This study aims to explore the impact of fatigue induced by different limb exercises on cerebral cortical oxygenation levels and functional connectivity strength using functional near-infrared spectroscopy(fNIRS).Fati...This study aims to explore the impact of fatigue induced by different limb exercises on cerebral cortical oxygenation levels and functional connectivity strength using functional near-infrared spectroscopy(fNIRS).Fatigue was induced using an upper limb ergometer or a lower limb ergometer,with the load increasing gradually each minute.fNIRS covering the prefrontal cortex and motor cortex were used to collect data during the resting state,both before and after fatigue induction.A two-way ANOVA was conducted to examine differences in oxyhemoglobin(HbO_(2))and functional connectivity before and after fatigue induction in both groups,with the significance level set at 0.05.Exercise-induced fatigue in both the upper and lower limbs leads to a significant decrease in cerebral cortical oxygenation levels.Upper limb fatigue leads to a significant reduction in functional connectivity,there were significant decreases in connectivity within the motor cortex,between the motor cortex and frontal regions,and between the right ventrolateral prefrontal cortex and other frontal regions.Conversely,no significant changes were observed before and after lower limb fatigue.Future studies should focus on examining the extent to which how changes in the cerebral cortex,induced by exercise fatigue,are linked to exercise-and/or performance-related outcomes.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
BACKGROUND:Preoperative liver function in children with congenital heart disease is often compromised to varying degrees because of the unique pathophysiology.We aimed to investigate the relationships between liver fu...BACKGROUND:Preoperative liver function in children with congenital heart disease is often compromised to varying degrees because of the unique pathophysiology.We aimed to investigate the relationships between liver function indicators at hospital admission and mortality in children receiving venoarterial extracorporeal membrane oxygenation(VA-ECMO)support following cardiac surgery.METHODS:We retrospectively analysed the clinical data of pediatric patients who received postcardiotomy VA-ECMO support at Fuwai Hospital between January 2010 and June 2020.Univariable and multivariable-adjusted Cox proportional hazard models were constructed to evaluate the risk factors associated with 30-day and 180-day mortality.The cut-off values for the liver function variables measured at hospital admission were categorized into high and low groups and then compared using Kaplan-Meier survival curves and log-rank tests.RESULTS:Our study included 96 pediatric patients who received VA-ECMO support after cardiotomy.Among the patients receiving VA-ECMO,the 30-day and 180-day mortality rates were 37.5% and 52.1%,respectively.The level of aspartate aminotransferase(AST)at admission was associated with 30-day mortality(hazard ratios[HRs]=1.852,95%CI 1.010-3.398,P=0.046).The AST and alkaline phosphatase(ALP)levels were predictors of 180-day mortality,with adjusted HRs of 1.799(95%CI 1.074-3.014;P=0.025)and 1.384(95%CI 1.050-1.825;P=0.021),respectively.The cut-off value for AST to predict mortality at 30 d was 77 U/L,and that for ALP to predict mortality at 180 d was 269 U/L.CONCLUSION:Liver function indicators,including AST and ALP,at hospital admission are associated with mortality risk in children with congenital heart disease receiving VA-ECMO after cardiac surgery.展开更多
Parkinson's disease is a neurodegenerative disorder caused by loss of dopamine neurons in the substantia nigra pars compacta. Tremor, rigidity, and bradykinesia are the major symptoms of the disease. These motor i...Parkinson's disease is a neurodegenerative disorder caused by loss of dopamine neurons in the substantia nigra pars compacta. Tremor, rigidity, and bradykinesia are the major symptoms of the disease. These motor impairments are often accompanied by affective and emotional dysfunctions which have been largely studied over the last decade. The aim of this study was to investigate emotional processing organization in the brain of patients with Parkinson's disease and to explore whether there are differences between recognition of different types of emotions in Parkinson's disease. We examined 18 patients with Parkinson's disease(8 men, 10 women) with no history of neurological or psychiatric comorbidities. All these patients underwent identical brain blood oxygenation level-dependent functional magnetic resonance imaging for emotion evaluation. Blood oxygenation level-dependent functional magnetic resonance imaging results revealed that the occipito-temporal cortices, insula, orbitofrontal cortex, basal ganglia, and parietal cortex which are involved in emotion processing, were activated during the functional control. Additionally, positive emotions activate larger volumes of the same anatomical entities than neutral and negative emotions. Results also revealed that Parkinson's disease associated with emotional disorders are increasingly recognized as disabling as classic motor symptoms. These findings help clinical physicians to recognize the emotional dysfunction of patients with Parkinson's disease.展开更多
Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron micro...Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron microscopy(SEM),Raman spectroscopy,and X-ray Photoelectron Spectroscopy(XPS).It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8% increase in specific capacitance compared to non-functionalized fibers.Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area.It was further established by Brunauer-Emmett-Teller(BET)measurements that the surface area of the CNT fibers was increased from 168.22 m^2/g to 208.01 m^2/g after plasma functionalization.The pore size distribution of the fibers was also altered by this processing.The improved electrochemical data was attributed to enhanced wettability,increased surface area,and the presence of oxygen functional groups,which promoted the capacitance of the fibers.Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems.The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles),flexibility,bendability,and good energy densities.At 0.5 m A/cm^2,the EMIMBF4 device revealed a specific capacitance,which is 27% and 65%greater than the specific capacitances of devices using EMIMTFSI and H2SO4 electrolytes,respectively.The practiced in this work plasma surface processing can be employed in other applications where fibers,yarns,ribbons,and sheets need to be chemically modified.展开更多
As the limiting factor for an energy storage technique from lab-scale to industrial-scale,cost means not only the price of raw materials but also the simplicity of processing technics.In this work,the oxygen functiona...As the limiting factor for an energy storage technique from lab-scale to industrial-scale,cost means not only the price of raw materials but also the simplicity of processing technics.In this work,the oxygen functionalized carbon materials were obtained from three representative different metamorphic-grade coals,that is,lignite,bitumite,anthracite.Oxygen functional groups like quinones,carboxylic anhydrides,and lactones are easier to form near defects according to the thermogravimetric-mass spectrometry measurements and density functional theory calculation.Considering the highest amount of defects and C=O contained functional groups,the low metamorphic-grade lignite derived carbon exhibits a reversible capacity of 259.7 mA h g^(-1)after 50 cycles at 0.03 A g^(-1),best among these micron sized coal-based carbons.The surface active sites contribute highly stable and majority of sodium storage capacity evidenced by in situ Raman spectra and cyclic voltammetry curves at different scan rates.The coal-based carbon materials in this work offer options for industrial applications of sodium-ion battery anode materials.展开更多
BACKGROUND： There is a growing research focus on the combination of blood oxygenation level dependent functional magnetic resonance imaging （BOLD-fMRI） and diffusion tensor imaging （DTI） to evaluate visual cortic...BACKGROUND： There is a growing research focus on the combination of blood oxygenation level dependent functional magnetic resonance imaging （BOLD-fMRI） and diffusion tensor imaging （DTI） to evaluate visual cortical function and structural changes in the cerebrum, as well as morphological changes to the white matter fiber tracks, after visual pathway lesions. However, the combined application of BOLD-fMRI and DTI in treating of visual pathway abnormalities still requires further studies. OBJECTIVE： To observe and evaluate the effects of hyperbaric oxygen on visual pathway abnormalities, and to evaluate the characteristics of cerebral function and anatomic structural changes by using BOLD-fMRI combined with DTI technique. DESIGN： Case contrast observation. SETTING： Fuzhou General Hospital of Nanjing Military Area Command of Chinese PLA. PARTICIPANTS： Sixteen patients （9 males and 7 females, 15-77 years old） with lateral or bilateral visual disorder induced by visual pathway lesions were selected from the Department of Neurology, Fuzhou General Hospital of Nanjing Military Area Command of Chinese PLA from January 2006 to May 2007. These patients comprised the lesion group. Measures of interventional therapy： hyperbaric oxygen of two normal atmospheres for three courses （10 d/course） and routine internal medicine treatment. In addition, 12 healthy subjects of similar sex and age to the lesion group were regarded as the control group. The control group underwent routine ophthalmological and ocular fundus examinations; diagnostic results were normal. The experiment received confirmed consent from the local ethic committee, and all patients provided informed consent. METHODS： BOLD-fMRI and DTI manifestations in the lesion group were observed before and after hyperbaric oxygen intervention, and the results were compared with the control group. The subjects were positioned on their back, and BOLD-fMRI images were collected with the following GRE EPI sequence： TR = 2 000 ms, TE = 40 ms, layer thickness = 5 mm, and 20-layer successive scanning to cover the whole brain. While, DTI images were collected with SE EPI sequence of single excitation： TR=10 000 ms, TE = 112 ms, layer thickness = 4 mm, layer spacing = 0.5 mm, and a 30-layer successive scanning, matrix = 128×128. A diffusion gradient was applied at 13 directions, and one layer without diffusion weighted imaging was collected at b =1 000 s/mm^2. Numbers of activated voxels in cortical-activated regions, and fractional anisotropy in bilateral cerebral optical radiation regions, were calculated. Displacement, continuity, and destruction of fibrous tracts were analyzed. MAIN OUTCOME MEASURES： Results of BOLD-fMRI and DTI examinations. RESULTS： All 16 patients and 12 controls were included in the final analysis. ① Numbers of activated voxels through the use of BOLD-fMRI： prior to hyperbaric oxygen therapy, the number of activated voxels in the bilateral cortex of occipital lobe were significantly less in the lesion group than in the control group （t =3.23, P 〈 0.01）. In addition, the number of activated voxels significantly increased after treatment compared to before treatment （t = 2.46, P 〈 0.05）. ② Fractional anisotropy in optical radiation regions of bilateral cerebrum： fractional anisotropy in the lesion group was significantly less than the control group （t =2.89, P 〈 0.05）. In addition, fractional anisotropy after treatment was significantly higher than before treatment （t = 2.48, P 〈 0.05）. Moreover, fractional anisotropy of optical neuropathy was significantly higher in 6 patients in the lesion group than the occipital lobe optical central lesion （t = 2.35, P 〈 0.05）. CONCLUSION： BOLD-fMRI combined with DTI can indicate the occurrence, development, and therapeutic course of action for optical pathway lesions. The results acquired from these methods can provide information for function and structure, which can provide reliable verification in the treatment of cerebral function.展开更多
Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structu...Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.展开更多
Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces pr...Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces problems such as precise doping for creating active sites and the destruction of graphdiyne skeleton calling for high temperature.Here,we achieved charge redistribution on graphdiyne surface through molecule functionalization.A p-type molecule–F4 TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodime thane)was introduced and the site-defined functionalization was accomplished.Theoretical calculations showed that the charge transfer ability is improved and graphdiyne becomes positively charged.The oxygen reduction electrocatalysis was conducted as a proof of principle,where the electronic states of sp hybridized C active site was tuned toward favorable reaction intermediates’adsorption.Such work from both theoretical prediction and experimental validation,found that molecule functionalization is effective to promote the electrocatalytic oxygen reduction,which creates new possibilities for graphdiyne’s applications in different electrochemical reactions.展开更多
Self-supporting electrocatalysts for the oxygen evolution reaction(OER)require a delicate balance of cost-effectiveness,high activity,substantial durability,and robust mechanical properties.Here,we leverage the chemic...Self-supporting electrocatalysts for the oxygen evolution reaction(OER)require a delicate balance of cost-effectiveness,high activity,substantial durability,and robust mechanical properties.Here,we leverage the chemical and structural complexity of Al_(16.7) Fe_(16.7) Co_(16.7) Ni_(16.7) Cr_(16.7) Mn_(16.7)(at.%)high-entropy alloy(HEA)to address these requirements.Utilizing spinodal decomposition,we achieve a nanoporous structure of Fe-Cr-rich phase(A2 phase),providing a large specific surface area and robust mechanical integrity for free-standing applications.During cyclic voltammetry(CV)activation,an amorphous Mn-Fe-based HEA oxide forms in-situ on the nanoporous A2 phase,serving as an efficient electrocatalyst for OER in alkaline conditions.This nanoporous HEA amorphous oxide catalyst exhibits a low overpotential of 238 mV at a current density of 10 mA cm^(-2) and a low Tafel slope of 46 mV dec^(-1),surpassing the state-of-the-art RuO_(2) catalyst.This study establishes a competitive,engineering-applicable OER electrocatalyst and underscores the high-entropy effect’s potential in tuning electronic structures for enhanced performance.展开更多
The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis.In this contribution,we have designed a FeN_(4)or CoN_(4)em...The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis.In this contribution,we have designed a FeN_(4)or CoN_(4)embedded graphene-based bilayer as active layer and TMC_(3)or TMN_(3)doped graphene as supporting layer,named as FeN_(4)/TMC_(3)or FeN_(4)/TMN_(3)and CoN_(4)/TMC_(3)or CoN_(4)/TMN_(3),wherein TM strands for transition metal.Based on density functional theory calculations,our results demonstrate that the interaction formed between dual metal atoms in the bilayer interspace leads to the coordination environment altered from flat four-coordination to spatial five-coordination,further stabilizing the bilayer structure and impairing its affinity toward the O-containing intermediates.According to thermodynamic analysis,the bilayers of CoN_(4)/CoN_(3),FeN_(4)/FeC_(3),FeN_(4)/CoC_(3),FeN_(4)/NiC_(3),FeN_(4)/ZnC_(3),FeN_(4)/FeN_(3),FeN_(4)/CrN_(3)and FeN_(4)/ZnN_(3)are attractively promising for bifunctional oxygen electrocatalysis due to the small overpotential differenceΔηbetween oxygen reduction and oxygen evolution that are less than 1 V.Density functional theory calculations combined with machine learning analysis directly identify the key role played by the interbinding formed between bilayers,that boosts catalytic activity,which establishes a predictable framework for a fast screen for graphene-based bilayer vertical heterojunction.This work opens up a new path for designing the efficient electrocatalysts via modification of coordination environment.展开更多
In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especia...In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.展开更多
Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations ...Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.展开更多
Global warming poses a severe threat to rice production and food security.We identified a heat-sensitive mutant hs1 through largescale screening of an established rice mutant library,and subsequently cloned the corres...Global warming poses a severe threat to rice production and food security.We identified a heat-sensitive mutant hs1 through largescale screening of an established rice mutant library,and subsequently cloned the corresponding gene HS1,which confers thermotolerance in rice.HS1 is localized to the chloroplast and functions by preserving chloroplast integrity under elevated temperatures through stabilizing the photosystem I subunit protein PsaC.Loss of HS1 function in the hs1 mutant leads to severe structural damage to the chloroplast under heat stress,accompanied by intracellular accumulation of reactive oxygen species(ROS),which in turn triggers DNA damage and leaf albinism,ultimately manifesting as a heat-sensitive phenotype.展开更多
Objectives To compare respiratory parameters of peripheral blood mononuclear cell mitochondria and iron metabolism indicators in patients with different NYHA functional classes of ischemic heart failure(HF).Methods Th...Objectives To compare respiratory parameters of peripheral blood mononuclear cell mitochondria and iron metabolism indicators in patients with different NYHA functional classes of ischemic heart failure(HF).Methods This single center, prospective, non-blinded study enrolled 20 patients with diagnosed chronic HF of ischemic genesis with reduced and mildly reduced left ventricle ejection fraction. The maximum oxygen consumption at the peak of the exercise test(VO2peak), iron metabolism parameters and respiratory activity of peripheral blood mononuclear cell mitochondria were assessed.Results Among the patients, a half of individuals were diagnosed with iron deficiency. Subgroups of patients with different HF severity did not significant differ in VO2peak(P=0.209), serum iron(P=0.468) and ferritin(P=0.235) levels. But there was a trend in increasing in these parameters with increasing NYHA HF functional class. Respiratory control coefficient(RC) in NADdependent and FAD-dependent mitochondrial oxidation were lower in patients with NYHA HF Ⅲ functional class compared to individuals with NYHA HF I functional class(P=0.028 and P=0.040, respectively). Serum iron(P=0.026), ferritin(P=0.045)levels, transferrin saturation(P=0.006) were negatively correlated with RC in NAD-dependent mitochondrial oxidation.Conclusions In aggravation of ischemic HF NYHA FC, there is a decrease in RC of PBMC mitochondria during the oxidation of NAD-dependent and FAD-dependent substrates. In the whole sample, patients with laboratory-confirmed iron deficiency accounted a half of the total number. Iron metabolism parameters had a paradoxical inverse relationship with the level of RC in PBMC mitochondria of patients with HF.展开更多
Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR cataly...Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR catalysts by density functional theory calculations,ranging from single-atom,nanocluster to bulk Pt catalysts.The results showed that the ORR overpotential of these Pt-based catalysts increased when its size enlarged to the nanoparticle scale or reduced to the single-atom scale,and the Pt_(38)cluster had the lowest ORR overpotential(0.46 V)compared with that of Pt_(111)(0.57 V)and single atom Pt(0.7 V).Moreover,we established a volcano curve relationship between the ORR overpotential and binding energy of O*(ΔE_(O*),confirming the intermediate species anchored on Pt38cluster with suitable binding energy located at top of volcano curve.The interaction between intermediate species and Pt-based catalysts were also investigated by the charge distribution and projected density of state and which further confirmed the results of volcano curve.展开更多
Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,...Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.展开更多
The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inha...The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inhared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS）, organic elemental anal- ysis （OEA） and Boehm titration. The results showed that the functionalization process occurred at defective sites （opened mouths, tube caps, debris, etc.） before opening caps and truncating walls, and finally the graphitic structure was deteriorated. The surface oxygen content first increased with the treatment time but kept at around 8.0 wt% after 5 h. The analysis of the distribution of oxygen-containing groups re- vealed that phenolic hydroxyl was gradually converted to carboxyl and lactone, The carboxyl was found to play a pivotal role to reduce the over-potentials when we used the functionalized MWCNTs as the cat- alyst for oxygen reduction reaction （ORR）.展开更多
Objective:To study the sedative effect of dexmedetomidine in elderly patients with prostate cancer undergoing three hole LRP,and its effect on nerve function and brain oxygen metabolism.Methods:From August 2016 to Dec...Objective:To study the sedative effect of dexmedetomidine in elderly patients with prostate cancer undergoing three hole LRP,and its effect on nerve function and brain oxygen metabolism.Methods:From August 2016 to December 2019,78 patients with LRP under general anesthesia in our hospital were randomly selected and divided into control group and observation group according to the random number table method,39 cases in each group.During the operation,the observation group was given dextromethoridine,while the control group was given the same amount of normal saline.The changes of cognitive function index(MoCA score,POCD incidence rate),neurological function index(TGF-β1,NSE,IGF-1),brain oxygen metabolism index(PaO2,map,PaCO2,rSO2)before and after operation were compared between the two groups.The visual analogue score(VAS),the amount of analgesic drugs and the times of pressing the analgesic pump were compared between the two groups.The incidence of adverse reactions was compared between the two groups.Results:Before operation,there was no significant difference in cognitive function index,neurological function index and brain oxygen metabolism index between the two groups(P>0.05).On the first and third days after operation,MOCA score of the two groups was significantly lower,MOCA score of the observation group was significantly higher than that of the control group,POCD incidence of the observation group was significantly lower than that of the control group;on the third day after operation,TGF-β1 and IGF-1 of the two groups were significantly lower,TGF-β1 and IGF-1 of the observation group were significantly lower-The NSE in the observation group was significantly lower than that in the control group(P<0.05).In this study,1 hour after the establishment of pneumoperitoneum,PaCO2 and rSO2 in the two groups were significantly increased,6 hours and 12 hours after the operation,the VAS score of the observation group was lower than that of the control group,and the dosage of analgesic pump and the number of times of compression of the analgesic pump were significantly lower than that of the control group(P<0.05).There was no difference in the incidence of adverse reactions between the two groups(P>0.05).Conclusion:DEX has a good sedative effect on the elderly prostate cancer patients undergoing LRP with three hole method.It has little effect on nerve function and brain oxygen metabolism,and has a good safety.展开更多
基金supported by National Natural Science Foundation of China[NO.11932013].
文摘This study aims to explore the impact of fatigue induced by different limb exercises on cerebral cortical oxygenation levels and functional connectivity strength using functional near-infrared spectroscopy(fNIRS).Fatigue was induced using an upper limb ergometer or a lower limb ergometer,with the load increasing gradually each minute.fNIRS covering the prefrontal cortex and motor cortex were used to collect data during the resting state,both before and after fatigue induction.A two-way ANOVA was conducted to examine differences in oxyhemoglobin(HbO_(2))and functional connectivity before and after fatigue induction in both groups,with the significance level set at 0.05.Exercise-induced fatigue in both the upper and lower limbs leads to a significant decrease in cerebral cortical oxygenation levels.Upper limb fatigue leads to a significant reduction in functional connectivity,there were significant decreases in connectivity within the motor cortex,between the motor cortex and frontal regions,and between the right ventrolateral prefrontal cortex and other frontal regions.Conversely,no significant changes were observed before and after lower limb fatigue.Future studies should focus on examining the extent to which how changes in the cerebral cortex,induced by exercise fatigue,are linked to exercise-and/or performance-related outcomes.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
基金supported by the CAMS Innovation Fund for Medical Sciences(2024-12M-C&T-B-045).
文摘BACKGROUND:Preoperative liver function in children with congenital heart disease is often compromised to varying degrees because of the unique pathophysiology.We aimed to investigate the relationships between liver function indicators at hospital admission and mortality in children receiving venoarterial extracorporeal membrane oxygenation(VA-ECMO)support following cardiac surgery.METHODS:We retrospectively analysed the clinical data of pediatric patients who received postcardiotomy VA-ECMO support at Fuwai Hospital between January 2010 and June 2020.Univariable and multivariable-adjusted Cox proportional hazard models were constructed to evaluate the risk factors associated with 30-day and 180-day mortality.The cut-off values for the liver function variables measured at hospital admission were categorized into high and low groups and then compared using Kaplan-Meier survival curves and log-rank tests.RESULTS:Our study included 96 pediatric patients who received VA-ECMO support after cardiotomy.Among the patients receiving VA-ECMO,the 30-day and 180-day mortality rates were 37.5% and 52.1%,respectively.The level of aspartate aminotransferase(AST)at admission was associated with 30-day mortality(hazard ratios[HRs]=1.852,95%CI 1.010-3.398,P=0.046).The AST and alkaline phosphatase(ALP)levels were predictors of 180-day mortality,with adjusted HRs of 1.799(95%CI 1.074-3.014;P=0.025)and 1.384(95%CI 1.050-1.825;P=0.021),respectively.The cut-off value for AST to predict mortality at 30 d was 77 U/L,and that for ALP to predict mortality at 180 d was 269 U/L.CONCLUSION:Liver function indicators,including AST and ALP,at hospital admission are associated with mortality risk in children with congenital heart disease receiving VA-ECMO after cardiac surgery.
文摘Parkinson's disease is a neurodegenerative disorder caused by loss of dopamine neurons in the substantia nigra pars compacta. Tremor, rigidity, and bradykinesia are the major symptoms of the disease. These motor impairments are often accompanied by affective and emotional dysfunctions which have been largely studied over the last decade. The aim of this study was to investigate emotional processing organization in the brain of patients with Parkinson's disease and to explore whether there are differences between recognition of different types of emotions in Parkinson's disease. We examined 18 patients with Parkinson's disease(8 men, 10 women) with no history of neurological or psychiatric comorbidities. All these patients underwent identical brain blood oxygenation level-dependent functional magnetic resonance imaging for emotion evaluation. Blood oxygenation level-dependent functional magnetic resonance imaging results revealed that the occipito-temporal cortices, insula, orbitofrontal cortex, basal ganglia, and parietal cortex which are involved in emotion processing, were activated during the functional control. Additionally, positive emotions activate larger volumes of the same anatomical entities than neutral and negative emotions. Results also revealed that Parkinson's disease associated with emotional disorders are increasingly recognized as disabling as classic motor symptoms. These findings help clinical physicians to recognize the emotional dysfunction of patients with Parkinson's disease.
基金funded by a NASA Grant NNX13AF46Apartly by the National Institute for Occupational Safety and Health through the UC Pilot Research Project Training Program ERC Grant #T42OH008432
文摘Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron microscopy(SEM),Raman spectroscopy,and X-ray Photoelectron Spectroscopy(XPS).It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8% increase in specific capacitance compared to non-functionalized fibers.Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area.It was further established by Brunauer-Emmett-Teller(BET)measurements that the surface area of the CNT fibers was increased from 168.22 m^2/g to 208.01 m^2/g after plasma functionalization.The pore size distribution of the fibers was also altered by this processing.The improved electrochemical data was attributed to enhanced wettability,increased surface area,and the presence of oxygen functional groups,which promoted the capacitance of the fibers.Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems.The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles),flexibility,bendability,and good energy densities.At 0.5 m A/cm^2,the EMIMBF4 device revealed a specific capacitance,which is 27% and 65%greater than the specific capacitances of devices using EMIMTFSI and H2SO4 electrolytes,respectively.The practiced in this work plasma surface processing can be employed in other applications where fibers,yarns,ribbons,and sheets need to be chemically modified.
基金financially supported the National Natural Science Foundation of China(No.21878207)Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province(2019)Key Research and Development Project(International Science and Technology Cooperation Program)(No.201803D421011)。
文摘As the limiting factor for an energy storage technique from lab-scale to industrial-scale,cost means not only the price of raw materials but also the simplicity of processing technics.In this work,the oxygen functionalized carbon materials were obtained from three representative different metamorphic-grade coals,that is,lignite,bitumite,anthracite.Oxygen functional groups like quinones,carboxylic anhydrides,and lactones are easier to form near defects according to the thermogravimetric-mass spectrometry measurements and density functional theory calculation.Considering the highest amount of defects and C=O contained functional groups,the low metamorphic-grade lignite derived carbon exhibits a reversible capacity of 259.7 mA h g^(-1)after 50 cycles at 0.03 A g^(-1),best among these micron sized coal-based carbons.The surface active sites contribute highly stable and majority of sodium storage capacity evidenced by in situ Raman spectra and cyclic voltammetry curves at different scan rates.The coal-based carbon materials in this work offer options for industrial applications of sodium-ion battery anode materials.
文摘BACKGROUND： There is a growing research focus on the combination of blood oxygenation level dependent functional magnetic resonance imaging （BOLD-fMRI） and diffusion tensor imaging （DTI） to evaluate visual cortical function and structural changes in the cerebrum, as well as morphological changes to the white matter fiber tracks, after visual pathway lesions. However, the combined application of BOLD-fMRI and DTI in treating of visual pathway abnormalities still requires further studies. OBJECTIVE： To observe and evaluate the effects of hyperbaric oxygen on visual pathway abnormalities, and to evaluate the characteristics of cerebral function and anatomic structural changes by using BOLD-fMRI combined with DTI technique. DESIGN： Case contrast observation. SETTING： Fuzhou General Hospital of Nanjing Military Area Command of Chinese PLA. PARTICIPANTS： Sixteen patients （9 males and 7 females, 15-77 years old） with lateral or bilateral visual disorder induced by visual pathway lesions were selected from the Department of Neurology, Fuzhou General Hospital of Nanjing Military Area Command of Chinese PLA from January 2006 to May 2007. These patients comprised the lesion group. Measures of interventional therapy： hyperbaric oxygen of two normal atmospheres for three courses （10 d/course） and routine internal medicine treatment. In addition, 12 healthy subjects of similar sex and age to the lesion group were regarded as the control group. The control group underwent routine ophthalmological and ocular fundus examinations; diagnostic results were normal. The experiment received confirmed consent from the local ethic committee, and all patients provided informed consent. METHODS： BOLD-fMRI and DTI manifestations in the lesion group were observed before and after hyperbaric oxygen intervention, and the results were compared with the control group. The subjects were positioned on their back, and BOLD-fMRI images were collected with the following GRE EPI sequence： TR = 2 000 ms, TE = 40 ms, layer thickness = 5 mm, and 20-layer successive scanning to cover the whole brain. While, DTI images were collected with SE EPI sequence of single excitation： TR=10 000 ms, TE = 112 ms, layer thickness = 4 mm, layer spacing = 0.5 mm, and a 30-layer successive scanning, matrix = 128×128. A diffusion gradient was applied at 13 directions, and one layer without diffusion weighted imaging was collected at b =1 000 s/mm^2. Numbers of activated voxels in cortical-activated regions, and fractional anisotropy in bilateral cerebral optical radiation regions, were calculated. Displacement, continuity, and destruction of fibrous tracts were analyzed. MAIN OUTCOME MEASURES： Results of BOLD-fMRI and DTI examinations. RESULTS： All 16 patients and 12 controls were included in the final analysis. ① Numbers of activated voxels through the use of BOLD-fMRI： prior to hyperbaric oxygen therapy, the number of activated voxels in the bilateral cortex of occipital lobe were significantly less in the lesion group than in the control group （t =3.23, P 〈 0.01）. In addition, the number of activated voxels significantly increased after treatment compared to before treatment （t = 2.46, P 〈 0.05）. ② Fractional anisotropy in optical radiation regions of bilateral cerebrum： fractional anisotropy in the lesion group was significantly less than the control group （t =2.89, P 〈 0.05）. In addition, fractional anisotropy after treatment was significantly higher than before treatment （t = 2.48, P 〈 0.05）. Moreover, fractional anisotropy of optical neuropathy was significantly higher in 6 patients in the lesion group than the occipital lobe optical central lesion （t = 2.35, P 〈 0.05）. CONCLUSION： BOLD-fMRI combined with DTI can indicate the occurrence, development, and therapeutic course of action for optical pathway lesions. The results acquired from these methods can provide information for function and structure, which can provide reliable verification in the treatment of cerebral function.
基金supported the Natural Science Foundation of Guangdong Province(Nos.2022A1515140085,2022A1515111022 and 2022A1515110275)the Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(No.2020ZDZX2067)+2 种基金the Natural Science Foundation of Huizhou University(No.HZU202004)the Professorial and Doctoral Scientific Research Foundation of Huizhou University(No.2020JB046)the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices,Huizhou University(No.EFMDN2021004M).
文摘Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.
基金supported by the National Natural Science Foundation of China(21773016,21971244,51932001)the National Key R&D Program of China(2018YFA0703504)。
文摘Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne.However,the current doping approach still faces problems such as precise doping for creating active sites and the destruction of graphdiyne skeleton calling for high temperature.Here,we achieved charge redistribution on graphdiyne surface through molecule functionalization.A p-type molecule–F4 TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodime thane)was introduced and the site-defined functionalization was accomplished.Theoretical calculations showed that the charge transfer ability is improved and graphdiyne becomes positively charged.The oxygen reduction electrocatalysis was conducted as a proof of principle,where the electronic states of sp hybridized C active site was tuned toward favorable reaction intermediates’adsorption.Such work from both theoretical prediction and experimental validation,found that molecule functionalization is effective to promote the electrocatalytic oxygen reduction,which creates new possibilities for graphdiyne’s applications in different electrochemical reactions.
基金financially supported by the National Natu-ral Science Foundation of China(Nos.52071024 and 52225103)the Project of International Cooperation and Exchanges NSFC(No.51961160729)+3 种基金the Funds for Creative Research Groups of China(No.51921001)the 111 Project(No.BP0719004)financial support from Projects of SKLAMM-USTB(No.2023-Z10)the Fundamental Research Fund for the Cen-tral Universities of China(No.FRF-TP-22-005C2).
文摘Self-supporting electrocatalysts for the oxygen evolution reaction(OER)require a delicate balance of cost-effectiveness,high activity,substantial durability,and robust mechanical properties.Here,we leverage the chemical and structural complexity of Al_(16.7) Fe_(16.7) Co_(16.7) Ni_(16.7) Cr_(16.7) Mn_(16.7)(at.%)high-entropy alloy(HEA)to address these requirements.Utilizing spinodal decomposition,we achieve a nanoporous structure of Fe-Cr-rich phase(A2 phase),providing a large specific surface area and robust mechanical integrity for free-standing applications.During cyclic voltammetry(CV)activation,an amorphous Mn-Fe-based HEA oxide forms in-situ on the nanoporous A2 phase,serving as an efficient electrocatalyst for OER in alkaline conditions.This nanoporous HEA amorphous oxide catalyst exhibits a low overpotential of 238 mV at a current density of 10 mA cm^(-2) and a low Tafel slope of 46 mV dec^(-1),surpassing the state-of-the-art RuO_(2) catalyst.This study establishes a competitive,engineering-applicable OER electrocatalyst and underscores the high-entropy effect’s potential in tuning electronic structures for enhanced performance.
基金financial support from the National Natural Science Foundation of China(Nos.21503097,52130101,51701152,21806023,and 51702345)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_3905)。
文摘The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis.In this contribution,we have designed a FeN_(4)or CoN_(4)embedded graphene-based bilayer as active layer and TMC_(3)or TMN_(3)doped graphene as supporting layer,named as FeN_(4)/TMC_(3)or FeN_(4)/TMN_(3)and CoN_(4)/TMC_(3)or CoN_(4)/TMN_(3),wherein TM strands for transition metal.Based on density functional theory calculations,our results demonstrate that the interaction formed between dual metal atoms in the bilayer interspace leads to the coordination environment altered from flat four-coordination to spatial five-coordination,further stabilizing the bilayer structure and impairing its affinity toward the O-containing intermediates.According to thermodynamic analysis,the bilayers of CoN_(4)/CoN_(3),FeN_(4)/FeC_(3),FeN_(4)/CoC_(3),FeN_(4)/NiC_(3),FeN_(4)/ZnC_(3),FeN_(4)/FeN_(3),FeN_(4)/CrN_(3)and FeN_(4)/ZnN_(3)are attractively promising for bifunctional oxygen electrocatalysis due to the small overpotential differenceΔηbetween oxygen reduction and oxygen evolution that are less than 1 V.Density functional theory calculations combined with machine learning analysis directly identify the key role played by the interbinding formed between bilayers,that boosts catalytic activity,which establishes a predictable framework for a fast screen for graphene-based bilayer vertical heterojunction.This work opens up a new path for designing the efficient electrocatalysts via modification of coordination environment.
文摘In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.
基金supported by the National Natural Science Foundation of China (Grant No.10974183)
文摘Oxygen vacancy formation and migration in La0.9Sr0.1Ga0.8Mg0.2O3-5 （LSGM） with various crystal symmetries （cubic, rhombohedral, orthorhombic, and monoclinic） are studied by employing first-principles calculations based on density functional theory （DFT）. It is shown that the cubic LSGM has the smallest band gap, oxygen vacancy formation energy, and migration barrier, while the other three structures give rise to much larger values for these quantities, implying the best oxygen ion conductivity of the cubic LSGM among the four crystal structures. In out calculations, one oxygen vacancy migration pathway is considered in the cubic and rhombohedral structures due to all the oxygen sites being equivalent in them, while two vacancy migration pathways with different migration barriers are found in the orthorhombic and monoclinic symmetries owing to the existence of nonequivalent O1 and 02 oxygen sites. The migration energies along the migration pathway linking the two 02 sites are obviously lower than those along the pathway linking the O1 and 02 sites. Considering the phase transitions at high temperatures, the results obtained in this paper can not only explain the experimentally observed different behaviours of the oxygen ionic conductivity of LSGM with different symmetries, but also predict the rational crystal structures of LSGM for solid oxide fuel cell applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.32372118 and 32188102)the Zhejiang Natural Science Foundation,China(Grant No.LZ25C130010)+1 种基金the Qian Qian Academician Workstation,and the specific research fund of the Innovation Platform for Academicians of Hainan Province,China(Grant No.YSPTZX202303)the Central Public-Interest Scientific Institution Basal Research Fund from Chinese Academy of Agricultural Sciences(Grant No.Y2025YC93)。
文摘Global warming poses a severe threat to rice production and food security.We identified a heat-sensitive mutant hs1 through largescale screening of an established rice mutant library,and subsequently cloned the corresponding gene HS1,which confers thermotolerance in rice.HS1 is localized to the chloroplast and functions by preserving chloroplast integrity under elevated temperatures through stabilizing the photosystem I subunit protein PsaC.Loss of HS1 function in the hs1 mutant leads to severe structural damage to the chloroplast under heat stress,accompanied by intracellular accumulation of reactive oxygen species(ROS),which in turn triggers DNA damage and leaf albinism,ultimately manifesting as a heat-sensitive phenotype.
基金supported by Russian Science Foundation,RSF 23-75-00009(part of the study corresponding to finding 1)Part of the study corresponding to finding 2 was carried out within the state assignment,FSR No.:122020300045-5(03.02.2022).
文摘Objectives To compare respiratory parameters of peripheral blood mononuclear cell mitochondria and iron metabolism indicators in patients with different NYHA functional classes of ischemic heart failure(HF).Methods This single center, prospective, non-blinded study enrolled 20 patients with diagnosed chronic HF of ischemic genesis with reduced and mildly reduced left ventricle ejection fraction. The maximum oxygen consumption at the peak of the exercise test(VO2peak), iron metabolism parameters and respiratory activity of peripheral blood mononuclear cell mitochondria were assessed.Results Among the patients, a half of individuals were diagnosed with iron deficiency. Subgroups of patients with different HF severity did not significant differ in VO2peak(P=0.209), serum iron(P=0.468) and ferritin(P=0.235) levels. But there was a trend in increasing in these parameters with increasing NYHA HF functional class. Respiratory control coefficient(RC) in NADdependent and FAD-dependent mitochondrial oxidation were lower in patients with NYHA HF Ⅲ functional class compared to individuals with NYHA HF I functional class(P=0.028 and P=0.040, respectively). Serum iron(P=0.026), ferritin(P=0.045)levels, transferrin saturation(P=0.006) were negatively correlated with RC in NAD-dependent mitochondrial oxidation.Conclusions In aggravation of ischemic HF NYHA FC, there is a decrease in RC of PBMC mitochondria during the oxidation of NAD-dependent and FAD-dependent substrates. In the whole sample, patients with laboratory-confirmed iron deficiency accounted a half of the total number. Iron metabolism parameters had a paradoxical inverse relationship with the level of RC in PBMC mitochondria of patients with HF.
基金supported by the National Natural Science Foundation of China(92061125,21978294)Beijing Natural Science Foundation(Z200012)+3 种基金Jiangxi Natural Science Foundation(20212ACB213009)DNL Cooperation Fund,CAS(DNL201921)Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055B003)Hebei Natural Science Foundation(B2020103043)。
文摘Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR catalysts by density functional theory calculations,ranging from single-atom,nanocluster to bulk Pt catalysts.The results showed that the ORR overpotential of these Pt-based catalysts increased when its size enlarged to the nanoparticle scale or reduced to the single-atom scale,and the Pt_(38)cluster had the lowest ORR overpotential(0.46 V)compared with that of Pt_(111)(0.57 V)and single atom Pt(0.7 V).Moreover,we established a volcano curve relationship between the ORR overpotential and binding energy of O*(ΔE_(O*),confirming the intermediate species anchored on Pt38cluster with suitable binding energy located at top of volcano curve.The interaction between intermediate species and Pt-based catalysts were also investigated by the charge distribution and projected density of state and which further confirmed the results of volcano curve.
文摘Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.21307142 and 21403261)Ningbo Science and Technology Bureau(No.2014D10004)
文摘The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inhared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS）, organic elemental anal- ysis （OEA） and Boehm titration. The results showed that the functionalization process occurred at defective sites （opened mouths, tube caps, debris, etc.） before opening caps and truncating walls, and finally the graphitic structure was deteriorated. The surface oxygen content first increased with the treatment time but kept at around 8.0 wt% after 5 h. The analysis of the distribution of oxygen-containing groups re- vealed that phenolic hydroxyl was gradually converted to carboxyl and lactone, The carboxyl was found to play a pivotal role to reduce the over-potentials when we used the functionalized MWCNTs as the cat- alyst for oxygen reduction reaction （ORR）.
基金Science and research projects of science and technology commission Shanghai municipality(No.19ZR1408000)
文摘Objective:To study the sedative effect of dexmedetomidine in elderly patients with prostate cancer undergoing three hole LRP,and its effect on nerve function and brain oxygen metabolism.Methods:From August 2016 to December 2019,78 patients with LRP under general anesthesia in our hospital were randomly selected and divided into control group and observation group according to the random number table method,39 cases in each group.During the operation,the observation group was given dextromethoridine,while the control group was given the same amount of normal saline.The changes of cognitive function index(MoCA score,POCD incidence rate),neurological function index(TGF-β1,NSE,IGF-1),brain oxygen metabolism index(PaO2,map,PaCO2,rSO2)before and after operation were compared between the two groups.The visual analogue score(VAS),the amount of analgesic drugs and the times of pressing the analgesic pump were compared between the two groups.The incidence of adverse reactions was compared between the two groups.Results:Before operation,there was no significant difference in cognitive function index,neurological function index and brain oxygen metabolism index between the two groups(P>0.05).On the first and third days after operation,MOCA score of the two groups was significantly lower,MOCA score of the observation group was significantly higher than that of the control group,POCD incidence of the observation group was significantly lower than that of the control group;on the third day after operation,TGF-β1 and IGF-1 of the two groups were significantly lower,TGF-β1 and IGF-1 of the observation group were significantly lower-The NSE in the observation group was significantly lower than that in the control group(P<0.05).In this study,1 hour after the establishment of pneumoperitoneum,PaCO2 and rSO2 in the two groups were significantly increased,6 hours and 12 hours after the operation,the VAS score of the observation group was lower than that of the control group,and the dosage of analgesic pump and the number of times of compression of the analgesic pump were significantly lower than that of the control group(P<0.05).There was no difference in the incidence of adverse reactions between the two groups(P>0.05).Conclusion:DEX has a good sedative effect on the elderly prostate cancer patients undergoing LRP with three hole method.It has little effect on nerve function and brain oxygen metabolism,and has a good safety.
