From the mobile proton to wandering hydride ion: mechanistic aspects of gas‐phase ion chemistry

Structural characterization of molecular species by mass spectrometry supposes the knowledge of the type of ions generated and the mechanism by which they dissociate. In this context, a need for a rationalization of electrospray ionization(+)(?) mass spectra of small molecules has been recently expressed. Similarly, at the other end of the mass scale, efforts are currently made to interpret the major fragmentation processes of protonated and deprotonated peptides and their reduced forms produced in electron capture or electron transfer experiments. Most fragmentation processes of molecular and pseudo‐molecular ions produced in the ion source of a mass spectrometer may be described by a combination of several key mechanistic steps: simple bond dissociation, formation of ion‐neutral complex intermediates, hydrogen atom, hydride ion or proton migrations and nucleophilic attack. Selected crucial aspects of these elementary reactions, occurring inside positively charged ions, will be recalled and illustrated by examples taken in recent mass spectrometry literature. Emphasis will be given on the protonation process and its consequence in terms of structure and energetic. Copyright © 2013 John Wiley & Sons, Ltd.     

NH4CNS与Fe3(CO)12反应的研究

Fe的簇合物,在温和的条件下(常压,低于200℃),可与各种不饱和分子生成各种有机功能团配位的簇合物。因此,我们想用Fe_3(CO)_(12)与NH_4CNS反应得到含-SCN的羰基铁簇合物。但实验中未得到这种化合物。不过,Fe_3(CO)_(12)与NH_4CNS的反应是一个新反应,穆斯堡尔谱的研究也得到了新信息。因此,我们认为报道研究结果仍然是十分有意义的。     

进口预旋对离心叶轮气动性能影响机理的研究

将理论推导和数值模拟相结合,对典型离心压缩机Eckardt叶轮流场进行分析,探讨了不同进气预旋对叶轮气动性能的影响;从叶片进口攻角、叶尖相对马赫数和流向压力变化的角度,阐述了预旋对内部流动以及气动性能的影响机理.结果表明:预旋角对进口攻角和叶尖相对马赫数同时产生显著影响,正预旋会降低进口来流的攻角及相对马赫数,使叶片前...     

激光片光流动显示技术在高机动飞机布局设计中的应用

采用激光片光流动显示技术,针对某高机动布局飞机开展大迎角流动机理研究.结果表明激光片光流动显示技术具备捕捉复杂流动结构的能力,可以清晰观察双前翼布局大迎角下机头涡、第一前翼涡、第二前翼涡以及机翼涡等涡结构的生成、发展、融合等复杂流动结构的演化,并且揭示出涡结构扫略垂尾内侧使布局航向更加安定,偏转前翼将使旋涡绕流的涡心降低,造成布局升力提高,低头力矩增加.片光流动显示结果进一步表明,布局航向安定性不足,垂尾需要沿展向外移动,为布局深化设计提供了设计依据.     

Transition prediction of a hypersonic boundary layer over a cone at small angle of attack—with the improvement of e<Superscript><Emphasis Type="Italic">N</Emphasis></Superscript> method

The problem of transition prediction for hypersonic boundary layers over a sharp cone has been studied in this work. The Mach number of the oncoming flow is 6, the cone half-angle is 5°, and the angle of attack is 1°. The conventional e ^N method is used, but the transition location so obtained is obviously incorrect. The reason is that in the conventional method, only the amplifying waves are taken into account, while in fact, for different meridians the decay processes of the disturbances before they begin to grow are different. Based on our own previous work, new interpretation and essential improvement for the e ^N method are proposed. Not only the amplification process but also the decay process is considered. The location, where by linear stability theory, the amplitude of disturbance wave is amplified from its initial small value to 1%, is considered to be the transition location. The new result for transition prediction thus obtained is found to be fairly satisfactory. It is also indicated that for the calculation of base flow, boundary layer equations can be used for a small angle of attack. Its computational cost is much smaller than those for DNS. Supported by the National Natural Science Foundation of China (Grant Nos. 10632050 and 90716007), the Special Foundation for the Authors of National Excellent Doctoral Dissertations (Grant No. 200328), and the Foundation of Liu-Hui Center of Applied Mathematics of Nankai University and Tianjin University     

AFRA: Argumentation framework with recursive attacks

The issue of representing attacks to attacks in argumentation is receiving an increasing attention as a useful conceptual modelling tool in several contexts. In this paper we present AFRA, a formalism encompassing unlimited recursive attacks within argumentation frameworks. AFRA satisfies the basic requirements of definition simplicity and rigorous compatibility with Dung’s theory of argumentation. This paper provides a complete development of the AFRA formalism complemented by illustrative examples and a detailed comparison with other recursive attack formalizations.     

基于多目标双层规划的智能电网虚假数据注入攻击研究

相对于传统电网,智能电网引入了先进的信息通信技术能显著提高企业生产效率和电力数据处理效率,但由于传统状态估计的漏洞,智能电网易受到虚假数据注入的攻击。现有的研究仅追求电力系统运营成本的最大化或攻击资源的最小化,没有考虑两者之间的均衡。基于此,本文考虑建立智能电网虚假数据注入攻击双层多目标规划模型,其中多目标表示电力系统运营成本与攻击成本之间的均衡,并结合IEEE 14总线算例进行分析,针对攻击者不同的攻击倾向给出了相应的虚假数据注入攻击策略。     

基于非对称半监督集成SVM的托攻击检测方法

受推荐系统在电子商务领域重大经济利益的驱动,恶意用户以非法牟利为目的实施托攻击,操纵改变推荐结果,使推荐系统面临严峻的信息安全威胁,如何识别和检测托攻击成为保障推荐系统信息安全的关键。传统支持向量机(SVM)方法同时受到小样本和数据不均衡两个问题的制约。为此,提出一种半监督SVM和非对称集成策略相结合的托攻击检测方法。首先训练初始SVM,然后引入K最近邻法优化分类面附近样本的标记质量,利用标记数据和未标记数据的混合样本集减少对标记数据的需求。最后,设计一种非对称加权集成策略,重点关注攻击样本的分类准确率,降低集成分类器对数据不均衡的敏感性。实验结果表明,本文方法有效地解决了小样本问题和数据不均衡分布问题,获得了较好的检测效果。     

虚拟化系统中的攻击与防护模型研究

针对目前的攻击模型不能充分表达虚拟化系统所面临的威胁,可信基设计忽略虚拟机监控器(virtual machine monitor,VMM)完整性,客户机资源保护不充分等问题,设计了基于协作型VMM的安全模型.采用非对称的地址映射和访问权限使安全部件及监控点隔离于易受感染代码,建立了双系统间引用监控机制验证VMM内存完整性,并根据恶意行为的语义映射在关键路径上保护系统资源.实验结果表明协作型VMM安全模型能够捕获到客户机中完整的信息流,并能准确识别出其中的异常系统调用序列.     

脱体涡流型的数值计算

本文在回顾空气动力体大迎角脱体涡流场数值计算的发展过程之后,详细讨论了各种势流计算模型。