a good treatment effect for refractory perfluorinated pollutants.展开更多
Honglian type-cytoplasmic male sterility(HL-CMS)is caused by the inter-communication between the nucleus and mitochondria.However,the mechanisms by which sterility genes regulate metabolic alterations and changes in m...Honglian type-cytoplasmic male sterility(HL-CMS)is caused by the inter-communication between the nucleus and mitochondria.However,the mechanisms by which sterility genes regulate metabolic alterations and changes in mitochondrial morphology in the pollen of HL-CMS remain unclear.In this study,we compared the morphological differences between the pollen of the male sterile line YA and the near-isogenic line NIL-Rf6 using hematoxylin-eosin staining and 4ʹ,6-diamidino-2-phenylindole(DAPI)staining.HL-CMS is characterized by gametophytic sterility,where the aborted pollen grains are empty,and the tapetal layer remains intact.Transmission electron microscopy was employed to observe mitochondrial morphological changes at the microspore stage,revealing significant mitochondrial alterations,characterized by the formation of'large spherical mitochondria',occurred at the binucleate stage in the YA line.Additionally,metabolomics analysis revealed decreased levels of metabolites associated with the carbohydrate and flavonoid pathways.Notably,the decrease in flavonoids was found to contribute to an elevation in reactive oxygen species(ROS)levels.Therefore,we propose a model in which rice fertility is modulated by the levels of pollen carbohydrates and flavonoid metabolites,with impaired mitochondrial energy production and reduced flavonoid biosynthesis as the main causes of ROS accumulation and pollen abortion in rice.展开更多
Flexible surface micro-discharge plasma is a non-thermal plasma technique used for treating wounds in a painless way, with significant efficacy for chronic or hard-to-heal wounds. In this study, a confined space was d...Flexible surface micro-discharge plasma is a non-thermal plasma technique used for treating wounds in a painless way, with significant efficacy for chronic or hard-to-heal wounds. In this study, a confined space was designed to simulate wound conditions, with gelatin used to simulate wound tissue. The distinction between open and confined spaces was explored, and the effects of temperature, humidity, discharge power and the gap size within the confined space on the plasma characteristics were analyzed. It was found that temperature, humidity and discharge power are important factors that affect the concentration distribution of active components and the mode transition between ozone and nitrogen oxides. Compared to open space, the concentration of ozone in confined space was relatively lower, which facilitated the formation of nitrogen oxides. In open space, the discharge was dominated by ozone initially. As the temperature,humidity and discharge power increased, nitrogen oxides in the gas-phase products were gradually detected. In confined space, nitrogen oxides can be detected at an early stage and at much higher concentrations than ozone concentration. Furthermore, as the gap of the confined space decreased, the concentration of ozone was observed to decrease while that of nitrate increased, and the rate of this concentration change was further accelerated at higher temperature and higher power. It was shown that ozone concentration decreased from 0.11 to 0.03 μmol and the nitrate concentration increased from 20.5 to 24.5 μmol when the spacing in the confined space was reduced from 5 to 1 mm, the temperature of the external discharge was controlled at 40 ℃, and the discharge power was 12 W. In summary, this study reveals the formation and transformation mechanisms of active substances in air surface micro-discharge plasma within confined space, providing foundational data for its medical applications.展开更多
Effect of sulfur impurity on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and impurities doping. And its mechanism was discussed by X-ray diffraction (XRD), scanning elect...Effect of sulfur impurity on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and impurities doping. And its mechanism was discussed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results show that sulfur has strong catalysis on both air and CO2 reactivity of coke in the case of no other impurity interference. Its catalysis is probably realized by triggering organic sulfur→H2S→SO2→COS and elemental sulfur (Sx)→SO2 and organic sulfur→H2S→COS→Sx→C2S→COS reaction systems during coke?O2 and coke?CO2 reactions, respectively, which are partly circular with functions of increasing carbon consumption and enlarging coke specific surface area.展开更多
The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory(DFT),and the reactivities of pyrite with oxygen and xanthate were discussed by fr...The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory(DFT),and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.展开更多
The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved ...The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved heat is helpful in terms of understanding the nature of the interactions be- tween the catalyst and the adsorbed species, and provides insights into the reactivity of the catalyst. Although various techniques have previously been applied to assessments of evolved heat, direct measurements using a Tian-Calvet microcalorimeter are currently the most reliable method for this purpose. In this review, we summarize the relationship between the adsorption/reaction energetics determined by microcalorimetry and the reactivities of supported catalysts, and examine the im- portant role of microcalorimetry in understanding catalytic performance from the energetic point of view.展开更多
Ambient volatile organic compounds (VOCs) were sampled at six sites in Beijing in the summer of 2004 and analyzed by GCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates (LO...Ambient volatile organic compounds (VOCs) were sampled at six sites in Beijing in the summer of 2004 and analyzed by GCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates (LOH) and ozone formation potentials (OFPs). Top 15 reactive species, mainly alkenes and aromatics, were identified by these two methods, and accounted for more than 70% of total reactivity of VOCs. In urban areas, isoprene was the most reactive species in term of OH loss rate, contributing 11.4% to the LOH of VOCs. While toluene, accounting for 9.4% of OFPs, appeared to have a long-time role in the photochemical processes. Tongzhou site is obviously influenced by local chemical industry, but the other five sites showed typical urban features influenced mainly by vehicular emissions.展开更多
More detailed analysis of a mutual relationship of impact sensitivity(detected by sound) and crystal lattice free volume, △V, for the 18 nitramines shows that its course is not unequivocal. For a part of the studied ...More detailed analysis of a mutual relationship of impact sensitivity(detected by sound) and crystal lattice free volume, △V, for the 18 nitramines shows that its course is not unequivocal. For a part of the studied compounds this sensitivity has increased with increase of the AV values, but for fairly big number of nitramines the relationship works in the opposite direction, especially for data of 1,3,5-trinitro-1,3,5-triazinane, 1,3,5,7-tetranitro-1,3,5,7-tetrazocane. and β-and ε-polymorphs of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. Initiation reactivity of technical ε-polymorph of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane gives the impression by disorderliness in distribution of the actions of forces in its crystal lattice in comparison with its RS(reduced sensitivity) or chemically pure analogue. Limitations of partial shapes of the mentioned relationship by the molecular-structural similarity, and already published information about the decisive factors governing the crystal structure, signalizes a higher influence of the intermolecular interactions in a crystal lattice in comparison with influence of the crystal lattice free volume for initiation of the crystalline EMs.展开更多
The relationship between friction sensitivity(FS) and the crystal lattice free space per molecule, △V. of thirteen nitramines is described by a linear equation, divided into a number of the partial relationships with...The relationship between friction sensitivity(FS) and the crystal lattice free space per molecule, △V. of thirteen nitramines is described by a linear equation, divided into a number of the partial relationships with strong limitations by their molecular structure characteristics. Increasing FS due to raising of the △V values is not clearly confirmed. The influence of the △V values on friction sensitivity of nitramines is similar to that of their aza atoms which influence the mutual orientations of nitro groups in neighboring molecules. The dipole-dipole interaction of the oxygen and nitrogen atoms of nitro groups in neighboring nitramine molecules has a major effect on their own FS. In accordance with this interaction, a directly proportional relationship was derived between FS and the intrinsic gas phase molecular volume, V_(int), of the nitramines mentioned, which is divided also into several straight lines according to relatively tight molecular structure similarity. The relationships found again confirm a level of disorder in the distribution of the forces in the crystal lattice of the "common" quality of ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, in comparison with its reduced sensitivity(RS) or chemically pure analogue.展开更多
Miniemulsion copolymerization of butyl mathacrylate (BMA) with fluoroacrylate (HFMA, TFMA) was carried out at 70 ℃ by employing potassium persulphate (KPS) as initiator. Copolymer compositions at low conversion...Miniemulsion copolymerization of butyl mathacrylate (BMA) with fluoroacrylate (HFMA, TFMA) was carried out at 70 ℃ by employing potassium persulphate (KPS) as initiator. Copolymer compositions at low conversion levels were determined by ^1H NMR spectra techniques. The reactivity ratios were evaluated by employing Kellen-Tudos (K-T) methods, which yields the apparent reactivity ratios, rBMA = 0.74, rHFMA = 0.87 and rBMA = 0.73, rTFMA = 0.75, respectively, and Q- and e-values of HFMA and TFMA were calculated by the Alfrey-Price method. The results show that HFMA and TFMA are more active than BMA, and the cross-propagation rate constant is greater than the self-propagation one in these two copolymerizations.展开更多
The interactions of a spherical flame with an incident shock wave and its reflected shock wave in a confined space were investigated using the three-dimensional reactive Navier-Stokes equations, with emphasis placed o...The interactions of a spherical flame with an incident shock wave and its reflected shock wave in a confined space were investigated using the three-dimensional reactive Navier-Stokes equations, with emphasis placed on the effect of chemical reactivity of mixture on the flame distortion and detonation initiation after the passage of the reflected shock wave. It is shown that the spatio-temporal characteristics of detonation initiation depend highly on the chemi- cal reactivity of the mixture. When the chemical reactivity enhances, the flame can be severely distorted to form a reactive shock bifurcation structure with detonations initiating at different three-dimensional spatial locations. Moreover, the detonation initiation would occur earlier in a mixture of more enhanced reactivity. The results reveal that the detona- tions arise from hot spots in the unburned region which are initiated by the shock-detonation-transition mechanism.展开更多
基金supported by the Key Projects and Innovation Group of National Natural Science Foundation of China(81830065),the Innovation Groups of NSFC(81721001),and the Young Scientists Fund(82102279).
文摘Background Vascular hyporeactivity and leakage are key pathophysiologic features that produce multi-organ damage upon sepsis.We hypothesized that pericytes,a group of pluripotent cells that maintain vascular integrity and tension,are protective against sepsis via regulating vascular reactivity and permeability.Methods We conducted a series of in vivo experiments using wild-type(WT),platelet-derived growth factor receptor-β(PDGFR-β)-Cre+mT/mG transgenic mice and Tie2-Cre+Cx43^(flox/flox)mice to examine the relative contribution of pericytes in sepsis,either induced by cecal ligation and puncture(CLP)or lipopolysaccharide(LPS)challenge.In a separate set of experiments with Sprague-Dawley(SD)rats,pericytes were depleted using CP-673451,a selective PDGFR-βinhibitor,at a dosage of 40 mg/(kg·d)for 7 consecutive days.Cultured pericytes,vascular endothelial cells(VECs)and vascular smooth muscle cells(VSMCs)were used for mechanistic investigations.The effects of pericytes and pericyte-derived microvesicles(PCMVs)and candidate miRNAs on vascular reactivity and barrier function were also examined.Results CLP and LPS induced severe injury/loss of pericytes,vascular hyporeactivity and leakage(P<0.05).Transplantation with exogenous pericytes protected vascular reactivity and barrier function via microvessel colonization(P<0.05).Cx43 knockout in either pericytes or VECs reduced pericyte colonization in microvessels(P<0.05).Additionally,PCMVs transferred miR-145 and miR-132 to VSMCs and VECs,respectively,exerting a protective effect on vascular reactivity and barrier function after sepsis(P<0.05).miR-145 primarily improved the contractile response of VSMCs by activating the sphingosine kinase 2(Sphk2)/sphingosine-1-phosphate receptor(S1PR)1/phosphorylation of myosin light chain 20 pathway,whereas miR-132 effectively improved the barrier function of VECs by activating the Sphk2/S1PR2/zonula occludens-1 and vascular endothelial-cadherin pathways.Conclusions Pericytes are protective against sepsis through regulating vascular reactivity and barrier function.Possible mechanisms include both direct colonization of microvasculature and secretion of PCMVs.
基金supported by the National Projects of the National Research Foundation(NRF)funded by Republic of Korea(#2022R1F1A1072739 and#2022R1A2C1004392)Prof.Nashrah is also grateful for financial supports by the YU Infra-Project in conjunction with BK21 FOUR National Program(#222A251009)by the Nano-Fab-NRF grant funded by Republic of Korea(#2009-0082580).
文摘The trade-off between efficiency and stability has limited the application of TiO_(2)as a catalyst due to its poor surface reactivity.Here,we present a modification of a TiO_(2)layer with highly stable Sub-5 nm Fe_(2)O_(3)nanoparticles(NP)by modulating its structure-surface reactivity relationship to attain efficiency-stability balance via a voltage-assisted oxidation approach.In situ simultaneous oxidation of the Ti substrate and Fe precursor using high-energy plasma driven by high voltage resulted in uniform distribution of Fe_(2)O_(3)NP embedded within porous TiO_(2)layer.Comprehensive surface characterizations with density functional theory demonstrated an improved electronic transition in TiO_(2)due to the presence of surface defects from reactive oxygen species and possible charge transfer from Ti to Fe;it also unexpectedly increased the active site in the TiO_(2)layer due to uncoordinated electrons in Sub-5 nm Fe_(2)O_(3)NP/TiO_(2)catalyst,thereby enhancing the adsorption of chemical functional groups on the catalyst.This unique embedded structure exhibited remarkable improvement in reducing 4-nitrophenol to 4-aminophenol,achieving approximately 99%efficiency in 20 min without stability decay after 20 consecutive cycles,outperforming previously reported TiO_(2)-based catalysts.This finding proposes a modified-electrochemical strategy enabling facile construction of TiO_(2)with nanoscale oxides extandable to other metal oxide systems.
基金supported by the National Science Centre of Poland within OPUS 16 Project,no.2018/31/B/ST8/01172。
文摘The sessile drop method was applied to the experimental investigation of the wetting and spreading behaviors of liquid Mg drops on pure Ni substrates.For comparison,the experiments were performed in two variants:(1)using the Capillary Purification(CP)procedure,which allows the non-contact heating and squeezing of a pure oxide-free Mg drop;(2)by classical Contact Heating(CH)procedure.The high-temperature tests were performed under isothermal conditions(CP:760℃for 30 s;CH:715℃for 300 s)using Ar+5 wt%H_(2) atmosphere.During the sessile drop tests,images of the Mg/Ni couples were recorded by CCD cameras(57 fps),which were then applied to calculate the contact angles of metal/substrate couples.Scanning and transmission electron microscopy analyses,both coupled with energy-dispersive X-ray spectroscopy,were used for detailed structural characterization of the solidified couples.It was found that an oxide-free Mg drop obtained by the CP procedure showed a wetting phenomenon on the Ni substrate(an average contact angleθ<90°in<1 s),followed by fast spreading and good wetting over the Ni substrate(θ_((CP))~20°in 5 s)to form a final contact angle ofθ_(f(CP))~18°.In contrast,a different wetting behavior was observed for the CH procedure,where the unavoidable primary oxide film on the Mg surface blocked the spreading of liquid Mg showing apparently non-wetting behavior after 300 s contact at the test temperature.However,in both cases,the deep craters formed in the Ni substrates under the Mg drops and significant change in the structure of initially pure Mg drops to Mg-Ni alloys suggest a strong dissolution of Ni in liquid Mg and apparent values of the final contact angles measured for the Mg/Ni system.
文摘Following publication of the original article,the authors observed that both Fig.5 and Fig.4 depict the same image.Figure 5 was inaccurately referenced and displayed.The correct Fig.5 is copied below:The original article has been updated.
基金the SINOPEC(124015)and the State Key Laboratory of Engines at Tianjin University(No.K2022-06).
文摘The aim of this study was to investigate the oxidation reactivity and behavior of exhaust particulate matter(PM)from diesel engines.PM samples from two diesel engines(1K,CY4102)with different emission levels were collected by a thermophoretic system and a quartz filter.The oxidation reactivity,oxidation behaviors,and physicochemical properties of the PM samples were analyzed using thermogravimetric analysis(TGA),high-resolution transmission electron microscopy(HRTEM),Fourier-transform infrared spectrometry(FTIR),and Raman spectroscopy.The results showed that there was a great difference in the oxidation reactivity of soot particles emitted by the two different diesel engines.A qualitative analysis of the factors influencing oxidation reactivity showed that the nanostructure,degree of graphitization,and relative concentration of aliphatic C—H functional groups were the most important factors,whereas no significant correlation was found between the primary particle size and activation energy of the diesel soot.Based on the oxidation behavior analysis,the diesel soot particles exhibited both internal and surface oxidation modes during the oxidation process.Surface oxidation was dominant during the initial stage,and as oxidation progressed,the mode gradually changed to internal oxidation.Internal oxidation mode of soot particles from the 1K engine was significantly higher than that of CY4102.
文摘The reactivity and stability of seventeen (17) imidazo [1,2-a]pyridine N-acylhydrazone derivatives were investigated using density functional theory at the B3LYP/6-31+ G (d, p) level. Analysis of the molecular electrostatic potential (MEP) and determination of the dual descriptor revealed that in most cases, the nitrogen atoms of the 6-πelectron conjugation, the oxygen, and the sulfur atom are nucleophilic site. Chemical reactivity of the compounds was assessed through analysis of frontier molecular orbitals (HOMO and LUMO), energy gap (Δℰ), chemical hardness (η), and the softness (S). Consequently, the compound 9e exhibited the lowest reactivity, least electron donating, and the highest stability. This comprehensive study offers valuable insights into the chemical behavior of these derivatives, crucial for further exploration and potential applications.
文摘Several works have been based on the study of thermal variations in biomass to derive more valuable products such as fuels capable of replacing oil in the event of a crisis or activated carbon used as an adsorbent material, widely used in industry for the elimination of unwanted materials, both in liquid and gaseous environments. A study of thermal parameters such as: heating speed, retention time, drying temperature, carbonization temperature, particle size, was carried out with the aim of determining the characteristic factors of the carbonization of Polyethylene terephthalate (PET), sawdust (SC) and sawdust/polyethylene terephthalate (CPS) mixture. The results of the immediate analysis revealed a very low level of ash in PET (0.013%) compared to the level of ash in sawdust (2.9%), as well as a high level of fixed carbon (82.960%), which suggests the presence of mineral oxides and a significant carbon matrix unlike PET, which indicates a very significant organic matrix (essentially made up of organic matter) with the absence of mineral oxides. The study of thermal parameters showed the water loss from Sawdust (SC) and the Sawdust/Polyethylene terephthalate (CPS) mixture, an increase with temperature, unlike that of PET whose variation is essentially zero. Without heat treatment, sawdust alone contains approximately 7% water. The optimal drying temperature for this study is 110˚C for a stay of 24 hours. It appears that the largest mass losses for the PET samples are between 87.19% and 96.05%, followed by that of the mixture, between 47.33% and 64.37%. And the lowest are observed, those of sawdust (from 24.02% to 62.6%). However, here we can say that the influence of the mass is not great, given the slight difference between the losses by temperature. The results of the study of the influence of grain size showed that the differences are insignificant, even if we vary the diameter of the grains from simple to triple. To better minimize physical constraints such as the intragranular diffusibility of the volatile matter and the homogeneity of the temperature in the grains, 75 μm particles are found to be optimal for our study. It can be noted when studying the heating rate that the mass loss at the end of the reaction is approximately the same depending on each precursor material. However, it has been demonstrated that the heating rate strongly influences the nature of the reaction products both for volatile materials and for the solid residue as well as on the kinetic parameters of the chemical reaction. Furthermore, the variation in apparent density shows a decrease as a function of the increase in the residence time of the materials in the reactor. As the carbonization time increases, the apparent density decreases. We note, for the lignocellulosic material, that the apparent density stabilizes after 60 minutes.
基金supported by Fondo Nacional de Desarrollo Científico y Tecnológico(FONDECYT)#1200836,#1210644,and#1240888,and Agencia Nacional de Investigación y Desarrollo(ANID)-FONDAP#15130011(to LL)FONDECYT#3230227(to MFG).
文摘Astrocytes are the most abundant type of glial cell in the central nervous system.Upon injury and inflammation,astrocytes become reactive and undergo morphological and functional changes.Depending on their phenotypic classification as A1 or A2,reactive astrocytes contribute to both neurotoxic and neuroprotective responses,respectively.However,this binary classification does not fully capture the diversity of astrocyte responses observed across different diseases and injuries.Transcriptomic analysis has revealed that reactive astrocytes have a complex landscape of gene expression profiles,which emphasizes the heterogeneous nature of their reactivity.Astrocytes actively participate in regulating central nervous system inflammation by interacting with microglia and other cell types,releasing cytokines,and influencing the immune response.The phosphoinositide 3-kinase(PI3K)/protein kinase B(AKT)signaling pathway is a central player in astrocyte reactivity and impacts various aspects of astrocyte behavior,as evidenced by in silico,in vitro,and in vivo results.In astrocytes,inflammatory cues trigger a cascade of molecular events,where nuclear factor-κB serves as a central mediator of the pro-inflammatory responses.Here,we review the heterogeneity of reactive astrocytes and the molecular mechanisms underlying their activation.We highlight the involvement of various signaling pathways that regulate astrocyte reactivity,including the PI3K/AKT/mammalian target of rapamycin(mTOR),αvβ3 integrin/PI3K/AKT/connexin 43,and Notch/PI3K/AKT pathways.While targeting the inactivation of the PI3K/AKT cellular signaling pathway to control reactive astrocytes and prevent central nervous system damage,evidence suggests that activating this pathway could also yield beneficial outcomes.This dual function of the PI3K/AKT pathway underscores its complexity in astrocyte reactivity and brain function modulation.The review emphasizes the importance of employing astrocyte-exclusive models to understand their functions accurately and these models are essential for clarifying astrocyte behavior.The findings should then be validated using in vivo models to ensure real-life relevance.The review also highlights the significance of PI3K/AKT pathway modulation in preventing central nervous system damage,although further studies are required to fully comprehend its role due to varying factors such as different cell types,astrocyte responses to inflammation,and disease contexts.Specific strategies are clearly necessary to address these variables effectively.
文摘BACKGROUND:Soft tissue damage induced by cobalt nanoparticles is currently the most noticeable complication in patients with artificial joint prostheses.Therefore,an effective therapeutic strategy is needed to limit the toxicity of cobalt nanoparticles.OBJECTIVE:To investigate the protective effect of a ferroptosis inhibitor on cobalt nanoparticles-induced cytotoxicity.METHODS:To evaluate the detoxification effect of ferroptosis inhibitor on mouse fibroblasts(Balb/3T3),Balb/3T3 cells were treated with cobalt nanoparticles and ferroptosis inhibitor for 24 hours.The cell viabilities were measured by cell viability assay.Based on the results of the cell viability assay,the concentrations of cobalt nanoparticles and deferiprone were determined.The experiment was divided into four groups:the cobalt nanoparticles group(400μmol/L cobalt nanoparticles),the cobalt nanoparticles+deferiprone group(400μmol/L cobalt nanoparticles and 25μmol/L deferiprone),the deferiprone group(25μmol/L deferiprone),and the control group.The expressions of glutathione peroxidase 4 and solute carrier family 7 member 11 protein were examined by western blot assay.RESULTS AND CONCLUSION:(1)The cell viability assay results showed that as the exposure time or the drug concentration increased,cell viability decreased further,indicating that the cytotoxic effect of cobalt nanoparticles was time-and dose-dependent.Additionally,after 24 hours of exposure,cobalt nanoparticles significantly reduced cell viability and glutathione levels compared with the control group(P<0.05).At the same time,compared with the control group,there was an increase in reactive oxygen species production,intracellular iron levels,and the expression of inflammatory cytokines such as tumor necrosis factorα,interleukin-1β,and interleukin-6.After the addition of deferiprone,compared with the cobalt nanoparticles group,cell viability significantly improved,and reactive oxygen species production,intracellular iron levels,and the expression of inflammatory cytokines(tumor necrosis factorα,interleukin-1β,and interleukin-6)significantly decreased(P<0.05).This demonstrated that deferiprone had a protective effect on cells exposed to cobalt nanoparticles.(2)Western blot assay results showed that cobalt nanoparticles reduced the expression of glutathione peroxidase 4 and solute carrier family 7 member 11 protein(P<0.05),while deferiprone inhibited this effect(P<0.05).(3)The above findings verify that cobalt nanoparticles are highly cytotoxic and ferroptosis inhibitor deferiprone has a detoxification effect on cytotoxicity induced by cobalt nanoparticles.Ferroptosis plays an important role in the process by which cobalt nanoparticles induce cytotoxicity.The inhibitory effect of ferroptosis inhibitors on the toxicity of cobalt nanoparticles may provide valuable insights for further research into the mechanisms of cobalt nanoparticle toxicity and potential detoxification strategies.
基金supported by National Natural Science Foundation of China(Nos.12475258,12111530008 and 11675031)Major Scientific Research Project of Hebei Transportation Investment Group in 2024([202]155)the support of the Fundamental Research Funds for the Central Universities(No.3132023503)。
文摘Microwave discharge plasma in liquid(MDPL)is a new type of water purification technology with a high mass transfer efficiency.It is a kind of low-temperature plasma technology.The reactive species produced by the discharge can efficiently act on the pollutants.To clarify the application prospects of MDPL in water treatment,the discharge performance,practical application,and pollutant degradation mechanism of MDPL were studied in this work.The effects of power,conductivity,pH,and Fe^(2+)concentration on the amount of reactive species produced by the discharge were explored.The most common and refractory perfluorinated compounds(perfluorooctanoic acid(PFOA)and perfluorooctane sulfonate(PFOS)in water environments are degraded by MDPL technology.The highest defluorination of PFOA was 98.8% and the highest defluorination of PFOS was 92.7%.The energy consumption efficiency of 50% defluorination(G_(50-F))of PFOA degraded by MDPL is 78.43 mg/kWh,PFOS is 42.19 mg/kWh.The results show that the MDPL technology is more efficient and cleaner for the degradation of perfluorinated compounds.Finally,the reaction path and pollutant degradation mechanisms of MDPL production were analyzed.The results showed that MDPL technology can produce a variety of reactive species and has a good treatment effect for refractory perfluorinated pollutants.
基金supported by the National Natural Science Foundation of China(Grant No.32472185)the Key Research and Development Program of Hubei Province,China(Grant No.2022BFE003)the Hubei Agriculture Science and Technology Innovation Center program,and the National Rice Industry Technology System,China(Grant No.CARS-01-07).
文摘Honglian type-cytoplasmic male sterility(HL-CMS)is caused by the inter-communication between the nucleus and mitochondria.However,the mechanisms by which sterility genes regulate metabolic alterations and changes in mitochondrial morphology in the pollen of HL-CMS remain unclear.In this study,we compared the morphological differences between the pollen of the male sterile line YA and the near-isogenic line NIL-Rf6 using hematoxylin-eosin staining and 4ʹ,6-diamidino-2-phenylindole(DAPI)staining.HL-CMS is characterized by gametophytic sterility,where the aborted pollen grains are empty,and the tapetal layer remains intact.Transmission electron microscopy was employed to observe mitochondrial morphological changes at the microspore stage,revealing significant mitochondrial alterations,characterized by the formation of'large spherical mitochondria',occurred at the binucleate stage in the YA line.Additionally,metabolomics analysis revealed decreased levels of metabolites associated with the carbohydrate and flavonoid pathways.Notably,the decrease in flavonoids was found to contribute to an elevation in reactive oxygen species(ROS)levels.Therefore,we propose a model in which rice fertility is modulated by the levels of pollen carbohydrates and flavonoid metabolites,with impaired mitochondrial energy production and reduced flavonoid biosynthesis as the main causes of ROS accumulation and pollen abortion in rice.
基金supported by Postgraduate Research&Practice Innovation Program of Jiangsu Province (No. 1003016001)。
文摘Flexible surface micro-discharge plasma is a non-thermal plasma technique used for treating wounds in a painless way, with significant efficacy for chronic or hard-to-heal wounds. In this study, a confined space was designed to simulate wound conditions, with gelatin used to simulate wound tissue. The distinction between open and confined spaces was explored, and the effects of temperature, humidity, discharge power and the gap size within the confined space on the plasma characteristics were analyzed. It was found that temperature, humidity and discharge power are important factors that affect the concentration distribution of active components and the mode transition between ozone and nitrogen oxides. Compared to open space, the concentration of ozone in confined space was relatively lower, which facilitated the formation of nitrogen oxides. In open space, the discharge was dominated by ozone initially. As the temperature,humidity and discharge power increased, nitrogen oxides in the gas-phase products were gradually detected. In confined space, nitrogen oxides can be detected at an early stage and at much higher concentrations than ozone concentration. Furthermore, as the gap of the confined space decreased, the concentration of ozone was observed to decrease while that of nitrate increased, and the rate of this concentration change was further accelerated at higher temperature and higher power. It was shown that ozone concentration decreased from 0.11 to 0.03 μmol and the nitrate concentration increased from 20.5 to 24.5 μmol when the spacing in the confined space was reduced from 5 to 1 mm, the temperature of the external discharge was controlled at 40 ℃, and the discharge power was 12 W. In summary, this study reveals the formation and transformation mechanisms of active substances in air surface micro-discharge plasma within confined space, providing foundational data for its medical applications.
基金Project(51374253)supported by the National Natural Science Foundation of China
文摘Effect of sulfur impurity on coke reactivity was investigated by simulating petroleum coke with low-impurity pitch coke and impurities doping. And its mechanism was discussed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results show that sulfur has strong catalysis on both air and CO2 reactivity of coke in the case of no other impurity interference. Its catalysis is probably realized by triggering organic sulfur→H2S→SO2→COS and elemental sulfur (Sx)→SO2 and organic sulfur→H2S→COS→Sx→C2S→COS reaction systems during coke?O2 and coke?CO2 reactions, respectively, which are partly circular with functions of increasing carbon consumption and enlarging coke specific surface area.
基金Project (50864001) supported by the National Natural Science Foundation of China
文摘The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory(DFT),and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.
基金supported by the National Natural Science Foundation of China (21573232, 21576251, 21676269)National Key Projects for Funda-mental Research and Development of China (2016YFA0202801)Department of Science and Technology of Liaoning province under contract of 2015020086–101~~
文摘The formations and transformations of the chemical bonds of reactants and intermediates on cata- lyst surfaces occur in conjunction with the evolution of heat during catalytic reactions. Measure- ment of this evolved heat is helpful in terms of understanding the nature of the interactions be- tween the catalyst and the adsorbed species, and provides insights into the reactivity of the catalyst. Although various techniques have previously been applied to assessments of evolved heat, direct measurements using a Tian-Calvet microcalorimeter are currently the most reliable method for this purpose. In this review, we summarize the relationship between the adsorption/reaction energetics determined by microcalorimetry and the reactivities of supported catalysts, and examine the im- portant role of microcalorimetry in understanding catalytic performance from the energetic point of view.
基金National Natural Science Foundation of China(No.40575059 and No.20637001).
文摘Ambient volatile organic compounds (VOCs) were sampled at six sites in Beijing in the summer of 2004 and analyzed by GCMS. The chemical reactivities of 73 quantified VOCs species were evaluated by OH loss rates (LOH) and ozone formation potentials (OFPs). Top 15 reactive species, mainly alkenes and aromatics, were identified by these two methods, and accounted for more than 70% of total reactivity of VOCs. In urban areas, isoprene was the most reactive species in term of OH loss rate, contributing 11.4% to the LOH of VOCs. While toluene, accounting for 9.4% of OFPs, appeared to have a long-time role in the photochemical processes. Tongzhou site is obviously influenced by local chemical industry, but the other five sites showed typical urban features influenced mainly by vehicular emissions.
基金financial support from the Students Grant Projects No. SGSFCHT_2016002 of the Faculty of Chemical Technology at the University of Pardubicefinancial support The State Administration of Foreign Experts Affairs, Peoples Republic of China
文摘More detailed analysis of a mutual relationship of impact sensitivity(detected by sound) and crystal lattice free volume, △V, for the 18 nitramines shows that its course is not unequivocal. For a part of the studied compounds this sensitivity has increased with increase of the AV values, but for fairly big number of nitramines the relationship works in the opposite direction, especially for data of 1,3,5-trinitro-1,3,5-triazinane, 1,3,5,7-tetranitro-1,3,5,7-tetrazocane. and β-and ε-polymorphs of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. Initiation reactivity of technical ε-polymorph of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane gives the impression by disorderliness in distribution of the actions of forces in its crystal lattice in comparison with its RS(reduced sensitivity) or chemically pure analogue. Limitations of partial shapes of the mentioned relationship by the molecular-structural similarity, and already published information about the decisive factors governing the crystal structure, signalizes a higher influence of the intermolecular interactions in a crystal lattice in comparison with influence of the crystal lattice free volume for initiation of the crystalline EMs.
基金financial support from the Students Grant Projects No. SGSFCHT_2016002 of the Faculty of Chemical Technology at the University of Pardubicefinancial support of the Chinese State Administration of Foreign Experts Affairs
文摘The relationship between friction sensitivity(FS) and the crystal lattice free space per molecule, △V. of thirteen nitramines is described by a linear equation, divided into a number of the partial relationships with strong limitations by their molecular structure characteristics. Increasing FS due to raising of the △V values is not clearly confirmed. The influence of the △V values on friction sensitivity of nitramines is similar to that of their aza atoms which influence the mutual orientations of nitro groups in neighboring molecules. The dipole-dipole interaction of the oxygen and nitrogen atoms of nitro groups in neighboring nitramine molecules has a major effect on their own FS. In accordance with this interaction, a directly proportional relationship was derived between FS and the intrinsic gas phase molecular volume, V_(int), of the nitramines mentioned, which is divided also into several straight lines according to relatively tight molecular structure similarity. The relationships found again confirm a level of disorder in the distribution of the forces in the crystal lattice of the "common" quality of ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, in comparison with its reduced sensitivity(RS) or chemically pure analogue.
基金supported by National Natural Science Foundation of China(Nos.20576117 and 20806067)China Postdoctoral Science Foundation(No.20070420230).
文摘Miniemulsion copolymerization of butyl mathacrylate (BMA) with fluoroacrylate (HFMA, TFMA) was carried out at 70 ℃ by employing potassium persulphate (KPS) as initiator. Copolymer compositions at low conversion levels were determined by ^1H NMR spectra techniques. The reactivity ratios were evaluated by employing Kellen-Tudos (K-T) methods, which yields the apparent reactivity ratios, rBMA = 0.74, rHFMA = 0.87 and rBMA = 0.73, rTFMA = 0.75, respectively, and Q- and e-values of HFMA and TFMA were calculated by the Alfrey-Price method. The results show that HFMA and TFMA are more active than BMA, and the cross-propagation rate constant is greater than the self-propagation one in these two copolymerizations.
基金supported by the National Natural Science Foundation of China (10972107)Open Fund of State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology (KFJJ12-4Y)Jiangsu Innovation Program for Graduate Education (CXLX11 0271)
文摘The interactions of a spherical flame with an incident shock wave and its reflected shock wave in a confined space were investigated using the three-dimensional reactive Navier-Stokes equations, with emphasis placed on the effect of chemical reactivity of mixture on the flame distortion and detonation initiation after the passage of the reflected shock wave. It is shown that the spatio-temporal characteristics of detonation initiation depend highly on the chemi- cal reactivity of the mixture. When the chemical reactivity enhances, the flame can be severely distorted to form a reactive shock bifurcation structure with detonations initiating at different three-dimensional spatial locations. Moreover, the detonation initiation would occur earlier in a mixture of more enhanced reactivity. The results reveal that the detona- tions arise from hot spots in the unburned region which are initiated by the shock-detonation-transition mechanism.