Visible-light-induced,autopromoted nickel-catalyzed three-component arylsulfonation of 1,3-enynes and mechanistic insights

Science China Chemistry - A light-induced, nickel-catalyzed three-component arylsulfonation of 1,3-enynes in the absence of photocatalyst is reported. This methodology exhibited mild conditions,...     

Fluorescence and aggregation behavior of poly(amidoamine) dendrimers peripherally modified with aromatic chromophores: the effect of dendritic architectures

PAMAM dendrimers of the zeroth to fifth generation (G0-5) have been peripherally modified with phenyl, naphthyl, pyrenyl, and dansyl chromophores. Their fluorescence behaviors are strongly affected by the dendritic architectures at different generations. These dendrimers modified with hydrophobic chromphores can self-organize into vesicular aggregates at the low generations G0-3 in water. The size and aggregation number of these vesicles decrease with increasing generation from G0 to G3. Critical aggregation concentration determined by fluorescence spectroscopy reveals that these aggregates can be favorably formed in the order of G3 > G2 > G1. In contrast to the vesicles made from traditional amphiphilic compounds, these dendrimer-based vesicles are very adhesive due to the H-bonding interaction and entanglement of dendritic branches located in the outer layer. A large number of multivesicle assemblies, i.e., "twins" and "quins" consisting of two and five vesicles, were clearly identifiable with transmission electron (TEM) and atomic force microscopy. For the dendrimers with peripheral pyrenyl chromophores, triangle-like vesicles were observed in water. The hydrophobic interphase thickness of the vesicular bilayer is ca. 2.0-3.2 nm determined by fluorescence resonance energy transfer methods, which agrees well with the thickness directly observed with TEM.     

不同磁路电子回旋共振离子源引出实验

空间推进所用的电子回旋共振离子源(ECRIS)应具有体积小、效率高的特点. 本文研究的ECRIS使用永磁体环产生磁场, 有效减小了体积, 该离子源利用微波在磁场中加热电子, 电子与中性气体发生电离碰撞产生等离子体. 磁场在微波加热电子的过程中起关键作用, 同时影响离子源内等离子体的约束和输运. 通过比较四种磁路结构离子源的离子电流引出特性来研究磁场对10 cm ECRIS性能的影响. 实验发现: 在使用氩气的条件下, 特定结构的离子源可引出160 mA的离子电流, 最高推进剂利用率达60%, 最小放电损耗为120 W·A^-1; 所有离子源均存在多个工作状态, 工作状态在微波功率、气体流量、引出电压变化时会发生突变. 离子源发生状态突变时的微波功率、气体流量的大小与离子源内磁体的位置有关. 通过比较不同离子源的引出离子束流、放电损耗、气体利用率、工作稳定性的差异, 归纳了磁场结构对此种ECRIS引出特性的影响规律, 分析了其中的机理. 实验结果表明: 保持输入微波功率、气体流量、引出电压不变时, 增大共振区的范围、减小共振区到栅极的距离, 离子源能引出更大的离子电流; 减小共振区到微波功率入口、气体入口的距离能降低维持离子源高状态所需的最小微波功率和最小气体流量, 提高气体利用率, 但会导致放电损耗增大. 研究结果有助于深化对此类离子源工作过程的认识, 为其设计和性能优化提供参考.     

静电场对强激光场非序列双电子电离的影响

利用半经典重碰模型计算并研究了He原子在强激光场与静电场的混合场下的非序列双电子电离过程. 由于静电场破坏了激光场电场的反演对称性，在平行于激光场偏振方向的He²⁺离子动量分布不再具有对称双峰结构. 由于超短脉冲具有相似的非对称性，研究静电场对原子在强场中非序列电离的影响，有助于分析超短脉冲非序列电离的过程，进一步了解非序列双电子电离的机理.     

压力及杂质氢对金属锂弹性特性的影响

针对六角密堆金属锂16个原子超晶胞(supercell)、填隙一个氢原子的周期单元，采用基于密度泛函理论的平面波-赝势方法，研究了零温条件下压力及填隙氢掺杂对体系弹性性质的影响.结果表明氢掺杂导致体系的体模量增加.常压下掺杂体系的弹性常数C₁₁，C₃₃，C₆₆和C₁₂高于单质体系，剪切模量C₄₄有所下降，而C₁₃则与单质体系持平.压力作用下C₁₁，C₃₃和C₆₆一直大于单质体系，但C₁₂的值低于单质体系.在2GPa—4GPa压力区间内，弹性常数C₁₃呈反常变化，小于单质体系；在高压区掺杂体系的C₄₄和C₁₃则高于单质体系的相应量值，压力导致掺杂体系和单质体系之间剪切模的偏离加剧.掺杂体系在压力作用下依然保持压缩模的各向同性，具有和单质体系相似的特性. 关键词： 第一性原理 压力效应 弹性常数 金属锂     

钙钛矿/硅异质结叠层太阳电池:光学模拟的研究进展

近几年,钙钛矿/硅异质结叠层太阳电池发展迅速,效率已经从13.7%提升到29.1%.由于叠层电池器件的制作工艺复杂,而叠层太阳电池中的光学损失对转换效率的影响很大,所以通过光学模拟进而获得高效电池至关重要.本文首先从商业软件和自建模型两方面概述了光学模拟的方法,接着从反射损失和寄生吸收两方面针对光学模拟研究进展进行了总结和分析,最后指出了叠层电池光学模拟过程中需要注意的问题.钙钛矿/硅异质结叠层太阳电池的转换效率极限最高可达40%,具备很大的提升空间,结合模拟工作的研究,叠层电池的发展将会取得更大的进步.     

水分子链受限于单壁碳纳米管结构的密度泛函理论研究

本文采用第一性原理的密度泛函理论,主要以(6,6)Armchair型,(11,0)Zigzag型单壁碳纳米管为研究对象,研究了水分子链在碳纳米管内部吸附的稳定结构,以及结合能随其结构的变化.结果表明:当水分子链受限于碳纳米管内部时,引起碳纳米管直径收缩,这主要是由于水分子链与碳纳米管之间的氢键作用以及范德华弱相互作用所引起的.随着碳纳米管半径的增加,两种单体之间的结合能逐渐减小,但当碳纳米管半径增加至6.78时,其结合能又有所增加,这是由于在优化过程中,水分子链单体之间的氢键作用大于水分子链与碳纳米管之 关键词： 水分子链/单壁碳纳米管 密度泛函理论 结构稳定性     

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates: Synthesis and catalysis towards the ring-opening polymerization of rac-lactide

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates were synthesized and characterized. In the presence of BnOH these complexes are highly active catalysts for the controlled ring-opening polymerization of rac-lactide. The polymerizations are iso-selective and the P_m of polylactide reached 0.77 when the polymerization was performed in toluene at ?60°C; whereas heterorich-polylactide was obtained when the polymerization was carried out in CH₂Cl₂ or THF.     

Interface self-assembly to construct vertical peptide nanorods on quartz template

A rationally designed glycyl-glycine derivative containing a light cleaved pyrenylmethyl ester tail was covalently bound onto the surface of quartz template. The interface self-assembly of this dipeptide building block induced the formation of chemically bound vertically aligned nanorods (CBVANs) with light sensitivity on the template.     

复杂网络时空混沌同步的Backstepping设计

利用Backstepping设计进行了复杂网络时空混沌的同步研究.首先将实现两个混沌系统同步的Backstepping设计推广到由m个时空混沌系统构成任意结构的复杂网络的同步研究中.进一步依据稳定性理论确定了网络同步时配置系数和控制增益满足的关系.整个网络实现同步仅需要在网络中的一个节点施加控制输入即可.进一步通过仿真实验验证了同步机理的有效性.