Tuned C?H Functionalization to Construct Aza‐Podophyllotoxin/Aza‐Conidendrin Derivatives by Means of Domino Cyclization

An efficient domino cyclization method for the construction of aza‐podophyllotoxin/aza‐conidendrin derivatives has been established. Reactions of different dienes with aryl halides in the presence of a palladium catalytic system produced different kinds of podophyllotoxin derivatives through a highly regioselective C? H functionalization. Treatment of dienes with aryl halides that have electron‐withdrawing substituents on the phenyl ring created aza‐podophyllotoxin derivatives by means of the functionalization of the C? H bonds ortho to the C? halide bonds of the incoming aryl halides. The reaction of dienes with 1‐iodobenzene or aryl halides that incorporate electron‐donating groups produced aza‐conidendrin derivatives by means of the functionalization of both sp³ C? H and sp² C? H bonds. The regioselective C? H functionalization for the formation of different pseudo‐podophyllotoxin/‐conidendrin derivatives is proven by analyses of the ¹H NMR spectra of the products and selective X‐ray analyses of the structures of the products. Thus, the palladium‐catalyzed domino cyclization of 1,6‐dienes for the preparation of aza‐podophyllotoxin/aza‐conidendrin derivatives can be controlled by selectively controlling the C? H functionalization.     

Electrical properties and sulfur tolerance of La0.75Sr0.25Cr1−xMnxO3 under anodic conditions

Complex metal oxides with composition of La_0.75Sr_0.25Cr_1−xMn_xO₃(x=0.4,0.5,0.6) (LSCM) have been synthesized and examined as anode materials for solid oxide fuel cells (SOFCs). LSCM compositions show excellent tolerance to both reduction and oxidation but the crystal structure transforms from hexagonal in air to orthorhombic in H₂. The volume change associated with this phase transformation is only about 1%, thus having little effect on other properties. The total electrical conductivity increases with the content of Mn, whereas the resistance to sulfur poisoning increases with the content of Cr. Fuel cells using LSCM as the anode show very good performance when pure hydrogen is used as the fuel. However, they do not appear to be stable in fuels containing 10% of H₂S.     

Construction of a novel Mo/Cu/S cluster with a closed double-cubane-like polyhedron and a chain polymer of W/Cu/S clusters

Reaction of [MoOS(3)](2)(-) and [WS(4)](2)(-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters [Bu(4)N](2)[(MoOS(3))(4)Cu(12)(dtp)(6)], 1, and [Et(4)N][(WS(4)Cu(4))(dtp)(3)], 2, respectively. In cluster 1, the dtp- ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like [Mo(2)O(2)S(6)Cu(6)](2+) core and two incomplete cubane-like [MoOS(3)Cu(3)]+ units. In cluster 2, the [WS(4)Cu(4)](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp- linkages.     

四价钼体系催化丁二烯聚合动力学

本文报导了MoCl₂(n-C₈H₁7O)₂-(i-Bu)₂AlOph体系催化丁二烯聚合动力学研究结果,得到聚合速率方程式R=k(C)_O(2)[M]=k_pa(c)_o(M),表观活化能18.6千卡/摩尔,指数前因子1.6×10¹⁰分^-1,以及不同温度下的催化剂利用率,活性中心浓度,活性中心平均寿命等,还证明了等聚合速率的聚合时间t_O与活性中心平均寿命相近。     

不同结构SOI交叉波导的损耗及串扰特性研究

利用高阶Pade近似的2D-BPM算法,对具有不同弯曲半径及交叉角度的SOI弯曲交叉波导的传输特性进行了模拟、分析和深入研究,发现交叉波导的串扰随弯曲半径及交叉角度增大而减小的规律.在此基础上,对由正弦弯曲、余弦弯曲以及圆弧弯曲三种弯曲波导构成的SOI交叉波导的损耗及串扰特性进行了分析比较.结果表明,由正弦弯曲构成的交叉波导传输损耗最小且串扰最小.     

非定常不定边界问题边界无法的若干进展

对于复杂的非线性工程问题的数值模拟,边界元法（ＢＥＭ）日益显示出优于区域解法的长处,特别是时间相关（需按时段逐步迭代推进）和含各种不定边界（造成可变区域,网络需不断重分）的情形,ＢＥＭ可显著减少存贮要求与计算量．针对非线性问题数值模拟的主要难点,即微分算子线性化,时间相关项与可动边界（非线性边条）的处理等,综述了国内外边界无法学术界的近期研究进展,总体目标是寻求一种适应多种微分算子、非线性迭代和时段推进计算效能高的稳定数值模式．      

若干含多硫基的配合物的合成方法及结构特征

本文综述了近年来我们合成的十二种多硫基的配合物，这些配合物含有Ｓ＾２－２，Ｓ＾２－４，Ｓ＾２－５，Ｓ＾２－６，Ｓ＾２－７等多硫革配体，总结了这些配合物中的金属配位构型，比较了各种多硫基的Ｓ－Ｓ键长及有关键角，归纳了配合物外光谱，并阐述了其中几个配合物与ＮＨ２ＮＨ２的反应性能。     

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Tri‐ or tetrasubstituted alkenes with various substituents can be constructed regio‐ and stereospecifically by treatment of acetylenic sulfones with organozinc reagents in tetrahydrofuran followed by hydrolysis or coupling with halohydrocarbon. Copyright © 2009 John Wiley & Sons, Ltd.     

HOMOMORPHISMS BETWEEN SYMPLECTIC GROUPS

Let F and F_1 be fields with |F| > 5, and n, n_1 integers satisfying $n\geq n_1$. The present paper determines the forms of homomorphisms from SP_{2n}(F) to SP_{2n}(F_1) and that from PSP_{2n}(F) to PSP{2n}(F_l).     

用易拉罐做的几个实验装置

本文介绍三种用易拉罐等旧物自制的简易实验装置。该装置具有取材方便，制作简单，造价低等优点。