AISI 4340钢干滑动摩擦磨损特性研究

室温条件下,采用CFT-Ⅰ型多功能材料表面综合性能测试仪对AISI 4340钢进行了往复干摩擦磨损试验,研究了其摩擦磨损特性.采用扫描电子显微镜(SEM)和能谱仪(EDS)对磨痕和亚表层进行了观察和检测,分析了磨损表面微观形貌、亚表层塑性变形和碳氧元素含量演化.结果表明:磨损形式以磨粒磨损为主,并伴随轻微黏着磨损和剥落磨损;磨损表面分布着长度、宽度、深度不一的划痕以及鳞片状和颗粒状磨屑;磨损表面出现轻微氧化,磨屑呈现不同程度的碳富集和氧化;亚表层出现明显摩擦影响层,距表层越近,塑性变形越明显,晶界角逐渐汇聚于表面,在表面处趋于平行;往复运动导致塑性变形方向不一致,磨痕中部,塑性变形向某位置聚集.     

均相体系中铱催化2-取代-1,2-二氢喹啉类化合物的脱氢芳构化

 采用原位制备的铱双膦(或膦氮)配合物在碘存在下催化2-取代-1,2-二氢喹啉、2-甲基-2,3-二氢吲哚、1,4-二氢吡啶及3,4-二氢异喹啉等化合物的脱氢芳构化反应, 并考察了不同金属前体、配体、催化剂用量、溶剂和碘等因素对反应速率和选择性的影响. 结果表明,原位制备的［Ir(COD)Cl］2/(±)-MeO-Biphep在碘的存在下催化2-取代-1,2-二氢喹啉的脱氢芳构化反应速率快, 选择性好,催化剂的用量少; 对1,4-二氢吡啶和2,3-二氢吲哚的催化脱氢芳构化反应则须在高温下进行; 而对 3,4-二氢异喹啉, 即使在加热回流条件下也只有不到5%的转化率. 催化体系中碘的存在可以明显提高反应速率.     

基于手性负离子置换策略的异喹啉不对称转移氢化研究

报道了一种手性负离子置换策略,并将其成功应用于异喹啉化合物的不对称转移氢化反应. 以手性磷酸作为催化剂,氯代甲酸酯作为底物活化试剂,Hantzsch酯为有机负氢供体的条件下,该反应能以优良收率得到手性1-取代-1,2-二氢异喹啉产物,ee值最高为79%. 这是首次实现异喹啉化合物不对称转移氢化.     

Access to spirocyclic oxindoles via N-heterocyclic carbene-catalyzed reactions of enals and oxindole-derived α,β-unsaturated imines

A diastereoselective access to β-lactam fused spirocyclic oxindoles and related compounds bearing all carbon spiro centers is described. This N-heterocyclic carbene-catalyzed process employed challenging β,β-disubstituted α,β-unsaturated imines to react with enals.     

Enantioselective activation of stable carboxylate esters as enolate equivalents via N-heterocyclic carbene catalysts

The first N-Heterocyclic Carbene (NHC) mediated activation of stable carboxylate esters to generate enolate intermediates is disclosed. The catalytically generated arylacetic ester enolates undergo enantioselective reactions with α,β-unsaturated imines.     

Robust polyazobenzene microcapsules with photoresponsive pore channels and tunable release profiles

Monodisperse silica particles coated with azobenzene polymer (PAzo) shell were synthesized through distillation precipitation polymerization. Robust PAzo microcapsules were obtained after selective removal of the silica templates by hydrofluoric acid (HF) etching. These PAzo microcapsules, confirmed by transmission electron microscopy (TEM) investigation, had excellent reversible photoisomerization with transformation between trans and cis isomers under ultraviolet (UV) and visible lights. Due to their compatibility with PAzo, acetonitrile would be trapped in the network of the shell during polymerization. Pore channels in the shell, confirmed by nitrogen adsorption–desorption test, would be produced after acetonitrile evaporation. Loading and release of rhodamine B (RhB) molecules in PAzo microcapsules were carried out and indicated that cis azobenzene showed larger pore diameter (named as “open switch”) under UV light which favored permeation of RhB molecules, while trans structure (named as “closed switch”) under visible light slowed down the process. In addition, both release profiles obeyed pure Fickian diffusion with a power law of t^0.42. Diffusion coefficient of RhB from PAzo microcapsules under visible light (1.47 × 10^?12 cm²/s) was lower than that under UV light (2.12 × 10^?12 cm²/s).     

砂-膨润土混合屏障材料渗透性影响因素研究

建立了一个新的结构-尾流振子耦合模型. 流场近尾迹动力学特征被模化为非线性阻尼 振子,采用van der Pol方程描述. 以控制体中结构与近尾迹流体间受力互为反作 用关系来实现流固耦合. 采用该模型进行了二维结构涡激振动计算,得到了合理的 振幅随来流流速的变化规律和共振幅值,并正确地预计了共振振幅值$A_{\max}^\ast$ 随着质量阻尼参数$\left( {m^\ast + C_A } \right)\zeta $的变化规律,给出了预测$A_{\max }^\ast $值的拟合公式. 采用该模型计算了三维柔性结构在均匀来流和简谐波形来流作用下的VIV 响应. 结构在均匀来流作用下振动呈现由驻波向行波的变化过程, 并最后稳定为行波振动形态. 在简谐波形来流作用下,结构呈现混合振动形态,幅值随时间呈周期变化.     

Asymmetric Reductive and Alkynylative Heck Bicyclization of Enynes to Access Conformationally Restricted Aza[3.1.0]bicycles

Conformationally restricted azabicycles are becoming increasingly important in medicinal research. Asymmetric Heck bicyclization of enynes proceeds to give medicinally useful aza[3.1.0] and aza[4.1.0] bicycles with excellent enantioselectivity. The key organopalladium species after bicyclization can be trapped by silanes and terminal alkynes.