Diastereoselective Synthesis of Polysubstituted Piperidines through Visible-Light-Driven Silylative Cyclization of Aza-1,6-Dienes: Experimental and DFT Studies

A visible-light-driven radical silylative cyclization of aza-1,6-dienes featuring an acrylonitrile or acrylate moiety and an electron-neutral olefin was developed, which allows for stereoselective synthesis of densely functionalized piperidines in a highly atom-economical manner. Depending on the substitution pattern of the electron-neutral olefin, poor-to-excellent diastereoselectivity was observed. It was suggested that the 6-exo-trig cyclization was initiated by a chemoselective addition of silyl radical toward electron-deficient olefin and the geometry of the remaining olefin is closely associated with the cis-stereoselectivity. DFT calculations supported that a transition state with a cyano group locating at the axial position of the forming piperidine ring might be involved, in which either the increase of 1,3-diaxial repulsion or the lack of hydrogen bonding interaction will diminish diastereoselectivity.     

Assessment of the in vitro toxicity of calixarenes and a metal-seamed calixarene: a chemical pathway for clinical application

Calixarenes are known to form host–guest complexes and supramolecular nanoassemblies with well-defined architectures. However, the use of these materials in conjunction with drug moieties is still under explored. One reason is the insufficient biocompatibility studies. Our present study represents a systematic in vitro investigation of the cytotoxicity associated with C-methylresorcin[4]arene, C-methylpyrogallol[4]arene, p-phosphonated calix[8]arene and a metal-seamed calixarene–copper(II) complex, using human HEK293 and rat C6G cell lines and two different cell viability assays (MTT and CellTiter-Glo) to avoid species-biased results. All compounds showed low to moderate toxicity. The trend in the CC₅₀ values indicated that the suppression of the coordination ability and the presence of phosphonate groups decrease the overall cytotoxicity of the compounds. The results of this study not only establish calixarenes and their immediate families as potential drug carriers and drug modifiers, but also reveal a pathway for fine-tuning their toxicological behaviour by appropriate chemical modification.     

北京谱仪III上利用神经网络方法进行粒子鉴别的研究

本文描述了一种多层感知器的神经网络系统在BESIII粒子鉴别技术中的应用。网络按照子探测器分别进行训练, 输出结果可以作为后续网络的输入或者可以为似然函数方法构建概率密度函数。蒙特卡罗模拟样本的检验结果表明, 利用神经网络方法可以在BESIII上获得较好的粒子鉴别效果。     

磁场对四端量子波导中电子输运性质的影响

采用模匹配方法，研究了非均匀磁场下开放的四端量子波导中的电子输运性质. 结果表明，从一端入射的电子可以透射到两个与之垂直的输出端和一个与之平行的输出端. 在没有外加磁场的情况下，两个垂直输出端的输运概率是相同的，但垂直端与水平端的输运概率不同；在外加磁场下，由于磁边缘态效应，两个垂直输出端的输运概率也有着相当大的差别. 通过施加不同的磁场，我们能获得丰富的电子输运结构，如台阶，宽谷，尖峰等；通过调节磁场的大小和比例以及结构参数可控制该量子结构在各输出端的输运概率. 关键词： 电子输运 介观体系 磁效应     

单甲基原位改性SiO2疏水减反膜的制备与性能研究

 在碱性条件下通过TEOS和MTES的共水解缩聚反应制备了单甲基原位改性的SiO₂溶胶，并使用提拉法在K9玻璃基片上镀制了疏水减反膜。通过透射电镜（TEM）考察了镀膜溶胶的微结构，分别使用红外光谱（FTIR）分析了薄膜的组分，用原子力显微镜（AFM）观察了薄膜的表面形貌和起伏状况，用紫外可见光谱（UV-vis）考察了薄膜的减反射性能，用接触角仪测量了薄膜对水的接触角。并使用“R-on-1”的方式测量了薄膜在Nd:YAG激光（1 064 nm，1 ns）作用下的损伤阈值。结果表明，通过共水解缩聚反应可以把甲基引入镀膜溶胶簇团中，改善了溶胶簇团的网络结构，使薄膜得到相当好的疏水性能和更好的抗激光损伤性能，同时薄膜能保持较好的减反射性能。     

甲胺分子的紫外光解离动力学实验研究

在280—287.5 nm区域内,通过实验测定共振增强多光子电离-时间飞行质谱、碎片离子的分质量激发谱以及光强指数等对甲胺分子的光解离通道进行了研究.实验结果证实甲胺分子在单光子能量范围内存在一个电子排斥态,主要的光解离过程为甲胺分子共振吸收1个光子到达该电子排斥态后解离成中性碎片,然后是中性碎片经多光子共振电离形成碎片离子和碎片离子的进一步解离.     

自聚焦透镜高效批量加工的双面研磨抛光法研究

依据双面研磨抛光原理,提出了加工自聚焦透镜平面和斜面辅助工装设计.从工艺技术特点和生产实际过程等方面对设计的工装使用情况进行分析验证.多次大批量加工实践证明,该辅助工装的设计完全满足了自聚焦透镜高效批量加工技术要求,简化整个生产线工艺,减少工艺流程时间,降低材辅料的消耗成本,从而验证了双面研磨抛光法是一种实用的加工自聚焦透镜的新方法.     

纳米TiO_2∶Zn薄膜电极紫外光电特性研究

采用sol-gel法制备了Zn2 掺杂的锐钛矿相纳米TiO2薄膜电极.通过光电流作用谱和电流-电位(I-U)曲线研究了掺杂不同浓度Zn2 的TiO2薄膜电极的光电特性.由光电流作用谱可知,Zn2 的掺杂可显著影响薄膜电极的光电流大小,且掺杂的最佳浓度与薄膜晶粒尺度有关.在320nm单色光照射下,掺杂浓度(摩尔浓度)为0.1%的薄膜电极光电流最大,与未掺杂的本征薄膜电极相比增幅达40%.I-U曲线表明,光照下,随电极电位由正到负逐渐降低,不同掺杂浓度的TiO2薄膜电极中均出现了阳极电流向阴极电流转换的现象,且Zn2 掺杂浓度可影响电极阳极电流的初始电位.另外,无光照的暗态下,各薄膜在负电位区域观察到了相似的随电位降低而迅速增大的阴极暗电流.