Danhong injection （DHI）, a Chinese Materia Medica standardized product extracted from Radix Salviae miltiorrhizae and Flos Carthami tinctorii, is widely used in China for treating acute isch-emic stroke. In the pres...Danhong injection （DHI）, a Chinese Materia Medica standardized product extracted from Radix Salviae miltiorrhizae and Flos Carthami tinctorii, is widely used in China for treating acute isch-emic stroke. In the present study, we explored the neuroprotective efficacy of DHI in a rat model of temporary middle cerebral artery ocdusion, and evaluated the potential mechanisms under-lying its effects. Pretreatment with DHI （0.9 and 1.8 mL/kg） resulted in a significantly smaller infarct volume and better neurological scores than pretreatment with saline. Furthermore, DHI significantly reduced the permeability of the blood-brain barrier, increased occludin protein expression and decreased neutrophil infiltration, as well as profoundly suppressing the upreg-ulation of matrix metallopeptidase-9 expression seen in rats that had received vehicle. Matrix metallopeptidase-2 expression was not affected by ischemia or DHI. Moreover, DHI （1.8 mL/kg） administered 3 hours after the onset of ischemia also improved neurological scores and reduced infarct size. Our results indicate that the neuroprotective efficacy of DHI in a rat model of cerebral ischemia-reperfusion injury is mediated by a protective effect on the blood-brain barrier and the reversal of neutrophil infiltration.展开更多
Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-...Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.展开更多
Extreme-mass-ratio inspiral(EMRI)signals pose significant challenges to gravitational wave(GW)data analysis,mainly owing to their highly complex waveforms and high-dimensional parameter space.Given their extended time...Extreme-mass-ratio inspiral(EMRI)signals pose significant challenges to gravitational wave(GW)data analysis,mainly owing to their highly complex waveforms and high-dimensional parameter space.Given their extended timescales of months to years and low signal-to-noise ratios,detecting and analyzing EMRIs with confidence generally relies on long-term observations.Besides the length of data,parameter estimation is particularly challenging due to non-local parameter degeneracies,arising from multiple local maxima,as well as flat regions and ridges inherent in the likelihood function.These factors lead to exceptionally high time complexity for parameter analysis based on traditional matched filtering and random sampling methods.To address these challenges,the present study explores a machine learning approach to Bayesian posterior estimation of EMRI signals,leveraging the recently developed flow matching technique based on ordinary differential equation neural networks.To our knowledge,this is also the first instance of applying continuous normalizing flows to EMRI analysis.Our approach demonstrates an increase in computational efficiency by several orders of magnitude compared to the traditional Markov chain Monte Carlo(MCMC)methods,while preserving the unbiasedness of results.However,we note that the posterior distributions generated by FMPE may exhibit broader uncertainty ranges than those obtained through full Bayesian sampling,requiring subsequent refinement via methods such as MCMC.Notably,when searching from large priors,our model rapidly approaches the true values while MCMC struggles to converge to the global maximum.Our findings highlight that machine learning has the potential to efficiently handle the vast EMRI parameter space of up to seventeen dimensions,offering new perspectives for advancing space-based GW detection and GW astronomy.展开更多
Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change ma...Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change materials.Here,we report a tiramisu-like composite(GMP),where the typical“crust-and-cheese”hierarchical structure is replicated by an innovative two-step bidirectional freezing assembly(BFA)and compressive densification.Hierarchical-aligned graphene array(G-GA)with ultralow thermal resistance is fabricated through 1st BFA and graphitization.During the 2nd BFA,the MXene-CNF crosslinking network with hydrogen-bond actions is used for encapsulating polyethylene glycol(PEG)onto the microlayers of the G-GA skeleton.Remarkably,the microlaminated GMP4 achieves a recorded TC of 34.05 W m^(-1) K^(-1),unprecedented EMI SE of 87.4 dB,and preferable enthalpy density of 179.4 J cm^(-3),along with leakage-free function,and eminent thermal durability.Furthermore,the GMP-loaded equipment is demonstrated for efficient microelectronics cooling and sustainable solar energy utilization.This work opens new avenues for multiscale designing multifunctional macro-composites,broadening the application prospects in advanced electronics and solar energy utilization systems.展开更多
Atomic hydrogen(H I)gas,mostly residing in dark matter halos after cosmic reionization,is the fuel for star formation.Its relation to the properties of the host halo is the key to understand the cosmic H I distributio...Atomic hydrogen(H I)gas,mostly residing in dark matter halos after cosmic reionization,is the fuel for star formation.Its relation to the properties of the host halo is the key to understand the cosmic H I distribution and to mock H I large scale structure accurately and conveniently for the large area H I intensity mapping surveys in the future.In this work,we propose a flexible empirical model of H I±halo relation.In this model,while the H I mass depends primarily on the mass of host halo,there is also secondary dependence on other halo properties.We apply our model to the observation data of the Arecibo Fast Legacy ALFA(ALFALFA)survey,and find it can successfully fit the cosmic H I abundance(Ω_(H I)),average H I±halo mass relation<M_(H I)M_(h)>,and the H I clustering.The best fit of the ALFALFA data rejects the model with no secondary halo dependence of H I and the model with secondary dependence on the halo spin parameter(λ),and shows a strong dependence on halo formation time(a_(1/2))and halo concentration(c_(vir)).In an attempt to explain these findings from the perspective of hydrodynamical simulations,the IllustrisTNG simulation confirms the dependence of H I mass on secondary halo parameters.However,the IllustrisTNG results show a strong dependence onλand a weak dependence on cvirand a1/2,and also predict a much larger value of H I clustering on large scales than observations.This interesting difference between simulation and observation calls for improvements in understanding the H I±halo relation from both theoretical and observational sides.展开更多
The Interpretation of Nursing Guidelines for Intravenous Thrombolysis in Acute Ischemic Stroke offers comprehensive recommendations across five key domains:hospital organizational management,patient condition monitori...The Interpretation of Nursing Guidelines for Intravenous Thrombolysis in Acute Ischemic Stroke offers comprehensive recommendations across five key domains:hospital organizational management,patient condition monitoring,complication observation and management,positioning and mobility away from the bed,and quality assurance.These Guidelines encompass all the phases of intravenous thrombolysis care for patients experiencing acute ischemic stroke.This article aims to elucidate the Guidelines by discussing their developmental background,the designation process,usage recommendations,and the interpretation of evolving perspectives,thereby providing valuable insights for clinical practice.展开更多
Objective:The objective of this study is to explore the current situation of nurses’participant activation for self-management of low back pain,analyze its influencing factors,and provide a reference for improving th...Objective:The objective of this study is to explore the current situation of nurses’participant activation for self-management of low back pain,analyze its influencing factors,and provide a reference for improving the participant activation for self-management of low back pain.Materials and Methods:A cross-sectional study was conducted with 5,120 nurses recruited through convenience sampling from hospitals across 25 provinces and municipalities in China.Participants completed two standardized instruments:General Information Questionnaire which collected demographic characteristics and work-related factors,and the Participant Activation for Self-Management of Back Pain Questionnaire which measured activation levels across three dimensions(including self-management beliefs,self-management awareness,and knowledge related to low back pain).Results:The score of nurses’participant activation for low back pain self-management was 38.00(33.00,44.00).The results of multiple linear regression showed that nurses of different gender,age,and professional titles,whether they had administrative positions,and whether they had back pain in the past year were influencing factors of nurses’participant activation for low back pain management.Conclusion:The overall participant activation for self-management of low back pain is at a medium level.Their self-management awareness is strong,but their beliefs about management of low back pain are insufficient.Targeted intervention measures can be taken to improve their activation for management of back pain and reduce the incidence of occupational low back pain.展开更多
Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that n...Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.展开更多
Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal...Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal centers and coordinated atoms remains under explored.Herein,nickel phthalocyanine is anchored to the metalexposed crystal face of TiO_(2),forming Ti-Ni-N_(4)coordination.This configuration reveals that the axially coordinated Ti atoms serve as a novel electron channel with electron-donating ability,transferring electrons to the Ni center through d-d coupling.It is found that the dynamic adjustment of bond lengths and d-band centers in Ti-Ni bonding during CO_(2)photoreduction process can effectively modulate the adsorption strengths of the Ni center for different intermediates.This leads to a significant enhancement in the photocatalytic performance for CO_(2)reduction to CO without a sacrificial reagent,achieving an exceptional CO evolution rate of 378.5μmol g^(-1).Furthermore,the d-d coupling mediated by Ti-Ni-N_(4)coordination increases the vacancy formation energy of active sites,preventing the leaching of Ni active centers.This study provides a strategy for the precise design of d-d orbital regulation and resistance to demetallization in photocatalysts for efficient CO_(2)conversion.展开更多
目的:探索分化抑制因子(inhibitor of differentiation,ID)家族在慢性髓系白血病(chronic myeloid leukemia,CML)中的表达和启动子甲基化水平,并分析其临床意义。方法:应用定量PCR及定量甲基化特异性PCR的方法检测2010年1月至2017年12...目的:探索分化抑制因子(inhibitor of differentiation,ID)家族在慢性髓系白血病(chronic myeloid leukemia,CML)中的表达和启动子甲基化水平,并分析其临床意义。方法:应用定量PCR及定量甲基化特异性PCR的方法检测2010年1月至2017年12月期间江苏大学附属人民医院就诊的非恶性血液病患者(对照组)和CML患者骨髓单个核细胞中ID2/ID3/ID4表达及ID4启动子甲基化水平,通过分组分析ID家族异常的临床意义。结果:ID2及ID3表达在CML患者中均呈现显著上调(P<0.001,P<0.05),而ID4表达在CML患者中呈现显著下调(P<0.01)。其中,接受者操作特征曲线分析揭示ID2表达可作为CML鉴别的潜在分子标志物(AUC=0.895,P<0.001)。CML患者中ID4启动子高甲基化概率显著高于对照组患者(P=0.001),且ID4启动子甲基化与ID4表达呈现负相关(r=-0.424,P=0.002)。通过分组分析发现ID2高表达较易发生于男性患者中(P=0.040);ID4低表达/高甲基化较易发生于加速/急变期患者(P=0.003,P<0.001)。此外,CML加速/急变期患者ID4表达水平低于慢性期患者(P<0.001),而ID4甲基化水平高于慢性期患者(P<0.001)。通过单因素及多因素Logistic回归分析发现ID4高甲基化是CML患者疾病进展的独立危险因素(P=0.007)。结论:ID家族在CML患者中表达态势不同,其中ID2/ID3表达上调;而ID4表达下调,与ID4启动子高甲基化相关。ID4表达/甲基化与CML疾病进展相关,其中ID4甲基化可能是CML疾病进展的独立危险因素。展开更多
基金supported by the National Natural Science Foundation of China,No.81173592National Science and Technology Major Project of the Ministry of Science and Technology of China,No.2011ZX09201-201,2012ZX09101201-004,2012ZX09101202,NCET-130935,2013ZX09201020+1 种基金Tianjin Municipal Applied Basic Research and Cutting-Edge Technology Research Scheme of China,No.14JCYBJC28900Program for Innovation Team Training in Universities in Tianjin,No.TD12-5035
文摘Danhong injection （DHI）, a Chinese Materia Medica standardized product extracted from Radix Salviae miltiorrhizae and Flos Carthami tinctorii, is widely used in China for treating acute isch-emic stroke. In the present study, we explored the neuroprotective efficacy of DHI in a rat model of temporary middle cerebral artery ocdusion, and evaluated the potential mechanisms under-lying its effects. Pretreatment with DHI （0.9 and 1.8 mL/kg） resulted in a significantly smaller infarct volume and better neurological scores than pretreatment with saline. Furthermore, DHI significantly reduced the permeability of the blood-brain barrier, increased occludin protein expression and decreased neutrophil infiltration, as well as profoundly suppressing the upreg-ulation of matrix metallopeptidase-9 expression seen in rats that had received vehicle. Matrix metallopeptidase-2 expression was not affected by ischemia or DHI. Moreover, DHI （1.8 mL/kg） administered 3 hours after the onset of ischemia also improved neurological scores and reduced infarct size. Our results indicate that the neuroprotective efficacy of DHI in a rat model of cerebral ischemia-reperfusion injury is mediated by a protective effect on the blood-brain barrier and the reversal of neutrophil infiltration.
基金financial support provided by National Natural Science Foundation of China(52303283,52372232,52064049)the Major Science and Technology Projects of Yunnan Province(202302AB080019-3)+2 种基金National Natural Science Foundation of Yunnan Province(202301AS070040,202401AU070201)the Analysis and Measurements Center of Yunnan University for the sample testing servicethe Electron Microscope Center of Yunnan University for the support of this work.
文摘Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.
基金supported by the National Key Research and Development Program of China(Grant Nos.2021YFC2201901,2021YFC2203004,2020YFC2200100 and 2021YFC2201903)International Partnership Program of the Chinese Academy of Sciences(Grant No.025GJHZ2023106GC)+4 种基金the financial support from Brazilian agencies Funda??o de AmparoàPesquisa do Estado de S?o Paulo(FAPESP)Funda??o de Amparoà Pesquisa do Estado do Rio Grande do Sul(FAPERGS)Fundacao de Amparoà Pesquisa do Estado do Rio de Janeiro(FAPERJ)Conselho Nacional de Desenvolvimento Científico e Tecnológico(CNPq)Coordenacao de Aperfeicoamento de Pessoal de Nível Superior(CAPES)。
文摘Extreme-mass-ratio inspiral(EMRI)signals pose significant challenges to gravitational wave(GW)data analysis,mainly owing to their highly complex waveforms and high-dimensional parameter space.Given their extended timescales of months to years and low signal-to-noise ratios,detecting and analyzing EMRIs with confidence generally relies on long-term observations.Besides the length of data,parameter estimation is particularly challenging due to non-local parameter degeneracies,arising from multiple local maxima,as well as flat regions and ridges inherent in the likelihood function.These factors lead to exceptionally high time complexity for parameter analysis based on traditional matched filtering and random sampling methods.To address these challenges,the present study explores a machine learning approach to Bayesian posterior estimation of EMRI signals,leveraging the recently developed flow matching technique based on ordinary differential equation neural networks.To our knowledge,this is also the first instance of applying continuous normalizing flows to EMRI analysis.Our approach demonstrates an increase in computational efficiency by several orders of magnitude compared to the traditional Markov chain Monte Carlo(MCMC)methods,while preserving the unbiasedness of results.However,we note that the posterior distributions generated by FMPE may exhibit broader uncertainty ranges than those obtained through full Bayesian sampling,requiring subsequent refinement via methods such as MCMC.Notably,when searching from large priors,our model rapidly approaches the true values while MCMC struggles to converge to the global maximum.Our findings highlight that machine learning has the potential to efficiently handle the vast EMRI parameter space of up to seventeen dimensions,offering new perspectives for advancing space-based GW detection and GW astronomy.
基金support from the National Natural Science Foundation of China(No.21878218)the Tianjin Research Innovation Project for Postgraduate Students(No.2023KJ262)+2 种基金the State Grid Corporation of China’s Research Program(No.5419-202019385A)the Fundamental Research Funds for the Central Universities(No.92320006)the Tianjin Key Science and Technology Program(No.18ZXSZSF00030)。
文摘Exploiting advanced nanocomposites isochronally integrating outstanding thermal conductivity(TC)and electromagnetic interference shielding effectiveness(EMI SE)can boost the cutting-edge application of phase change materials.Here,we report a tiramisu-like composite(GMP),where the typical“crust-and-cheese”hierarchical structure is replicated by an innovative two-step bidirectional freezing assembly(BFA)and compressive densification.Hierarchical-aligned graphene array(G-GA)with ultralow thermal resistance is fabricated through 1st BFA and graphitization.During the 2nd BFA,the MXene-CNF crosslinking network with hydrogen-bond actions is used for encapsulating polyethylene glycol(PEG)onto the microlayers of the G-GA skeleton.Remarkably,the microlaminated GMP4 achieves a recorded TC of 34.05 W m^(-1) K^(-1),unprecedented EMI SE of 87.4 dB,and preferable enthalpy density of 179.4 J cm^(-3),along with leakage-free function,and eminent thermal durability.Furthermore,the GMP-loaded equipment is demonstrated for efficient microelectronics cooling and sustainable solar energy utilization.This work opens new avenues for multiscale designing multifunctional macro-composites,broadening the application prospects in advanced electronics and solar energy utilization systems.
基金supported by National SKA Program of China(grant Nos.2020SKA0110100,2020SKA0110401)National Key R&D Program of China(grant Nos.2018YFA0404502,2018YFA0404503)+1 种基金the National Natural Science Foundation of China(NSFC,grant Nos.11922305,11833005,11821303,and 12011530159)the science research grants from the China Manned Space Project with NO.CMS-CSST-2021-A02。
文摘Atomic hydrogen(H I)gas,mostly residing in dark matter halos after cosmic reionization,is the fuel for star formation.Its relation to the properties of the host halo is the key to understand the cosmic H I distribution and to mock H I large scale structure accurately and conveniently for the large area H I intensity mapping surveys in the future.In this work,we propose a flexible empirical model of H I±halo relation.In this model,while the H I mass depends primarily on the mass of host halo,there is also secondary dependence on other halo properties.We apply our model to the observation data of the Arecibo Fast Legacy ALFA(ALFALFA)survey,and find it can successfully fit the cosmic H I abundance(Ω_(H I)),average H I±halo mass relation<M_(H I)M_(h)>,and the H I clustering.The best fit of the ALFALFA data rejects the model with no secondary halo dependence of H I and the model with secondary dependence on the halo spin parameter(λ),and shows a strong dependence on halo formation time(a_(1/2))and halo concentration(c_(vir)).In an attempt to explain these findings from the perspective of hydrodynamical simulations,the IllustrisTNG simulation confirms the dependence of H I mass on secondary halo parameters.However,the IllustrisTNG results show a strong dependence onλand a weak dependence on cvirand a1/2,and also predict a much larger value of H I clustering on large scales than observations.This interesting difference between simulation and observation calls for improvements in understanding the H I±halo relation from both theoretical and observational sides.
文摘The Interpretation of Nursing Guidelines for Intravenous Thrombolysis in Acute Ischemic Stroke offers comprehensive recommendations across five key domains:hospital organizational management,patient condition monitoring,complication observation and management,positioning and mobility away from the bed,and quality assurance.These Guidelines encompass all the phases of intravenous thrombolysis care for patients experiencing acute ischemic stroke.This article aims to elucidate the Guidelines by discussing their developmental background,the designation process,usage recommendations,and the interpretation of evolving perspectives,thereby providing valuable insights for clinical practice.
文摘Objective:The objective of this study is to explore the current situation of nurses’participant activation for self-management of low back pain,analyze its influencing factors,and provide a reference for improving the participant activation for self-management of low back pain.Materials and Methods:A cross-sectional study was conducted with 5,120 nurses recruited through convenience sampling from hospitals across 25 provinces and municipalities in China.Participants completed two standardized instruments:General Information Questionnaire which collected demographic characteristics and work-related factors,and the Participant Activation for Self-Management of Back Pain Questionnaire which measured activation levels across three dimensions(including self-management beliefs,self-management awareness,and knowledge related to low back pain).Results:The score of nurses’participant activation for low back pain self-management was 38.00(33.00,44.00).The results of multiple linear regression showed that nurses of different gender,age,and professional titles,whether they had administrative positions,and whether they had back pain in the past year were influencing factors of nurses’participant activation for low back pain management.Conclusion:The overall participant activation for self-management of low back pain is at a medium level.Their self-management awareness is strong,but their beliefs about management of low back pain are insufficient.Targeted intervention measures can be taken to improve their activation for management of back pain and reduce the incidence of occupational low back pain.
基金financial support provided by the National Natural Science Foundation of Yunnan Province(202301AS070040)Major Science and Technology Projects of Yunnan Province(202302AB080019-3)。
文摘Covalent organic frameworks(COFs)play a crucial role in metal-free electrocatalysts for promoting oxygen reduction reaction(ORR)due to their adjustable skeleton structure and catalytic activity.While it is true that numerous studies have explored COFs for ORR,the critical gap by providing a systematic framework for ligand-driven electronic state manipulation is essential for designing highly active COF-based ORR catalysts.Herein,a series of COF-based metal-free materials have been conceived and synthesized by linkage-engineered strategy with dicarboxaldehyde(BPC),bipyridine-dicarbaldehyde(BPA)and benzodithiophene(BDA)as electronic linkages.Consequently,by incorporating different linkages into COFs,the surface area,electronic state,hydrophobic properties and affinities towards intermediates are optimized.Notably,the benzodithiophene-linked COF(denoted as BDA-COF)has greater catalytic ability with a half-wave potential of 0.74 V vs.RHE and an onset potential of 0.86 V vs.RHE than dicarboxaldehyde(denoted as BPC-COF)and dicarbaldehyde(denoted as BPA-COF).Relevant characterizations,in situ techniques and theoretical calculations confirm that thiophene-S-based COF promotes the electronic migration and enhances the interaction with the intermediate.The result provides insight into for illustration of a high-performance COF-based electrocatalyst via a linkage-engineered approach.
基金financially supported by the National Natural Science Foundation of China(No.22476042)the Natural Science Foundation of Hena.(No.242300421189)
文摘Photocatalytic CO_(2)reduction using atomically dispersed catalysts holds significant potential for addressing global energy and environmental challenges.However,the influence of d-d orbital interactions between metal centers and coordinated atoms remains under explored.Herein,nickel phthalocyanine is anchored to the metalexposed crystal face of TiO_(2),forming Ti-Ni-N_(4)coordination.This configuration reveals that the axially coordinated Ti atoms serve as a novel electron channel with electron-donating ability,transferring electrons to the Ni center through d-d coupling.It is found that the dynamic adjustment of bond lengths and d-band centers in Ti-Ni bonding during CO_(2)photoreduction process can effectively modulate the adsorption strengths of the Ni center for different intermediates.This leads to a significant enhancement in the photocatalytic performance for CO_(2)reduction to CO without a sacrificial reagent,achieving an exceptional CO evolution rate of 378.5μmol g^(-1).Furthermore,the d-d coupling mediated by Ti-Ni-N_(4)coordination increases the vacancy formation energy of active sites,preventing the leaching of Ni active centers.This study provides a strategy for the precise design of d-d orbital regulation and resistance to demetallization in photocatalysts for efficient CO_(2)conversion.
文摘目的:探索分化抑制因子(inhibitor of differentiation,ID)家族在慢性髓系白血病(chronic myeloid leukemia,CML)中的表达和启动子甲基化水平,并分析其临床意义。方法:应用定量PCR及定量甲基化特异性PCR的方法检测2010年1月至2017年12月期间江苏大学附属人民医院就诊的非恶性血液病患者(对照组)和CML患者骨髓单个核细胞中ID2/ID3/ID4表达及ID4启动子甲基化水平,通过分组分析ID家族异常的临床意义。结果:ID2及ID3表达在CML患者中均呈现显著上调(P<0.001,P<0.05),而ID4表达在CML患者中呈现显著下调(P<0.01)。其中,接受者操作特征曲线分析揭示ID2表达可作为CML鉴别的潜在分子标志物(AUC=0.895,P<0.001)。CML患者中ID4启动子高甲基化概率显著高于对照组患者(P=0.001),且ID4启动子甲基化与ID4表达呈现负相关(r=-0.424,P=0.002)。通过分组分析发现ID2高表达较易发生于男性患者中(P=0.040);ID4低表达/高甲基化较易发生于加速/急变期患者(P=0.003,P<0.001)。此外,CML加速/急变期患者ID4表达水平低于慢性期患者(P<0.001),而ID4甲基化水平高于慢性期患者(P<0.001)。通过单因素及多因素Logistic回归分析发现ID4高甲基化是CML患者疾病进展的独立危险因素(P=0.007)。结论:ID家族在CML患者中表达态势不同,其中ID2/ID3表达上调;而ID4表达下调,与ID4启动子高甲基化相关。ID4表达/甲基化与CML疾病进展相关,其中ID4甲基化可能是CML疾病进展的独立危险因素。
