Planar Tetracoordinate Silicon in Organic Molecules As Carbenoid-Type Amphoteric Centers: A Computational Study

Designing and synthesizing a stable compound with a planar tetracoordinate silicon (ptSi) center is a challenging goal for chemists. Here, a series of potential aromatic ptSi compounds composed of four conjugated rings shared by a centrally embedded Si atom are theoretically designed and computationally verified. Both Born–Oppenheimer molecular dynamics (BOMD) simulations and potential energy surface scannings verify the high stability and likely existence of these compounds, particularly Si-16-5555 (SiN₄C₈H₈) with 16 π electrons, under standard ambient temperature and pressure. Notably, the Hückel aromaticity rule, which works well for single rings, is inconsistent with the high stability of Si-16-5555 where the 16 p electrons are spread over four five-membered rings fused together. Bonding analyses show that the strong electron donation from the peripheral 12-membered conjugated ring with 16 π electrons to the vacant central atomic orbital Si 3p_z leads to the stabilization for both the ptSi coordination and planar aromaticity. The partial occupation of Si 3p_z results in the peculiar carbenoid-type behaviors for the amphoteric center. By modulating the electron density on the ring with substituent groups, we can regulate the nucleophilic and electrophilic properties of the central Si.     

带变量核的广义高阶Marcinkiewicz积分交换子在Herz型Hardy空间的有界性

设A是R~n上的一个m阶可导函数,且D~λA∈Λ_β(0β1,|λ|=m),Ω(x,z)∈L~∞(R~n)×L~s(S~(n-1))(sn/(n-β))是零阶齐次函数且关于变量z满足消失条件.该文证明了广义高阶Marcinkiewicz积分交换子μ_Ω~A及其变形μ_Ω~A在Herz型Hardy空间的有界性.     

GaN材料的高速生长对其C污染以及光致发光光谱的影响

利用金属有机化学气相沉积对GaN的高速生长进行了研究.结果表明,随着GaN生长速率的提高,其非故意掺杂的C含量也在提高,并且呈现出良好的线性关系.当生长速率由2μm/h增加至7.2μm/h时,利用SIMS测量发现其GaN中的C含量由2.9×1017增加至5.7×1018 cm-3 .研究表明,N空位的存在与C浓度之间存在紧密的联系。在高氨气分压生长条件下,N空位的浓度也在急剧下降。此时,与具有相近生长速率的常规样品相比,其C含量几乎下降了一个数量级。.光致发光光谱表明,黄带以及蓝带的强度与C污染存在线性关系.这个结果也证实了与C相关的缺陷是导致黄带以及蓝带发光的主要来源。     

基于自适应控制电路实现的宽带高性能频率源

基于自适应控制技术,在宽带捷变频频率合成器的设计方案中同时引入自动调节滤波电路和带温度预校准功能的自动电平控制电路,有效降低了输出信号杂散,提高了输出信号的功率平坦度, 相比传统的利用分段滤波方式实现的宽带频率源,减小了模块体积。文中不仅详细介绍了这2个电路的实现过程,还从易于工程实现的角度出发,着重介绍了一些能有效降低调试工作量的方法。设计所得的频率合成器输出频率1 000 MHz~1 900 MHz,步进2 MHz,在–45 ℃~ +85 ℃的温度范围内,实现了杂散抑制优于–70 dBc,输出功率10 dBm±0.3 dBm的技术指标。     

基于DES密码电路的差分功耗分析仿真研究

差分功耗分析技术是目前应用广泛、技术发展较成熟的非侵入攻击技术,设计了一个功耗分析仿真平台,该平台具有自动化程度高、精度高和仿真速度快的特点.此外,还基于该平台实现了对DES密码电路的差分功耗分析,对数字电视机项盒安全性的提高具有参考意义.     

等离子体周期结构带通特性研究

本文在Lee W.Cross研究等离子立方体加载频选单元结构的基础上,进一步分析结构带通特性受频选单元、等离子体密度、入射方向及上中下三层介质之间的影响,设计优化等离子周期结构模型,采用高介电常数介质封装等离子体,使其具有恒定带宽和随入射角变化保持稳定的谐振频率,大入射角时3d B带宽比在1.4:1以下,拓展等离子周期结构研究前景。     

Application of heating microscopy to the study of thermal behaviour of ZnO–P2O5–WO3 glasses

The effect of WO₃ on thermal behaviour and thermal stability of ZnO–P₂O₅–WO₃ glasses prepared in compositional series (100 ? x)[0.5ZnO–0.5P₂O₅] ? xWO₃ (x = 0–60) was investigated by heating microscopy and the results were correlated with the results determined by conventional thermodilatometry and differential thermal analysis. Thermoanalytical studies showed that the glass transformation temperature and dilatation softening temperature increase with increasing WO₃ content while thermal expansion coefficient decreases. The highest stability towards crystallization possess glasses containing 20–30 mol% WO₃. Major compounds formed by the crystallization of the glasses were Zn(PO₃)₂, WO₃ and W₁₈P₂O₅₉. The values of sphere temperature, hemisphere temperature and flow temperature obtained using heating microscopy were strongly influenced by the degree of crystallization process at the sintering.     

Comparative pyrolysis upcycling of polystyrene waste: thermodynamics, kinetics, and product evolution profile

Pyrolysis is one important way to treat polystyrene waste and upcycle it into useful materials. A comparative pyrolysis study of virgin polystyrene (VPS) and two types of commonly used polystyrene products, expanded polystyrene (EPS) and polystyrene container (CPS) was carried out. Various values were found in the thermodynamic study and kinetic study of VPS, EPS, and CPS pyrolysis, suggesting distinct thermal degradation characteristics of these materials. The energy barrier order of the pyrolysis processes was EPS, CPS, VPS, showing activation energy of 230, 219, and 145 kJ mol^?1, respectively. The order of amount of heat absorbed was EPS, CPS, VPS, with enthalpy of 224, 213, and 139 kJ mol^?1, respectively. The reaction favorability order was EPS, CPS, and VPS with Gibbs free energy of 118, 132, and 210 kJ mol^?1, respectively. Thermogravimetric analysis indicated the use of high heating rate would increase the reaction rate and shorten the reaction time. Product evolution profiles showed that VPS and CPS pyrolysis produced mainly aromatics, while EPS pyrolysis produced aromatics at the initial phase of the reaction and aliphatic hydrocarbon at the latter phase. The diverse pyrolysis behaviors of VPS, EPS, and CPS demonstrated that an examination on different polystyrene materials was desired to optimize the pyrolysis conditions and product distribution, and thus benefit the process of valuable materials recovery.     

One-Pot Synthesis of 1-Alkynylphosphonates

1-Alkynylphosphonates 3 are prepared in a one-pot procedure from diethyl phosphorochloridates 2 and alkynyllithiums 1, which are readily generated by the reaction of 1-alkynes with n-BuLi.     

Synthesis and properties of near IR induced self-healable polyurethane/graphene nanocomposites

A series of self-healable polyurethane (SHPU)/modified graphene (MG) nanocomposites were synthesized from poly(tetramethylene glycol) (PTMG) and 4,4′-methylene diphenyl diisocyanate (MDI) with minute amounts (0–1 wt%) of MG which was chemically modified graphene oxide (GO) with phenyl isocyanate and reduced in the presence of phenylhydrazine.