Organocatalytic asymmetric chlorinative dearomatization of naphthols

An organocatalytic asymmetric chlorinative dearomatization of naphthols was realized for the first time, providing chiral naphthalenones with a Cl-containing all-substituted stereocenter in excellent yields and enantioselectivity (up to 97% yield and 96% ee). The reaction features mild reaction conditions, good tolerance of diverse functional groups and simple reaction operation.     

零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Highly dispersed palladium nanoclusters incorporated in amino‐functionalized silica spheres for the selective hydrogenation of succinic acid to γ‐butyrolactone

Highly dispersed palladium nanoclusters incorporated on amino‐functionalized silica sphere surfaces (Pd/SiO₂‐NH₂) were fabricated by a simple one‐pot synthesis utilizing 3‐(2‐aminoethylamino)propyltrimethoxysilane (AAPTS) as coordinating agent. Uniform palladium nanoclusters with an average size of 1.1 nm can be obtained during the co‐condensation of tetraethyl orthosilicate and AAPTS owing to the strong interaction between palladium species and amino groups in AAPTS. The palladium particle size can be controlled by addition of AAPTS and plays a significant role in the catalytic performance. The Pd/SiO₂‐NH₂ catalyst exhibits high catalytic activity for succinic acid hydrogenation with 100% conversion and 94% selectivity towards γ‐butyrolactone using 1,4‐dioxane as solvent at 240°C and 60 bar for 4 h. Moreover, the Pd/SiO₂‐NH₂ catalyst is robust and readily reusable without loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

激光能量对反钙钛矿GaCMn_3薄膜结构与物性的影响

本文采用脉冲激光沉积方法在LaAlO3(001)单晶衬底上制备了反钙钛矿GaCMn3薄膜,通过控制制备过程中脉冲激光的能量,研究了不同激光能量条件对GaCMn3薄膜结构与物理性能的影响.分别利用X射线衍射仪、原子力显微镜、超导量子干涉仪和物理性能测试系统,对所制备的薄膜的晶体结构、表面形貌和磁性、电输运性质进行了研究.结果表明,制备的样品均为具有多个晶面取向的反钙钛矿薄膜,且薄膜结构和物性明显随制备激光能量的变化而变化.当激光能量为450mJ时,制备的薄膜多晶面取向性最弱,结晶性和表面形貌最优良.实验所得的薄膜均表现出顺磁-铁磁-反铁磁相转变,然而转变过程比块材较平缓,同时薄膜的电阻率并未表现出块材中的突变特征,我们推测该现象很可能是由衬底的应力及衬底的晶格膨胀对薄膜反常晶格变化的抑制作用造成的.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

扩宽OMA-Ⅵ同时谱宽的新方法

OMA－Ⅵ存在同时谱宽窄的缺点，本文用一种新方法大幅度地扩宽了它的同时谱宽，且不降低其系统分辨率，应用效果甚佳。     

The acoustic characteristics of clause, sentence and paragraph boundaries in Chinese Putonghua

The acoustic and perceptive characteristics of discourse units, including clauses, simple sentences, compound sentences and paragraphs, were studied. The acoustic characteristics were based on the analysis of a speech corpus consisted of ten monologues. The Perceived Boundary Strength (PBS) of the monologues was labeled on a five-point scale by 25 participants. The main results are as follows: (1) There is a significant difference in the PBS of clauses (corresponding to intonational phrase), sentences (including simple sentences and compound sentences) and paragraphs. But the PBS of simple sentences and compound sentences is the same, and the pitch reset and pause are also not significantly different between these two kinds of boundaries. (2) The pitch-based cue used to distinguish clauses, sentences and paragraphs appears to be the difference between pre- and post-boundary syllables, but not simply the pitch value of either syllable alone. (3) Declination mainly occurs within intonational phrases, whereas there is no consistent global declination in sentences or in paragraphs. (4) Pauses are longer and more varied at the boundary of larger discourse units. Moreover, there is a significant positive correlation between pause duration and degree of pitch reset at clause boundaries, but not at sentence or paragraph boundaries.     

具Hardy-Sobolev临界指数的奇异椭圆方程多解的存在性

运用变分方法研究了下面问题-Δpu=μupx(s)s-2u f(x,u),x∈Ω,u=0,x∈Ω,多重解的存在性,其中Ω是一个具有光滑边界的有界区域.