Density functional theory study of substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of m‐G‐C6H4OFe(CO)2(η5‐C5H5) and m‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of (meta‐substituted phenoxy)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η⁵‐cyclopentadienyl) iron [m‐G‐C₆H₄SFp ( 2 )] complexes. In this study, Fp is (η⁵‐C₅H₅)Fe(CO)₂, and G is NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂. The results show that Tao–Perdew–Staroverov–Scuseria and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free energy relations [r = 1.00 (g, 1e), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and δΔG⁰ of O?H bonds of m‐G‐C₆H₄OH or ΔΔH_het(Fe–S)'s and ΔpK_a's of S?H bonds of m‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And, the linear correlations [r = ?0.97 (g, 1 g), ?0.97 (g, 2 h)] among the ΔΔH_het (Fe–O)'s or ΔΔH_het(Fe–S)'s and the substituent σ_m constants show that these correlations are in accordance with Hammett linear free energy relationships. The inductive effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. The ΔΔH_het(Fe–O)'s(g) (1) and ΔΔH_het(Fe–S)'s(g)(2) follow the capto‐dative Principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of Residual Stress on Corrosion Sensitivity of Carbon Steel Studied by SECM

The effect of compressive residual stress on the reactivity of carbon steel in a neutral chloride solution was investigated by means of potentiodynamic polarization and local electrochemical measurement with scanning electrochemical microscope（SECM）. Meanwhile, X-ray diffraction, as a nondestructive technique, was employed to determine the levels of residual stress in near-surface layers of carbon steel specimen. The results show that the resi- dual stress existed in the specimen fell into the category of compressive residual stress which was inversely propor- tional to the corrosion sensitivity of carbon steel specimen. By using I/I3 couple as a redox mediator in the current feedback mode of SECM measurements, the Faradaic current on Pt tip, which was relevant to the rate of the I3- ion reduction, fell with the increase of compressive residual stress. The correlation between compressive residual stress and heterogeneous electron transfer rate has been proposed based on the inference of the localized electrochemical reactions occurred on the specimen surface,     

一种凝血酶亲和色谱介质的制备方法

对凝血酶-琼脂糖亲和色谱介质的制备方法进行了研究。首先使用凝血酶和溴化氰活化的琼脂糖制备凝血酶-琼脂糖亲和色谱介质,然后用生色底物法考察亲和色谱介质上凝血酶的活性,以凝血酶活性为指标对最佳偶联条件进行了优化。结果表明最佳条件为使用pH 8.3的Na₂CO₃-NaHCO₃溶液(含0.5 mol/L NaCl)为缓冲溶液,凝血酶用量为每1 g色谱介质加入凝血酶200 U,室温反应10 h。在最佳条件下所制备的色谱介质有较好的稳定性,在4℃条件下存放40天,亲和介质上的凝血酶活性仍有70.6%保留。该亲和色谱介质可广泛用于含凝血酶抑制剂的天然药物筛选和分离纯化。     

循环软化45碳钢和循环硬化304不锈钢的棘轮行为实验研究

对循环软化45碳钢的单轴应力循环下的平均应力、应力幅值以及先前应变循环对棘轮效应的影响进行了实验研究;并对循环硬化的304不锈钢进行了多种非比例循环加载路径下路径形状、路径等效应力幅值、平均应变与平均应力对材料棘轮变形行为的影响实验．发现平均应力和应力幅值及其历史对于材料的棘轮行为都有很大的影响．     

高速列车的关键力学问题

在过去10 年时间, 中国和谐号系列高速列车经历了一系列速度上的飞跃. 在最初引进消化吸收基础上, 研制了新一代高速列车并大规模投入运营, 伴随这一过程的大量试验与工程实践, 大大促进了对高速铁路这样一个车- 线- 网- 气流强耦合的复杂大系统中的关键力学问题的深入理解和全面研究. 该文将从6 个方面对高速列车研制和运行过程中的典型力学问题的研究进展以及未来的研究方向做一个梳理. 考虑到这样一个大系统的复杂性,同时也为了使对高速列车感兴趣的技术与科研人员对这些力学问题有一个比较全面的认识, 文中将分别就高速列车的空气动力学、弓网关系、车体振动与车体模态设计、车体运行稳定性、高速轮轨关系、关键结构的运行可靠性和列车噪声等方面的研究进行总结和展望. 同时也对中国及国际高速列车发展趋势及其中的力学问题做了一个简要介绍.      

基于气相色谱-质谱联用技术的乙型肝炎血清代谢标志物的探究

探索了乙型肝炎患者和健康人血清代谢组的差异,寻找与疾病相关的潜在标志物。收集乙肝患者30例、健康对照35例,以气相色谱-质谱联用技术作为研究平台,应用主成分分析、正交偏最小二乘法-判别分析进行模式识别,然后通过变量重要性因子、非参数检验,结合数据库检索筛选鉴定有差异的代谢物。确认10个代谢物存在显著差异,其中柠檬酸、乌头酸、谷氨酰胺、N,N-二甲基甘氨酸、丙二酸与乙型肝炎患者组的相关性较好,受试者工作特征曲线下面积为0.975,具有较好的特异度和敏感度。因此这5个代谢物能够作为潜在的区分乙型肝炎患者和正常人的血清小分子标志物,有助于进一步了解病理机制,确定治疗目标。     

NEW STRUCTURAL DESIGN OF SPHERICAL PRESSURE HULL FOR DEEP-SEA SUBMERSIBLES:A MULTILAYER AND PRESSURE REDISTRIBUTION APPROACH

耐压壳是深海潜水器中最关键的结构,直接关系到潜水器安全性和总体性能.本文对当今的单层耐压壳结构设计进行了评述,并设计了一种基于分层/分压的新型耐压壳结构,该结构借鉴了自然界的两种深潜动物的结构：抹香鲸分层结构和鹦鹉螺隔片分割螺壳亚结构.综合了这两种结构特性的双层壳结构能够有效提高抗压能力,从而提升深潜能力.与以往单层球壳的耐压壳结构相比,该结构不仅提高了强度,也提高了抗屈曲能力.同时,该结构还兼具大容积、高可靠性、以及避免超厚壳制备上的难点等特征,使得深海潜水器的综合性能得到显著提高.新结构中的桁架将圆壳分割为若干个柱壳亚结构,本文针对此亚结构严格推导了桁架增强壳体抗屈曲的公式.从实验数据中总结出来的泰勒水池公式是目前广泛使用的潜水器壳体设计依据,新推导的公式与之相比只有6%的差别,这使得新型结构设计有了更坚实的理论基础.     

递推-组合法推求j-j耦合光谱项

本文提出了推求等价组态j-j耦合原子光谱项的新方法－－递推－组合法。该法计算过程简单，易于掌握。     

卤代铂络合物与烯烃络合的价键特征及催化作用的量子化学讨论

本文利用量子化学CNDO/2方法,计算了一乙烯三卤化铂,二乙烯二卤化铂体系。以乙烯为例,探讨了有机烯烃分子与过渡金属原子铂络合的价键特征,同时考查了卤素(F、Cl、Br、Ⅰ)对其的影响规律。为络合催化机理的探讨提供有益的信息。