The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and...The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and homonuclear double-atom catalysts have been preliminarily explored,but the relationship between the inherent properties and catalytic activity of heteronuclear double-atom catalysts with better performance remains unclear.Therefore,it is very significant to explore the prediction expressions of catalytic activity of heteronuclear double-atom catalysts based on their inherent properties and find the rule for selecting catalytic centers.Herein,by summarizing the free energy for the key steps of NRR on 55 catalysts calculated through the first-principle,the expressions of predicting the free energy and the corresponding descriptors are deduced by the machine learning,and the strategy for selecting the appropriate catalytic center is proposed.The selection strategy for the central atom of heteronuclear double-atom catalysts is that the atomic number of central B atom should be between group VB and VIIIB,and the electron difference between central A atom and B atom should be large enough,and the selectivity of NRR or hydrogen evolution reaction(HER)could be calculated through the prediction formula.Moreover,five catalysts are screened to have low limiting potential and excellent selectivity,and are further analyzed by electron transfer.This work explores the relationship between the inherent properties of heteronuclear double-atom catalysts and the catalytic activity,and puts forward the rules for selecting the heteronuclear double-atom catalytic center,which has guiding significance for the experiment.展开更多
The minimax path location problem is to find a path P in a graph G such that the maximum distance d_(G)(v,P)from every vertex v∈V(G)to the path P is minimized.It is a well-known NP-hard problem in network optimizatio...The minimax path location problem is to find a path P in a graph G such that the maximum distance d_(G)(v,P)from every vertex v∈V(G)to the path P is minimized.It is a well-known NP-hard problem in network optimization.This paper studies the fixed-parameter solvability,that is,for a given graph G and an integer k,to decide whether there exists a path P in G such that max v∈V(G)d_(G)(v,P)≤k.If the answer is affirmative,then graph G is called k-path-eccentric.We show that this decision problem is NP-complete even for k=1.On the other hand,we characterize the family of 1-path-eccentric graphs,including the traceable,interval,split,permutation graphs and others.Furthermore,some polynomially solvable special graphs are discussed.展开更多
新能源并网比例的不断攀升降低了电力系统惯量,导致系统调频能力下降。为此,开展了储能参与调频的研究。储能参与调频受到单元数量、荷电状态(state of charge,SOC)、充放电策略等因素影响,提出一种考虑频率死区的储能单元协同控制策略...新能源并网比例的不断攀升降低了电力系统惯量,导致系统调频能力下降。为此,开展了储能参与调频的研究。储能参与调频受到单元数量、荷电状态(state of charge,SOC)、充放电策略等因素影响,提出一种考虑频率死区的储能单元协同控制策略,根据SOC一致性对储能单元进行分组,不同组别单独执行下垂控制或虚拟惯量控制,简化出力控制指令。依据系统频率偏差或频率变化率进行控制指令切换,并分别设置频率偏差和频率变化率死区,以减少小扰动干扰导致储能系统频率充放电。基于Matlab/Simulink进行仿真验证,结果表明:所提控制策略简单便于执行,能够快速响应调频需求,并且能保证储能电池使用寿命。展开更多
Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental...Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.展开更多
While prokaryotes play key roles in nutrient cycling and energy flow during Phaeocystis globosa blooms,the information on the spatial and diel temporal distribution of the prokaryotic community during Phaeocystis bloo...While prokaryotes play key roles in nutrient cycling and energy flow during Phaeocystis globosa blooms,the information on the spatial and diel temporal distribution of the prokaryotic community during Phaeocystis blooms remains scarce.In January 2019,we used high-throughput sequencing of the 16S rRNA gene to explore the spatial and diel variations of particle-attached(PA)and free-living(FL)prokaryotic communities during the blooming phase of P.globosa in Beibu Gulf,Guangxi,China.The results suggested a significant spatial variation pattern in the horizontal distribution of prokaryotic communities,while there was no significant difference in the vertical direction.Both spatial distance and environmental variables shaped the horizontal distribution of the prokaryotic community structure,while environmental variables,particularly the abundance of P.globosa colony and Chl a,showed more significant influence and were closely related to the structure and variation of the prokaryotic community.Strong vertical mixing of the water column disrupted the vertical structure heterogeneity of the prokaryotic community in winter.There were significant differences in the diel samples of PA prokaryotic communities,but not in the FL prokaryotic communities.Nitrate,ammonium and the abundance of P.globosa colony were the key environmental variables impacting the diel variations of prokaryotic communities over the sampling period.The present study provided valuable information to depict the spatial-temporal variations of the microbial community and its association with environmental parameters during P.globosa bloom in the tropical gulf.展开更多
Objective:To study the dynamic contrast-enhanced MRI (DCE-MRI) parameters of breast cancer tissue and their correlation with cancer cell proliferation and invasion.Methods: A total of 92 patients with breast mass who ...Objective:To study the dynamic contrast-enhanced MRI (DCE-MRI) parameters of breast cancer tissue and their correlation with cancer cell proliferation and invasion.Methods: A total of 92 patients with breast mass who underwent surgical treatment in our hospital between July 2012 and June 2016 were collected as research subjects. According to the results of pathological examination, the patients were divided into breast adenoma group (n=52) and breast cancer group (n=40). DCE-MRI parameter levels of breast mass were analyzed between two groups of patients, and the mRNA expression of proliferation and invasion genes in tumor samples were compared. Pearson test was used to further evaluate the relationship between the DCE-MRI parameter levels of breast cancer tissue and the malignant degree of tumor.Results:The DCE-MRI parameter TTP level in breast cancer group was lower than that in breast adenoma group while EER and SLOPE levels were higher than those in breast adenoma group. Proliferation genes C6orf106, HMGB2, ETS-1 and BRG1 mRNA expression in tumor tissue of breast cancer group were higher than those of breast adenoma group, and invasion genes ADAM9, Ezrin and Nanog mRNA expression were higher than those of breast adenoma group while CRM197 and EBP50 mRNA expression were lower than those of breast adenoma group. The Pearson test showed that the DCE-MRI parameter levels of breast cancer tissues were directly correlated with the mRNA expression of proliferation and invasion genes.Conclusion:DCE-MRI parameter levels are abnormal in breast cancer tissues, and the abnormal degree is directly correlated with the malignant biological behavior of tumor cells.展开更多
纳米多孔硅由于其海绵状的孔隙结构,氧化剂很难充分填充,导致多孔硅复合含能材料多为富燃料体系;同时其孔隙率难以调节,无法精确控制氧燃比。针对以上问题,以紧密排列的单层聚苯乙烯微球为模板,通过反应性离子刻蚀(Reaction Ion Etching...纳米多孔硅由于其海绵状的孔隙结构,氧化剂很难充分填充,导致多孔硅复合含能材料多为富燃料体系;同时其孔隙率难以调节,无法精确控制氧燃比。针对以上问题,以紧密排列的单层聚苯乙烯微球为模板,通过反应性离子刻蚀(Reaction Ion Etching,RIE)技术结合金属辅助化学刻蚀(Metal-Assisted Chemical Etching,MACE)制备得到了形貌结构可控的多孔硅纳米线,通过控制RIE时间能够精准调节多孔硅复合体系的氧燃比,同时二维线状结构非常有利于氧化剂的高效填充。结果表明,在RIE时间为80s,即硅纳米线直径为150nm左右时,复合含能体系达到最佳化学计量反应平衡,能量输出最佳。同时,选用不同电阻率的硅片制备得到不同结构形貌的硅纳米线,电阻率越低,纳米复合含能体系中的硅纳米线结构越疏松多孔,不仅能够有效缩短传质传热距离,降低反应活化能,有利于增强反应放热;而且能提升燃烧性能,有利于点火,为硅基含能材料的发展提供了新的思路。展开更多
Electrocatalytic nitrogen reduction reaction(NRR) is an efficient and green way to produce ammonia,which offers an alternative option to the conventional Haber-Bosch process.Unfortunately,the large-scale industrial ap...Electrocatalytic nitrogen reduction reaction(NRR) is an efficient and green way to produce ammonia,which offers an alternative option to the conventional Haber-Bosch process.Unfortunately,the large-scale industrial application of NRR processes is still hindered by poor Faraday efficiency and high overpotential,which need to be overcome urgently.Herein,combined with density functional theory and particle swarm optimization algorithm for the nitrogen carbide monolayer structural search(C_mN_(8-m),m=1-7),the surprising discovery is that single transition metal-atom-doped C_(4)N_(4) monolayers(TM@C_(4)N_(4)) could effectively accelerate nitrogen reduction reaction.TM@C_(4)N_(4)(TM=29 transition metals) as single-atom catalysts are evaluated via traditional multi-step screening method,and their structures,NRR activity,selectivity and solvation effect are investigated to evaluate their NRR performance,Through the screening steps,W@C_(4)N_(4) possesses the highest activity for NRR with a very low limiting potential of-0.29 V.Moreover,an intrinsic descriptor φ is proposed with machine learning,which shortens the screening process and provides a new idea for finding efficient SACs.This work not only offers promising catalysts W@C_(4)N_(4) for NRR process but also offers a new intrinsic and universal descriptor φ.展开更多
For a spanning tree T of graph G,the centroid of T is a vertex v for which the largest component of T-v has as few vertices as possible.The number of vertices of this component is called the centroid branch weight of ...For a spanning tree T of graph G,the centroid of T is a vertex v for which the largest component of T-v has as few vertices as possible.The number of vertices of this component is called the centroid branch weight of T.The minimum centroid branch spanning tree problem is to find a spanning tree T of G such that the centroid branch weight is minimized.In application to design of communication networks,the loads of all branches leading from the switch center should be as balanced as possible.In this paper,we prove that the problem is strongly NP-hard even for bipartite graphs.Moreover,the problem is shown to be polynomially solvable for split graphs,and exact formulae for special graph familis,say Kn_(1),n_(2),...,n_(k)and P_(m)×P_(n),are presented.展开更多
基金supports by the National Natural Science Foundation of China(NSFC,52271113)the Natural Science Foundation of Shaanxi Province,China(2020JM 218)+1 种基金the Fundamental Research Funds for the Central Universities(CHD300102311405)HPC platform,Xi’an Jiaotong University。
文摘The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and homonuclear double-atom catalysts have been preliminarily explored,but the relationship between the inherent properties and catalytic activity of heteronuclear double-atom catalysts with better performance remains unclear.Therefore,it is very significant to explore the prediction expressions of catalytic activity of heteronuclear double-atom catalysts based on their inherent properties and find the rule for selecting catalytic centers.Herein,by summarizing the free energy for the key steps of NRR on 55 catalysts calculated through the first-principle,the expressions of predicting the free energy and the corresponding descriptors are deduced by the machine learning,and the strategy for selecting the appropriate catalytic center is proposed.The selection strategy for the central atom of heteronuclear double-atom catalysts is that the atomic number of central B atom should be between group VB and VIIIB,and the electron difference between central A atom and B atom should be large enough,and the selectivity of NRR or hydrogen evolution reaction(HER)could be calculated through the prediction formula.Moreover,five catalysts are screened to have low limiting potential and excellent selectivity,and are further analyzed by electron transfer.This work explores the relationship between the inherent properties of heteronuclear double-atom catalysts and the catalytic activity,and puts forward the rules for selecting the heteronuclear double-atom catalytic center,which has guiding significance for the experiment.
文摘The minimax path location problem is to find a path P in a graph G such that the maximum distance d_(G)(v,P)from every vertex v∈V(G)to the path P is minimized.It is a well-known NP-hard problem in network optimization.This paper studies the fixed-parameter solvability,that is,for a given graph G and an integer k,to decide whether there exists a path P in G such that max v∈V(G)d_(G)(v,P)≤k.If the answer is affirmative,then graph G is called k-path-eccentric.We show that this decision problem is NP-complete even for k=1.On the other hand,we characterize the family of 1-path-eccentric graphs,including the traceable,interval,split,permutation graphs and others.Furthermore,some polynomially solvable special graphs are discussed.
文摘新能源并网比例的不断攀升降低了电力系统惯量,导致系统调频能力下降。为此,开展了储能参与调频的研究。储能参与调频受到单元数量、荷电状态(state of charge,SOC)、充放电策略等因素影响,提出一种考虑频率死区的储能单元协同控制策略,根据SOC一致性对储能单元进行分组,不同组别单独执行下垂控制或虚拟惯量控制,简化出力控制指令。依据系统频率偏差或频率变化率进行控制指令切换,并分别设置频率偏差和频率变化率死区,以减少小扰动干扰导致储能系统频率充放电。基于Matlab/Simulink进行仿真验证,结果表明:所提控制策略简单便于执行,能够快速响应调频需求,并且能保证储能电池使用寿命。
基金supports by the National Natural Science Foundation of China(52271113)the Natural Science Foundation of Shaanxi Province,China(2020JM 218)+1 种基金the Fundamental Research Funds for the Central Universities(CHD300102311405)HPC platform,Xi’an Jiaotong University.
文摘Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.
基金We thank Drs Chenbing Guan and Kui Cui (Institute of Neuroscience, Shanghai Institute for Biological Science, China) for technical support in setting up the single-cell migration assay, and Dr Qian Hu (Institute of Neuroscience, Shanghai Institute for Biological Science, China) for microscopic imaging. This study was supported by the National Key Basic Research Program (2006CB500702), Ministry of Science and Technology of China (2007CB947100), National Natural Science Foundation of China (30530240 and 30770657), Program for Changdiang Scholars and Innovative Research Teams in Universities (IRT0528), and Shanghai Metropolitan Fund for Research and Development (07DJ14005).
基金The National Key Research and Development Program of the Ministry of Science and Technology,China,under contract No.2017YFC1404300the Scientific and Technological Innovation Project of the Pilot National Laboratory for Marine Science and Technology(Qingdao)under contract No.2016ASKJ02the Aoshan Talents Program of the Pilot National Laboratory for Marine Science and Technology(Qingdao)under contract No.2015ASTP.
文摘While prokaryotes play key roles in nutrient cycling and energy flow during Phaeocystis globosa blooms,the information on the spatial and diel temporal distribution of the prokaryotic community during Phaeocystis blooms remains scarce.In January 2019,we used high-throughput sequencing of the 16S rRNA gene to explore the spatial and diel variations of particle-attached(PA)and free-living(FL)prokaryotic communities during the blooming phase of P.globosa in Beibu Gulf,Guangxi,China.The results suggested a significant spatial variation pattern in the horizontal distribution of prokaryotic communities,while there was no significant difference in the vertical direction.Both spatial distance and environmental variables shaped the horizontal distribution of the prokaryotic community structure,while environmental variables,particularly the abundance of P.globosa colony and Chl a,showed more significant influence and were closely related to the structure and variation of the prokaryotic community.Strong vertical mixing of the water column disrupted the vertical structure heterogeneity of the prokaryotic community in winter.There were significant differences in the diel samples of PA prokaryotic communities,but not in the FL prokaryotic communities.Nitrate,ammonium and the abundance of P.globosa colony were the key environmental variables impacting the diel variations of prokaryotic communities over the sampling period.The present study provided valuable information to depict the spatial-temporal variations of the microbial community and its association with environmental parameters during P.globosa bloom in the tropical gulf.
文摘Objective:To study the dynamic contrast-enhanced MRI (DCE-MRI) parameters of breast cancer tissue and their correlation with cancer cell proliferation and invasion.Methods: A total of 92 patients with breast mass who underwent surgical treatment in our hospital between July 2012 and June 2016 were collected as research subjects. According to the results of pathological examination, the patients were divided into breast adenoma group (n=52) and breast cancer group (n=40). DCE-MRI parameter levels of breast mass were analyzed between two groups of patients, and the mRNA expression of proliferation and invasion genes in tumor samples were compared. Pearson test was used to further evaluate the relationship between the DCE-MRI parameter levels of breast cancer tissue and the malignant degree of tumor.Results:The DCE-MRI parameter TTP level in breast cancer group was lower than that in breast adenoma group while EER and SLOPE levels were higher than those in breast adenoma group. Proliferation genes C6orf106, HMGB2, ETS-1 and BRG1 mRNA expression in tumor tissue of breast cancer group were higher than those of breast adenoma group, and invasion genes ADAM9, Ezrin and Nanog mRNA expression were higher than those of breast adenoma group while CRM197 and EBP50 mRNA expression were lower than those of breast adenoma group. The Pearson test showed that the DCE-MRI parameter levels of breast cancer tissues were directly correlated with the mRNA expression of proliferation and invasion genes.Conclusion:DCE-MRI parameter levels are abnormal in breast cancer tissues, and the abnormal degree is directly correlated with the malignant biological behavior of tumor cells.
文摘纳米多孔硅由于其海绵状的孔隙结构,氧化剂很难充分填充,导致多孔硅复合含能材料多为富燃料体系;同时其孔隙率难以调节,无法精确控制氧燃比。针对以上问题,以紧密排列的单层聚苯乙烯微球为模板,通过反应性离子刻蚀(Reaction Ion Etching,RIE)技术结合金属辅助化学刻蚀(Metal-Assisted Chemical Etching,MACE)制备得到了形貌结构可控的多孔硅纳米线,通过控制RIE时间能够精准调节多孔硅复合体系的氧燃比,同时二维线状结构非常有利于氧化剂的高效填充。结果表明,在RIE时间为80s,即硅纳米线直径为150nm左右时,复合含能体系达到最佳化学计量反应平衡,能量输出最佳。同时,选用不同电阻率的硅片制备得到不同结构形貌的硅纳米线,电阻率越低,纳米复合含能体系中的硅纳米线结构越疏松多孔,不仅能够有效缩短传质传热距离,降低反应活化能,有利于增强反应放热;而且能提升燃烧性能,有利于点火,为硅基含能材料的发展提供了新的思路。
基金supports by the National Natural Science Foundation of China (NSFC, Grant No. 52271113)the Natural Science Foundation of Shaanxi Province, China (2020JM-218)+1 种基金the Fundamental Research Funds for the Central Universities (CHD300102311405)HPC platform, Xi’an Jiaotong University。
文摘Electrocatalytic nitrogen reduction reaction(NRR) is an efficient and green way to produce ammonia,which offers an alternative option to the conventional Haber-Bosch process.Unfortunately,the large-scale industrial application of NRR processes is still hindered by poor Faraday efficiency and high overpotential,which need to be overcome urgently.Herein,combined with density functional theory and particle swarm optimization algorithm for the nitrogen carbide monolayer structural search(C_mN_(8-m),m=1-7),the surprising discovery is that single transition metal-atom-doped C_(4)N_(4) monolayers(TM@C_(4)N_(4)) could effectively accelerate nitrogen reduction reaction.TM@C_(4)N_(4)(TM=29 transition metals) as single-atom catalysts are evaluated via traditional multi-step screening method,and their structures,NRR activity,selectivity and solvation effect are investigated to evaluate their NRR performance,Through the screening steps,W@C_(4)N_(4) possesses the highest activity for NRR with a very low limiting potential of-0.29 V.Moreover,an intrinsic descriptor φ is proposed with machine learning,which shortens the screening process and provides a new idea for finding efficient SACs.This work not only offers promising catalysts W@C_(4)N_(4) for NRR process but also offers a new intrinsic and universal descriptor φ.
基金Key Research Project of Henan Higher Education Institutions(No.20A110003).
文摘For a spanning tree T of graph G,the centroid of T is a vertex v for which the largest component of T-v has as few vertices as possible.The number of vertices of this component is called the centroid branch weight of T.The minimum centroid branch spanning tree problem is to find a spanning tree T of G such that the centroid branch weight is minimized.In application to design of communication networks,the loads of all branches leading from the switch center should be as balanced as possible.In this paper,we prove that the problem is strongly NP-hard even for bipartite graphs.Moreover,the problem is shown to be polynomially solvable for split graphs,and exact formulae for special graph familis,say Kn_(1),n_(2),...,n_(k)and P_(m)×P_(n),are presented.