Sterically Demanding AgI and CuI N-Heterocyclic Carbene Complexes: Synthesis,Structures, Steric Parameters,and Catalytic Activity

The synthesis and full characterization of new air-stable Ag^I and Cu^I complexes bearing structurally bulky expanded-ring N-heterocyclic carbene (erNHC) ligands is presented. The condensation of protonated NHC salts with Ag₂O afforded a collection of Ag^I complexes, and their first use as ligand transfer reagents led to novel isostructural Cu^I or Au^I complexes. In situ deprotonation of the NHC salts in the presence of a copper(I) source, provides a library of new Cu^I complexes. The solid-state structures feature large N-C_NHC-N angles (118–128°) and almost identical angles between the aryl groups on the nitrogen atoms and the plane of the N-C-N unit of the carbene (i.e. torsion angles close to 0°). Among the steric parameters, the percent buried volume (%V_bur) values span easily in the 50–57 % range, and that one of (9-Dipp)CuBr complex (%V_bur=57.5) overcomes to other known erNHC–metal complexes reported to date. Preliminary catalytic experiments in the copper-catalyzed coupling between N-tosylhydrazone and phenylacetylene, afforded 76–93 % product at the 0.5–2.5 mol % catalyst loading, proving the stability of Cu^I erNHC complexes at elevated temperatures (100 °C).     

Charge Transfer and Metastable Ion Dissociation of Multiply Charged Molecular Cations Observed by Using Reflectron Time-of-Flight Mass Spectrometry

A multiply charged molecule expands the range of a mass window and is utilized as a precursor to provide rich sequence coverage; however, reflectron time-of-flight mass spectrometer has not been well applied to the product ion analysis of multiply charged precursor ions. Here, we demonstrate that the range of the mass-to-charge ratio of measurable product ions is limited in the cases of multiply charged precursor ions. We choose C₆F₆ as a model molecule to investigate the reactions of multiply charged molecular cations formed in intense femtosecond laser fields. Measurements of the time-of-flight spectrum of C₆F₆ by changing the potential applied to the reflectron, combined with simulation of the ion trajectory, can identify the species detected behind the reflectron as the neutral species and/or ions formed by the collisional charge transfer. Moreover, the metastable ion dissociations of doubly and triply charged C₆F₆ are identified. The detection of product ions in this manner can diminish interference by the precursor ion. Moreover, it does not need precursor ion separation before product ion analysis. These advantages would expand the capability of mass spectrometry to obtain information about metastable ion dissociation of multiply charged species.     

连续埋地管线沉陷情况下可靠度分析

场地的不均匀沉陷是埋地管线破坏的重要原因之一.运用均值一次二阶矩法和ANSYS中的蒙特卡罗法对埋地管线在地面沉陷位移、材料性能参数、内水压力等随机变量下的可靠度进行计算分析,得到考虑和不考虑管道内水压力时的可靠度系数和失效概率.结果表明,地面沉陷位移的变异性对沉陷区埋地管线的可靠度有着十分重要的影响,与不考虑管道内水压力作用的结果相比,考虑管道内水压力时的失效概率较大,可靠度系数较小;管道壁厚和直径的变异性对沉陷区埋地管线的可靠度也存在着不可忽视的影响.     

适于全断面岩石掘进机的围岩分类方法

为了研究影响全断面岩石掘进机(TBM)掘进速率的地质因素,利用三维离散元程序3DEC建立TBM滚刀破岩三维仿真模型,分析不同的地质条件对TBM掘进速率的影响,根据TBM在围岩中的可钻性对南水北调西线工程中的围岩进行分类。分析结果表明:TBM掘进速率与岩石物理力学性质及岩体中的节理条件密切相关,在一定范围内,围岩强度越低,节理分布越密集,TBM掘进速率越高;而围岩强度越高,节理间距越大,使得TBM掘进速率大大降低。     

隧道健康动态评价模型与应用

在隧道健康安全评价的指标体系及其等级标准的基础上,通过规范化处理样本资料库中的元素,消除了指标类型和量纲的影响后,提出用集对分析方法构造可变模糊集的相对差异度函数,合理的确定了各层相关隧道健康评价指标处于级别标准区间的相对隶属函数,采用乘积标度法确定相关指标权重后,得出了隧道健康模糊综合评价动态模型。确定健康级别指标特征值后,结合实例计算证明了文中所提方法的科学性与合理性,有利于推动可变模糊集理论在土木工程领域的进一步发展。     

建筑结构风致内压的研究进展

从理论分析方面概括了内压控制方程的发展过程,评述了结构柔度、Helmholtz共振、干扰效应及结构内部分区等几个影响风致内压的主要因素,并从风洞试验、现场实测与CFD(计算流体动力学)模拟3个方面回顾与总结了国内外风致内压的研究进展,列举了各国风荷载规范对内压的描述.通过分析内压控制方程、影响因素以及研究方法中所存在的...     

外形几何参数对双坡屋盖升力系数极值的影响

对我国浙江沿海多个风灾频发区域进行深入调研,全面地确定了新农村典型低矮建筑双坡屋盖的外形几何参数.基于此进行了刚性模型测压风洞试验,研究了屋盖升力系数极值的变化规律,讨论了最不利屋盖升力系数随建筑外形几何参数的变化,用多参数非线性最小二乘法将最不利屋盖升力系数拟合为屋盖坡角、高宽比和厚宽比的函数,并对拟合函数进行了误差...     

爆破振动作用下巷道围岩微裂纹扩展研究

考虑开挖二次应力场和矿体回采爆破振动对圆形巷道围岩微裂纹的影响,探讨巷道围岩裂纹尖端应力场及单节理微裂纹的Ⅰ、Ⅱ型应力强度因子,基于双剪统一强度理论,研究圆形巷道围岩微裂纹裂尖在二次开挖应力场及爆破振动动力场作用下的裂尖起裂角和裂尖塑性区统一解.根据计算式及所得图形,分析比较爆破振动影响下微裂纹扩展角及裂纹尖端塑性区范...     

埋地管道防腐层缺陷检测技术及其应用

研究了防腐层缺陷检测技术。比较了多种检测技术的优缺点．综合分析埋地管道检测技术组合方法及其实际应用。     

黏弹性材料扁球壳轴对称弯曲分析

研究了承受均布荷载的粘弹性材料扁球壳的轴对称弯曲问题,利用弹性一粘弹性相应原理,求解了随时间变化的挠度和内力的解析解。