DFT insight into asymmetric alkyl–alkyl bond formation via nickel-catalysed enantioconvergent reductive coupling of racemic electrophiles with olefins

A DFT study has been conducted to understand the asymmetric alkyl–alkyl bond formation through nickel-catalysed reductive coupling of racemic alkyl bromide with olefin in the presence of hydrosilane and K₃PO₄. The key findings of the study include: (i) under the reductive experimental conditions, the Ni(ii) precursor is easily activated/reduced to Ni(0) species which can serve as an active species to start a Ni(0)/Ni(ii) catalytic cycle. (ii) Alternatively, the reaction may proceed via a Ni(i)/Ni(ii)/Ni(iii) catalytic cycle starting with a Ni(i) species such as Ni(i)–Br. The generation of a Ni(i) active species via comproportionation of Ni(ii) and Ni(0) species is highly unlikely, because the necessary Ni(0) species is strongly stabilized by olefin. Alternatively, a cage effect enabled generation of a Ni(i) active catalyst from the Ni(ii) species involved in the Ni(0)/Ni(ii) cycle was proposed to be a viable mechanism. (iii) In both catalytic cycles, K₃PO₄ greatly facilitates the hydrosilane hydride transfer for reducing olefin to an alkyl coupling partner. The reduction proceeds by converting a Ni–Br bond to a Ni–H bond via hydrosilane hydride transfer to a Ni–alkyl bond via olefin insertion. On the basis of two catalytic cycles, the origins for enantioconvergence and enantioselectivity control were discussed.

The enantioconvergent alkyl–alkyl coupling involves two competitive catalytic cycles with nickel(0) and nickel(i) active catalysts, respectively. K₃PO₄ plays a crucial role to enable the hydride transfer from hydrosilane to nickel–bromine species.     

表面等离子体子共振技术用于分析手性药物与蛋白作用差异的研究

利用自行设计组装的一套以白色发光二极管为光源的新型表面等离子体子共振传感器实验装置测量了手性药物D-苯甘氨酸与L-苯甘氨酸与人血清白蛋白和鼠血清白蛋白的结合程度, 可以看到这一对手性药物与血清蛋白的结合程度的差异, 通过这种方法可以区分一对手性药物中的不同异构体. 与现在的手性分析方法比较, 这种方法具有不用标记、样品用量少、仪器易于自动化及小型化等优点.     

自动回流萃取-MPT全谱仪测定航空润滑油中磨损金属的含量

将萃取与回流相结合, 建立了一种处理航空润滑油中磨损金属的新方法, 并用MPT全谱仪对磨损金属含量进行了同时检测. 该方法基本上实现了样品处理的全自动化,克服了常用方法的部分缺点, 对Zn, Cd, Cu, Fe和Pb的检出限(3σ)分别为0.084, 0.043, 0.022, 0.052和0.064 μg/g; 相对标准偏差均小于5%(n=5); 回收率为94.5%~107.4%. 对3个润滑油样品的检测结果令人满意.     

$lt;i$gt;γ$lt;/i$gt;射线总剂量辐照效应对应变Sip型金属氧化物半导体场效应晶体管阈值电压与跨导的影响研究

分析了双轴应变Si p型金属氧化物半导体场效应晶体管(PMOSFET)在γ射线辐照下载流子的微观输运过程, 揭示了γ射线的作用机理及器件电学特性随辐照总剂量的演化规律, 建立了总剂量辐照条件下的双轴应变Si PMOSFET 阈值电压与跨导等电学特性模型, 并对其进行了模拟仿真. 由仿真结果可知, 阈值电压的绝对值会随着辐照总剂量的积累而增加, 辐照总剂量较低时阈值电压的变化与总剂量基本呈线性关系, 高剂量时趋于饱和; 辐照产生的陷阱电荷增加了沟道区载流子之间的碰撞概率, 导致了沟道载流子迁移率的退化以及跨导的降低. 在此基础上, 进行实验验证, 测试结果表明实验数据与仿真结果基本相符, 为双轴应变Si PMOSFET辐照可靠性的研究和应变集成电路的应用与推广提供了理论依据和实践基础. 关键词： 应变Sip型金属氧化物半导体场效应晶体管 总剂量辐照 阈值电压 跨导     

The doping effects of BiFe_1-xCo_xO₃（x=0.0-0.8） in layered perovskite Bi₄Ti₃O₁₂ ceramics

Bi5Fe1-xCoxTi3O15(x = 0.0, 0.2, 0.4, 0.5, 0.6, and 0.8) multiferroic ceramics are synthesized in two steps using the solid state reaction technique. X-ray diffraction patterns show that the samples have four-layer Aurivillius phases. At room temperature (RT), the samples each present a remarkable coexistence of ferromagnetism (FM) and ferroelectricity (FE). The remnant polarization (2P r ) reaches its greatest value of 14 μC/cm 2 at x = 0.6. Remnant magnetization (2M r ) first increases and then decreases, and the greatest 2M r is 7.8 menu/g when x = 0.5. The magnetic properties for x = 0.4 are similar to those for x = 0.6, indicating that the magnetic properties originate mainly from the coupling between Fe 3+ and Co 3+ ions, rather than from their own magnetic moments.     

一种高增益低雷达散射截面的新型圆极化微带天线设计

设计了一种基于人工电磁材料覆层的高增益低雷达散射截面(radar cross section, RCS)圆极化微带天线. 人工电磁材料覆层是由介质板及其两侧的人工周期表面构成, 上表面是加载集总电阻的方环贴片, 具有宽带吸波特性; 下表面是开条带缝和圆环缝的金属贴片, 具有部分反射特性. 将其加载到圆极化微带天线上方, 通过覆层上表面的电阻可吸收入射的雷达波, 结合下表面与接地板构成Fabry-Perot谐振腔的多次反射, 可实现圆极化微带天线辐射和散射性能的同时改善. 实测结果表明: 加载人工电磁材料覆层后, 天线的相对轴比带宽由5.9%扩展为7.1%; 天线增益在整个工作频带内都得到了提升, 最大提高了6.61 dB; 天线RCS在宽频带宽角域内实现了明显的减缩, 在天线工作频带内也实现了3 dB以上减缩. 实测结果与仿真结果符合较好.     

气体团簇离子束两步能量修形法的平坦化效应

本文提出采用气体团簇离子束的两步能量修形法来改善4H-SiC(1000)晶片表面形貌.先用15 keV的高能Ar团簇离子进行整体修形,再用5 keV的低能团簇离子优化表面.结果表明,在相同的团簇离子剂量下,与单一15 keV的高能团簇处理相比,两步法修形后的表面具有更低的均方根粗糙度,两者分别为1.05 nm和0.78 nm.本文还以原子级平坦表面为研究对象,揭示了载能团簇引起的半球形离子损伤(弧坑)与团簇能量的关系,及两步能量修形法在弧坑修复中的优势.在原子力显微镜表征的基础上,引入了二维功率谱密度函数,以直观全面地给出材料的表面形貌特征及其随波长(频率)的分布.结果表明,经任何能量的团簇离子轰击的表面,在0.05—0.20μm波长范围内,团簇轰击都能有效地降低粗糙度,而在0.02—0.05μm范围内,则出现了粗化效应,这是由于形成了半球形离子损伤,但第二步更低能量的团簇离子处理可以削弱这种粗化效应.     

退火处理Fe43Co43Hf7B6Cu1非晶合金的正电子湮没研究

对熔体急冷法制备的Fe₄₃Co₄₃Hf₇B₆Cu₁非晶合金进行了200,300,400和500 ℃保温30 min的退火处理,用正电子湮没寿命谱、X射线衍射、穆斯堡尔谱等方法研究了退火后试样的结构及结构缺陷变化.结果表明,在非晶合金的制备态,正电子主要在非晶基体相空位尺寸的自由体积中湮没,湮没寿命τ₁为158.4 ps,强度I₁关键词： 43Co₄₃Hf₇B₆Cu₁非晶')" href="#">Fe₄₃Co₄₃Hf₇B₆Cu₁非晶 退火处理 正电子湮没寿命 结构与结构缺陷     

苯在Pluronic F127和P123胶束水溶液中的增溶动力学

发展了不分离胶束的增溶动力学数据分析模型,以此考察苯在F127和P123胶束水溶液中的增溶动力学行为.实验发现,这二种胶束增溶苯的速度较快,温度升高进一步促进了增溶.     

苯基重氮盐-冠醚分子嵌合物的FAB-MS及其准分子离子生成机理的研究

Fast atom bombardment mass spectra of a series of arenediazonium salts with various substituents complexed with 18-crown-6 and dibenzo-24-crown-8 ethers were examined. The correlation between quasi-molecular ion abundance of various complexes and the properties, coordination ability of donor-acceptor linkages in the complexes were studied. By using molecular orbital calculation we have successfully demonstrated that the correlation cited is related to the electron cloud densities on the heteroatoms α-N and β-N of arenediazonium salts.