CBS还原合成手性1-苯乙醇实验设计*

将学科热点之一催化不对称合成策略引入实验教学中,通过CBS还原制备手性醇。实验以苯乙酮为原料,还原得到粗产物手性1-苯乙醇,经制备色谱仪分离提纯,气相色谱和自动旋光仪表征产物的光学性质。实验为综合型有机化学实验,通过此实验,学生在掌握手性醇合成原理与方法的同时,进一步学习手套箱、气相色谱、制备色谱仪、自动旋光仪等新技术,以提升学生综合科研素质。     

Challenges in the Highly Selective [3 + 1]-Cycloaddition of an Enoldiazoacetamide to Form a Donor–Acceptor Cis-Cyclobutenecarboxamide

A substituted donor–acceptor cyclobutenecarboxamide is synthesized with modest enantiocontrol through a chiral copper(I) complex catalyzed [3 + 1]-cycloaddition reaction of α-acyl diphenylsulfur ylides with 3-siloxy-2-diazo-3-butenamides. With a methyl substituent on the 4-position of the 3-butenamide, the cis-vicinal-3,4-disubstituted cyclobutenecarboxamide is formed with >20:1 diastereocontrol. Donor-acceptor 3-methyl-2-siloxycyclopropenecarboxamide is rapidly formed from the reactant enoldiazoamide and undergoes catalytic ring opening to give only the Z-γ-substituted metallo-enolcarbene. Elimination from 3-siloxy-2-diazo-3-pentenamide to form the conjugated 3-siloxy-2,4-pentadienamide is competitive but minimized at low temperature.     

Non-linear interactions in imperfect beams at veering

Non-linear interactions in a hinged-hinged uniform moderately curved beam with a torsional spring at one end are investigated. The two-mode interaction is a one-to-one autoparametric resonance activated in the vicinity of veering of the frequencies of the lowest two modes and results from the non-linear stretching of the beam centerline. The excitation is a base acceleration that is involved in a primary resonance with either the first mode only or with both modes. The ensuing non-linear responses and their stability are studied by computing force- and frequency-response curves via bifurcation analysis tools. Both the sensitivity of the internal resonance detuning—the gap between the veering frequencies—and the linear modal structure are investigated by varying the rise of the beam half-sinusoidal rest configuration and the torsional spring constant. The internal and external resonance detunings are varied accordingly to construct the non-linear system response curves. The beam mixed-mode response is shown to undergo several bifurcations, including Hopf and homoclinic bifurcations, along with the phenomenon of frequency island generation and mode localization.     

Principal parametric and three-to-one internal resonances of flexible beams undergoing a large linear motion

A set of nonlinear differential equations is established by using Kane‘s method for the planar oscillation of flexible beams undergoing a large linear motion. In the case of a simply supported slender beam under certain average acceleration of base, the second natural frequency of the beam may approximate the tripled first one so that the condition of 3 : 1 internal resonance of the beam holds true. The method of multiple scales is used to solve directly the nonlinear differential equations and to derive a set of nonlinear modulation equations for the principal parametric resonance of the first mode combined with 3 : 1 internal resonance between the first two modes. Then, the modulation equations are numerically solved to obtain the steady-state response and the stability condition of the beam. The abundant nonlinear dynamic behaviors, such as various types of local bifurcations and chaos that do not appear for linear models, can be observed in the case studies. For a Hopf bifurcation,the 4-dimensional modulation equations are reduced onto the central manifold and the type of Hopf bifurcation is determined. As usual, a limit cycle may undergo a series of period-doubling bifurcations and become a chaotic oscillation at last.     

Mechanical behaviour of the upper layers of a sandy loam soil under shear loading

The mechanical behaviour of the upper layers of a sandy loam soil was studied under standard triaxial compression and direct shear box tests. Variations of soil material properties were investigated at four different initial dry bulk densities of 1410, 1520, 1610 and 1670 kg/m³. Soil deformation and volume change under the triaxial compression loading were also studied at these bulk densities. Results from the two tests showed increases in the soil mechanical properties with the initial dry bulk density. The internal friction angle values measured with the triaxial compression apparatus exceeded those measured with the direct shear box. In contrast, the soil cohesion values measured with the direct shear box exceeded those measured with the triaxial compression apparatus. Under the triaxial compression test, the loose soil samples underwent contraction and volume reduction, whereas the dense samples swelled and failure cracks appeared clearly at various planes. The soil contraction for the former case characterizes the occurrence of soil compaction, whereas the cracks propagation and volume increase in the latter case characterizes the breaking up and loosening of soil during tillage operations. For the loose and moderately compacted states, the engineering Poisson's ratio increased with the axial strain until loading was completed. It also increased at the compacted and very compacted states until reaching given loading stages, after which its value started to decrease. This shifting in the engineering Poisson's ratio during loading may provide another identification of the moment of soil failure occurrence, in addition to that of the maximum shear stress.     

简支梁振台的理论解及位移测试

利用由机械振动理论推导出的等截面简支梁的理论解,推导出了带集中质量的简支梁振动台的理论解,并通过分析动态条件下简支梁的位移与应变之间的关系,证明了:在动态条件下梁的位移与应变之间存在很好的正比关系。利用梁的位移与应变之间正比关系,如果在梁上适当位置粘贴应变片,通过测试应变就能准确地测得梁的动态位移。本文通过实例证明了该方法确实可行,理论解与实测结果非常吻合。这为简支梁的动态测试提供了有效而简便的方法。     

不连续岩石梁的失稳解析

本文根据不连续岩石梁的物理力学特性提出了无拉力岩石梁的力学解析模型。根据Ｆｒｅｅｂｏｄｙ法及Ｃａｓｔｉｇｌｉａｎｏ定量导出了不连续梁各物理量的求解方程式。进而采用挠度增量δｍａｘ＾ｉ＋１＝δｍａｘ＾ｉ＋Δδ↑－的逐次解析方法，求解了不连续梁的失稳问题，得出了与Ｆ．Ｄ．Ｗｒｉｇｈｔ的试验值相吻合的结果。探讨了不连续岩石梁在不同荷载条件下的失稳特性。     

STATIC STUDY OF CANTILEVER BEAM STICTION UNDER ELECTROSTATIC FORCE INFLUENCE

I. INTRODUCTION For capacitor-like microelectromechanical systems (MEMS) structure[1??6], the voltage betweenthe structure and substrate causes attractive force. The sources of the voltage can be an arti?ciallymounted device[2 , 7??9] or the temporar…     

剪切弯曲下短深梁位移数值计算精度的研究

分析了短深梁位移的基本解，评述了有限元解法中关于高次分布力简化为节点力的问题。使用虚功原理和位移线性插值推导了满足二次分布力作用的精确节点力分配公式。通过矩形截面悬臂梁自由终端受集中载荷的算例，阐明了提高短深梁位移计算精度的途径。     

梁板结构埋入压电片的深度和厚度优化研究

根据梁的弯曲变形理论，以及压电材料的压电效应，对压电复合材料梁结构的应变和应力状态进行了分析。推导了压电材料埋入梁结构时其埋入深度和压电材料本身厚度的优化目标函数。根据优化目标函数，绘制出了在给定的基体材料和压电材料弹性模量比之下，压电材料的驱动力矩随埋入深度和压电材料厚度变化的三维曲面和等高线图，直观地表示出了埋入型压电材料智能结构获得最佳驱动力矩的配置方案。同时也分析了结构和压电材料两者的弹性模量之比对其结果的影响。结果表明，压电材料对于结构的作动力矩与其埋入基体材料的深度、本身厚度以及基体材料和压电材料的弹性模量之比都有着密切的联系。同时将结果也推广到了压电板结构，此时压电材料和基体材料的泊松比时其结果也有一定的影响。