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Corrigendum to“Atomic-scale electromagnetic theory bridging optics in microscopic world and macroscopic world”
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作者 李志远 陈剑锋 《Chinese Physics B》 SCIE EI CAS CSCD 2024年第2期586-586,共1页
The signs of the electric field markers in Figs.2 and 4 of the paper[Chin.Phys.B 32104211(2023)]have been corrected.These modifications do not affect the results derived in the paper.
关键词 CORRIGENDUM atomic-scale electromagnetic theory two-dimensional materials transfer matrix method
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Optimal and robust control of population transfer in asymmetric quantum-dot molecules
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作者 郭裕 马松山 束传存 《Chinese Physics B》 SCIE EI CAS CSCD 2024年第2期353-359,共7页
We present an optimal and robust quantum control method for efficient population transfer in asymmetric double quantum-dot molecules.We derive a long-duration control scheme that allows for highly efficient population... We present an optimal and robust quantum control method for efficient population transfer in asymmetric double quantum-dot molecules.We derive a long-duration control scheme that allows for highly efficient population transfer by accurately controlling the amplitude of a narrow-bandwidth pulse.To overcome fluctuations in control field parameters,we employ a frequency-domain quantum optimal control theory method to optimize the spectral phase of a single pulse with broad bandwidth while preserving the spectral amplitude.It is shown that this spectral-phase-only optimization approach can successfully identify robust and optimal control fields,leading to efficient population transfer to the target state while concurrently suppressing population transfer to undesired states.The method demonstrates resilience to fluctuations in control field parameters,making it a promising approach for reliable and efficient population transfer in practical applications. 展开更多
关键词 population transfer quantum optimal control theory quantum-dot molecules
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Stability Analysis of Transfer Alignment Filter Based on theμTheory 被引量:1
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作者 Lihua Zhu Yu Wang +1 位作者 Lei Wang Zhiqiang Wu 《Computers, Materials & Continua》 SCIE EI 2019年第6期1015-1026,共12页
The performance of the transfer alignment has great impact on inertial navigation systems.As the transfer alignment is generally implemented using a filter to compensate the errors,its accuracy,rapidity and anti-distu... The performance of the transfer alignment has great impact on inertial navigation systems.As the transfer alignment is generally implemented using a filter to compensate the errors,its accuracy,rapidity and anti-disturbance capability are key properties to evaluate the filtering process.In terms of the superiority in dealing with the noise,H∞filtering has been used to improve the anti-disturbance capability of the transfer alignment.However,there is still a need to incorporate system uncertainty due to various dynamic conditions.Based on the structural value theory,a robustness stability analysis method has been proposed for the transfer alignment to evaluate the impact of uncertainty on the navigation system.The mathematical derivation has been elaborated in this paper,and the simulation has been carried out to verify the effectiveness of the algorithm. 展开更多
关键词 Robustness stability transfer alignment inertial navigation system μtheory
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Thermal Analysis of Organic Light Emitting Diodes Based on Basic Heat Transfer Theory 被引量:1
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作者 张稳稳 吴朝新 +3 位作者 刘迎文 董军 严学文 侯洵 《Chinese Physics Letters》 SCIE CAS CSCD 2015年第8期139-143,共5页
We investigate the thermal characteristics of standard organic light-emitting diodes (OLEDs) using a simple and clear 1D thermal model based on the basic heat transfer theory. The thermal model can accurately estima... We investigate the thermal characteristics of standard organic light-emitting diodes (OLEDs) using a simple and clear 1D thermal model based on the basic heat transfer theory. The thermal model can accurately estimate the device temperature, which is linearly with electrical input power. The simulation results show that there is almost no temperature gradient within the OLED device working under steady state conditions. Furthermore, thermal analysis simulation results show that the surface properties (convective heat transfer coetficient and surface emissivity) of the substrate or cathode can significantly affect the temperature distribution of the OLED. 展开更多
关键词 OLEDS Thermal Analysis of Organic Light Emitting Diodes Based on Basic Heat transfer theory EML
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The Implementation Strategy of Language Transfer under the Theory of Constructivism 被引量:2
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作者 Zhang Yuan 《学术界》 CSSCI 北大核心 2013年第6期269-274,共6页
In recent years,the theory of constructivism has attracted increasingly more attention from people.As for English language transfer of colleges and universities,the theory of constructivism is of extremely theoretical... In recent years,the theory of constructivism has attracted increasingly more attention from people.As for English language transfer of colleges and universities,the theory of constructivism is of extremely theoretical significance and practical significance.At present,there are many problems necessary to solve in the language transfer practice of colleges and universities.For this reason,the application of the constructivism theory to language transfer should be practically enhanced.In practice,the materials of language learning and training should be not only greatly enriched,and also the role of practical teaching in language transfer should be fully played.Meanwhile,all sorts of rich teaching resources should be actively used for the selection and design. 展开更多
关键词 建构主义理论 语言学习 迁移 教学语言 教学资源 高校 传递 分发
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Density Functional Theory Study on the Histidine-assisted Mechanism of Arylamine N-Acetyltransferase Acetylation
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作者 乔青安 高善民 +3 位作者 靳月庆 陈鑫 孙孝敏 杨传路 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2008年第9期1127-1133,共7页
Arylamine N-acetyltransferases (NATs, EC 2.3.1.5) catalyze the N-acetylation of primary arylamines, and play a key role in the biotransformation and metabolism of drugs, carcinogens, etc. In this paper, three possib... Arylamine N-acetyltransferases (NATs, EC 2.3.1.5) catalyze the N-acetylation of primary arylamines, and play a key role in the biotransformation and metabolism of drugs, carcinogens, etc. In this paper, three possible reaction mechanisms are investigated and the results indicate that if the acetyl group directly transfers from the donor to the acceptor, the high activation energies will make it hard to obtain the target products. When using histidine to mediate the acetylation process, these energies will drop in the 15-45 kJ/mol range. If the histidine residue is protonated, the corresponding energies will be decreased by about 35-87 kJ/mol. The calculations predict an enzymatic acetylation mechanism that undergoes a thiolate-imidazolium pair, which agrees with the experimental results very well. 展开更多
关键词 arylamine N-acetyltransferase density functional theory acetyl group transfer histidine-assisted mechanism
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OBLIVIOUS TRANSFER WITH ACCESS CONTROL AND IDENTITY-BASED ENCRYPTION WITH ANONYMOUS KEY ISSUING
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作者 Xu Lingling Zhang Fangguo Wen Yamin 《Journal of Electronics(China)》 2011年第4期571-579,共9页
In ACM'CCS 2009,Camenisch,et al.proposed the Oblivious Transfer with Access Control(AC-OT) in which each item is associated with an attribute set and can only be available,on request,to the users who have all the ... In ACM'CCS 2009,Camenisch,et al.proposed the Oblivious Transfer with Access Control(AC-OT) in which each item is associated with an attribute set and can only be available,on request,to the users who have all the attributes in the associated set.Namely,AC-OT achieves access control policy for conjunction of attributes.Essentially,the functionality of AC-OT is equivalent to the sim-plified version that we call AC-OT-SV:for each item,one attribute is associated with it,and it is requested that only the users who possess the associated attribute can obtain the item by queries.On one hand,AC-OT-SV is a special case of AC-OT when there is just one associated attribute with each item.On the other hand,any AC-OT can be realized by an AC-OT-SV.In this paper,we first present a concrete AC-OT-SV protocol which is proved to be secure in the model defined by Camenisch,et al..Then from the protocol,interestingly,a concrete Identity-Based Encryption(IBE) with Anonymous Key Issuing(AKI) is given which is just a direct application to AC-OT-SV.By comparison,we show that the AKI protocol we present is more efficient in communications than that proposed by Chow. 展开更多
关键词 Oblivious transfer(OT) access Control(AC) Identity-Based Encryption(IBE) Anonymous Key Issuing(AKI)
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Theoretical investigation on the excited state intramolecular proton transfer in Me_(2)N substituted flavonoid by the time-dependent density functional theory method
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作者 Hang Yin Ying Shi 《Chinese Physics B》 SCIE EI CAS CSCD 2018年第5期534-538,共5页
Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^... Time-dependent density functional theory(TDDFT)method is used to investigate the details of the excited state intramolecular proton transfer(ESIPT)process and the mechanism for temperature effect on the Enol^(*)/Keto^(*)emission ratio for the Me_(2)N-substited flavonoid(MNF)compound.The geometric structures of the S_(0) and S_(1) states are denoted as the Enol,Enol^(*),and Keto*.In addition,the absorption and fluorescence peaks are also calculated.It is noted that the calculated large Stokes shift is in good agreement with the experimental result.Furthermore,our results confirm that the ESIPT process happens upon photoexcitation,which is distinctly monitored by the formation and disappearance of the characteristic peaks of infrared(IR)spectra involved in the proton transfer and in the potential energy curves.Besides,the calculations of highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)reveal that the electronegativity change of proton acceptor due to the intramolecular charge redistribution in the S_(1) state induces the ESIPT.Moreover,the thermodynamic calculation for the MNF shows that the Enol^(*)/Keto^(*)emission ratio decreasing with temperature increasing arises from the barrier lowering of ESIPT. 展开更多
关键词 time-dependent density functional theory excited state intramolecular proton transfer intramolecular charge transfer transition state
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Nonequilibrium Solvent Free Energy Curve from Molecular Theory in Electron Transfer Reaction
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作者 Jian XIJ Zheng YM ZHOU(Department of Chendstry, Qufu Normal University, Qufu, 273165)Ke Zhong ZHANG(Linyi Anucahon College, Linyi, 276000) 《Chinese Chemical Letters》 SCIE CAS CSCD 1997年第5期439-442,共4页
The microscopic moleeular theory for electron transfer in a model solvent ishahr developed. The nonlinear response of the solvent molecules is be computedquanitatively in a new way. Adopting computer simulation daa an... The microscopic moleeular theory for electron transfer in a model solvent ishahr developed. The nonlinear response of the solvent molecules is be computedquanitatively in a new way. Adopting computer simulation daa and choosingappropriate reaction coordinae, a reasonable free energy dinram is constructed and thercorganhaion energy for the product state is calculated. 展开更多
关键词 Free Nonequilibrium Solvent Free Energy Curve from Molecular theory in Electron transfer Reaction CM
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Overview of Earth-Moon Transfer Trajectory Modeling and Design
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作者 Jiye Zhang Huichang Yu Honghua Dai 《Computer Modeling in Engineering & Sciences》 SCIE EI 2023年第4期5-43,共39页
TheMoon is the only celestial body that human beings have visited.The design of the Earth-Moon transfer orbits is a critical issue in lunar exploration missions.In the 21st century,new lunar missions including the con... TheMoon is the only celestial body that human beings have visited.The design of the Earth-Moon transfer orbits is a critical issue in lunar exploration missions.In the 21st century,new lunar missions including the construction of the lunar space station,the permanent lunar base,and the Earth-Moon transportation network have been proposed,requiring low-cost,expansive launch windows and a fixed arrival epoch for any launch date within the launch window.The low-energy and low-thrust transfers are promising strategies to satisfy the demands.This review provides a detailed landscape of Earth-Moon transfer trajectory design processes,from the traditional patched conic to the state-of-the-art low-energy and low-thrust methods.Essential mechanisms of the various utilized dynamic models and the characteristics of the different design methods are discussed in hopes of helping readers grasp thebasic overviewof the current Earth-Moon transfer orbitdesignmethods anda deep academic background is unnecessary for the context understanding. 展开更多
关键词 Earth-Moon transfer traditional direct transfer low-energy transfer manifold theory weak stability boundary theory low-thrust transfer
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Atomic-scale electromagnetic theory bridging optics in microscopic world and macroscopic world
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作者 李志远 陈剑锋 《Chinese Physics B》 SCIE EI CAS CSCD 2023年第10期483-502,共20页
Atoms in the microscopic world are the basic building blocks of the macroscopic world. In this work, we construct an atomic-scale electromagnetic theory that bridges optics in the microscopic and macroscopic worlds. A... Atoms in the microscopic world are the basic building blocks of the macroscopic world. In this work, we construct an atomic-scale electromagnetic theory that bridges optics in the microscopic and macroscopic worlds. As the building block of the theory, we use the microscopic polarizability to describe the optical response of a single atom, solve the transport of electromagnetic wave through a single atomic layer under arbitrary incident angle and polarization of the light beam, construct the single atomic layer transfer matrix for light transport across the atomic layer. Based on this transfer matrix, we get the analytical form of the dispersion relation, refractive index, and transmission/reflection coefficient of the macroscopic medium. The developed theory can handle single-layer and few-layers of homogeneous and heterogeneous 2D materials, investigate homogeneous 2D materials with various vacancies or insertion atomic-layer defects, study compound 2D materials with a unit cell composed of several elements in both the lateral and parallel directions with respect to the light transport. 展开更多
关键词 atomic-scale electromagnetic theory two-dimensional materials transfer matrix method
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New insights into the mechanism of reactive adsorption desulfurization on Ni/ZnO catalysts:Theoretical evidence showing the existence of interfacial sulfur transfer pathway and the essential role of hydrogen
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作者 Hou-Yu Zhu Nai-You Shi +8 位作者 Dong-Yuan Liu Rui Li Jing-Gang Yu Qi-Tang Ma Tu-Ya Li Hao Ren Yuan Pan Yun-Qi Liu Wen-Yue Guo 《Petroleum Science》 SCIE EI CSCD 2023年第5期3240-3250,共11页
As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO ... As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation. 展开更多
关键词 Reactive adsorption desulfurization Ni/ZnO Interface Sulfur transfer Density functional theory
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基于GIS的公交换乘网络构建及可达性分析 被引量:3
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作者 程刚 郭磊善 《江苏大学学报(自然科学版)》 CAS 北大核心 2024年第2期191-197,共7页
为了提高公交换乘效率、优化公交系统,基于GIS软件构建公交换乘网络,运用该网络对换乘可达性进行了测度和分析.结合Space-P模型和网络分析法,以拉萨市城关区为研究区域,基于公交线路路径、站点、交叉口等基本信息构建同站换乘子网络.结... 为了提高公交换乘效率、优化公交系统,基于GIS软件构建公交换乘网络,运用该网络对换乘可达性进行了测度和分析.结合Space-P模型和网络分析法,以拉萨市城关区为研究区域,基于公交线路路径、站点、交叉口等基本信息构建同站换乘子网络.结合公交站点服务范围、步行通道路径、交叉口等信息构建异站换乘子网络.二者协同实现了基于ArcGIS的公交换乘网络构建,并依据该网络对公交线路的乘客在车时间和换乘系数进行测度和分析.结果表明:构建的换乘网络能够对乘客在车时间进行良好的测度,乘客在车时间最大值为68.68 min,最小值为2.00 min,乘客换乘在车时间平均值为29.90 min.该换乘网络能够对换乘系数进行良好的测度,得到有效换乘线路90 300条,换乘系数最大为4条(线路为62条),最小为0条(线路为1 354条).采用可达性度量模型,可实现对公交站点时间可达性和换乘可达性的良好测度和分析. 展开更多
关键词 公共交通 公交网络 换乘网络 GIS 可达性 Space-P模型 网络分析法
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基于扎根理论的知识转移粘滞过程机制研究——以在孵企业为例 被引量:1
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作者 蒋永康 梅强 《科技进步与对策》 北大核心 2024年第15期109-117,共9页
知识转移粘滞现象会阻碍知识流动和分享,厘清知识转移粘滞的过程机制有助于进行高效的知识管控。通过对16家在孵企业的深度访谈,运用扎根理论方法构建知识转移粘滞过程机制的ISIA理论模型,具体包含知识启动粘滞、知识发送粘滞、知识互... 知识转移粘滞现象会阻碍知识流动和分享,厘清知识转移粘滞的过程机制有助于进行高效的知识管控。通过对16家在孵企业的深度访谈,运用扎根理论方法构建知识转移粘滞过程机制的ISIA理论模型,具体包含知识启动粘滞、知识发送粘滞、知识互动粘滞和知识吸收粘滞4个主范畴,以及对应的18个子范畴。在此基础上,对理论模型进行饱和度检验,探讨主范畴的作用路径,并提出知识转移粘滞的管控措施。研究结论有助于丰富和完善知识转移粘滞理论体系,并为知识转移粘滞治理提供启示。 展开更多
关键词 知识转移粘滞 过程机制 扎根理论 ISIA模型 在孵企业
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技术转移分层靶向机制构建研究 被引量:1
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作者 李娟 潘国轩 赵金梅 《科技进步与对策》 北大核心 2024年第7期31-39,共9页
技术成果“转出去”是发挥创新驱动效能与缓解技术转移困境的重要举措,其离不开技术需求管理的有效支撑。研究发现,缺乏对技术需求微观层次属性的关注是导致技术成果转不出去的重要原因。基于分层次管理理论,从技术需求微观层次视角出发... 技术成果“转出去”是发挥创新驱动效能与缓解技术转移困境的重要举措,其离不开技术需求管理的有效支撑。研究发现,缺乏对技术需求微观层次属性的关注是导致技术成果转不出去的重要原因。基于分层次管理理论,从技术需求微观层次视角出发,构建以技术需求精细化分层体系为核心,以精准识别、分层靶向、精准反馈、精准管理为关键要点的技术转移分层靶向机制。依托知识产权制度保障与大数据驱动的有效支撑,技术转移分层靶向机制可有效促进技术供需主体精准对接,引导技术创新要素分层次组合与配置,更有效地将技术成果“转出去”。 展开更多
关键词 技术转移 分层次管理理论 分层靶向 精准对接
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从社会实践到个人信息世界——基于“实践—经验—心灵”交互性的信息分化理论框架 被引量:1
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作者 于良芝 《图书馆理论与实践》 2024年第1期1-8,35,共9页
本文阐释了作者根据其主持的数项国家自然科学基金课题的研究结果而提出的、旨在解释社会成员之间信息分化成因的整体性理论框架。该理论采纳、发展或提出了实践、实践的信息环境、信息获取、信息活动、信息经验效应、心灵状态、个人信... 本文阐释了作者根据其主持的数项国家自然科学基金课题的研究结果而提出的、旨在解释社会成员之间信息分化成因的整体性理论框架。该理论采纳、发展或提出了实践、实践的信息环境、信息获取、信息活动、信息经验效应、心灵状态、个人信息世界等概念,并通过这些概念间的关系解释了信息分化(特别是其中的信息获取差异)的发生。本研究比较了该理论与以往信息分化理论的区别,同时针对老年人的数字化落伍现象展示了该理论框架的解释力优势。 展开更多
关键词 信息分化 信息获取差异 实践理论 个人信息世界
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基于场景感知的访问控制模型
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作者 单棣斌 杜学绘 +2 位作者 王文娟 王娜 刘敖迪 《网络与信息安全学报》 2024年第1期58-78,共21页
动态访问控制模型是构建大数据动态访问控制系统的理论基础,而现有访问控制模型大多只能满足单一情景下的动态访问控制,无法适应大数据上下文环境变化、实体关系变更和客体状态变迁等多类型动态情景中的访问控制。针对上述问题,在现有... 动态访问控制模型是构建大数据动态访问控制系统的理论基础,而现有访问控制模型大多只能满足单一情景下的动态访问控制,无法适应大数据上下文环境变化、实体关系变更和客体状态变迁等多类型动态情景中的访问控制。针对上述问题,在现有访问控制模型的研究的基础上,对大数据动态因素进行分析,提出基于场景感知的访问控制(SAAC,scenario-aware access control)模型。将各类型动态因素转换为属性、关系等基本元素;并引入场景信息对各类组成元素进行统一建模;基于场景信息构建大数据动态访问控制模型,以实现对多类型动态因素、扩展动态因素的支持。设计SAAC模型的工作框架,并提出框架工作流程对应的基于场景感知的访问控制模型规则学习算法和SAAC规则执行算法,以实现访问控制规则自动学习和动态访问控制决策。通过引入非传递无干扰理论,分析并验证了对所提模型的安全性。为验证所提模型访问控制策略挖掘方法的有效性,将SAAC模型与ABAC-L、PBAC-X、DTRM和FB-CAAC等基线模型在4个数据集上进行了实验对比。实验结果表明,SAAC模型及其策略挖掘方法的ROC曲线的线下面积、单调性和陡峭度等指标的结果均优于基线模型,验证了所提模型能够支持多类型动态因素和动态因素扩展,其挖掘算法所得的访问控制规则的综合质量相对较高。 展开更多
关键词 大数据 访问控制 动态因素 场景 无干扰理论
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水液相下Eda酮式异构体与超氧化氢自由基反应的DFT理论计算
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作者 潘宇 姜春旭 +4 位作者 王颢霖 杨应 董雷刚 王佐成 李冰 《吉林大学学报(理学版)》 CAS 北大核心 2024年第5期1254-1266,共13页
在M06-2X/SMD/6-311+G(d,p)理论水平下,研究水液相1个大气压、 310.15 K温度下依达拉奉(Eda)酮式异构体与超氧化氢自由基(·HO_(2))的反应机理.结果表明:Eda酮式异构体与·HO_(2)的反应有抽H、加成和单电子转移3个过程;抽H反应... 在M06-2X/SMD/6-311+G(d,p)理论水平下,研究水液相1个大气压、 310.15 K温度下依达拉奉(Eda)酮式异构体与超氧化氢自由基(·HO_(2))的反应机理.结果表明:Eda酮式异构体与·HO_(2)的反应有抽H、加成和单电子转移3个过程;抽H反应主要通过·HO_(2)抽取杂环H和甲基H实现,反应的自由能垒为77.1~78.7 kJ/mol;加成反应可通过·HO_(2)加成不饱和C的过程实现,加成自由能垒为48.2~95.0 kJ/mol;加成到杂环上与甲基相连的C原子的放热反应最具优势,自由能垒为48.2 kJ/mol;单电子转移的自由能垒为141.1 kJ/mol,该过程不能实现.可见,水液相下Eda酮式异构体可通过抽H和加成反应消除·HO_(2). 展开更多
关键词 依达拉奉酮式异构体 超氧化氢自由基 密度泛函理论 过渡态 Marcus理论 电子转移 自由能垒
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水液相下羟自由基与谷氨酸分子反应机理的量子化学研究
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作者 牛鹤丽 杨应 +5 位作者 徐岩 孙艳雨 郝成欣 王佐成 姜春旭 赵丽红 《复旦学报(自然科学版)》 CAS CSCD 北大核心 2024年第1期143-154,共12页
采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水液相下羟自由基(OH)与谷氨酸分子(Glu)反应的机理。研究发现:Glu的损伤可通过OH抽取其不同位置的H原子、OH加成到羧基和去质子羧基C以及单电子从Glu分子... 采用密度泛函理论的M06-2X和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水液相下羟自由基(OH)与谷氨酸分子(Glu)反应的机理。研究发现:Glu的损伤可通过OH抽取其不同位置的H原子、OH加成到羧基和去质子羧基C以及单电子从Glu分子向OH转移3个途径实现。势能面计算表明:OH加成到羧基和去质子羧基C的反应通道最具优势,反应无势垒;OH抽取质子化氨基H、α-H、β-H、γ-H和羧基H的最低能垒分别是28.7、17.6、8.0、18.3和29.0 kJ/mol;电子从Glu分子向OH转移为劣势通道,反应能垒是255.2 kJ/mol。结果表明,水液相下OH加成和抽H均可诱导Glu分子损伤,损伤的Glu绝大多数难以修复,Glu具有清除羟自由基的能力。 展开更多
关键词 谷氨酸 羟自由基 密度泛函理论 过渡态 电子转移 能垒 损伤
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水溶剂环境下Eda酮式异构体消除超氧负离子自由基O^(-)_(2)·的反应机理
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作者 刘立新 陈静思 +3 位作者 杨应 王佐成 姜春旭 李冰 《江西师范大学学报(自然科学版)》 CAS 北大核心 2024年第3期221-232,共12页
该文在M06-2X/SMD/6-311+G(d,p)水平上,研究了在水溶剂环境1 atm压力和310.15 K温度下Eda酮式异构体与超氧负离子自由基O^(-)_(2)·的反应机理.研究发现:Eda酮式异构体与O^(-)_(2)·的反应有抽H、加成以及单电子转移3种方式.反... 该文在M06-2X/SMD/6-311+G(d,p)水平上,研究了在水溶剂环境1 atm压力和310.15 K温度下Eda酮式异构体与超氧负离子自由基O^(-)_(2)·的反应机理.研究发现:Eda酮式异构体与O^(-)_(2)·的反应有抽H、加成以及单电子转移3种方式.反应势能面研究表明:抽H反应的自由能垒为38.0~176.1 kJ·mol^(-1),优势通道是O^(-)_(2)·抽取杂环H,反应能垒为38.0~41.0 kJ·mol^(-1).加成反应的自由能垒为84.2~196.6 kJ·mol^(-1),优势通道是O^(-)_(2)·加成到杂环与甲基相连的C原子上,反应能垒为84.2 kJ·mol^(-1).单电子从Eda酮式异构体向O^(-)_(2)·转移的反应的能垒为409.2 kJ·mol^(-1),该反应不能实现.研究结果表明:在水溶剂环境下Eda酮式异构体可通过提供杂环H以及甲基邻位C与自由基加成2种途径消除O^(-)_(2)·. 展开更多
关键词 依达拉奉酮式异构体 超氧负离子自由基 密度泛函理论 过渡态 马库斯(Marcus)理论 电子转移 能垒
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