Fabrication of PbTiO3 Ceramic Fibers by Sol-Gel Processing

The sol-gel processing was applied to the fabrication of PbTiO₃ fibers. Pb(CH₃COO)₂·3H₂O and Ti(OC₃H ₇ ⁱ )₄ were refluxed with stirring in 2-methoxyethanol to form Pb-methoxyethoxide and Ti-methoxyethoxide, respectively, followed by mixing with stirring in 2-methoxyethanol to form Pb−Ti double alkoxide. The hydrolysis and polycondensation reaction of this double alkoxide gave polymerized products, and as a result the viscosity of the solution increased, suggesting that linear polymers were produced through the hydrolysis and polycondensation reaction. Homogeneous PbTiO₃ gel fibers were drawn from the spinnable viscous solutions, which were wellcrystallized into perovskite type PbTiO₃ at 650°C. The heat-treated fibers were a few centimeters long and from 10 to 100 μm in diameter. The fiber was made up of extremely uniform grains. Electron diffraction revealed a preferred growth of (101) planes along the fiber axis, which might be due to the linear molecular characteristics of the alkoxide.     

硝酸甲酯与不同亲核试剂的SN2反应的理论研究

用从头计算和半经验分子轨道ＡＭ１方法分别对系列亲核试剂和硝酸甲酯的电子结构以及它们之间的气相ＳＮ２反应进行了理论研究，揭示了反应过程中体系的结构，能量和电荷的递变规律，由反应活化能得了这些亲核试剂的亲核性次序为：ＯＨ＾－〉Ｆ＾－〉Ｉ＾－〉ＮＯ＾－３〉ＣＮ＾－〉Ｂｒ＾－〉Ｃｌ＾－〉Ｎ＾－３。     

Novel Reactions of Organomolybdenum and Organotungsten Compounds: Additive–Reductive Carbonyl Dimerization,Spontaneous Transformation of Methyl Ligands into μ-Methylene Ligands,and Selective Carbonylmethylenation

Hitherto there was no reaction known that permits transformations of R¹R²-CO → 0.5 R¹R²R³C–CR¹R²R³ in one step. This type of additive–reductive carbonyl dimerization is now possible using alkoxy(alkyl)tungsten(v) complexes with aromatic, heteroaromatic or α,β-unsaturated aldehydes and ketones. When a corresponding phenyl complex was employed in a test experiment, it was revealed that an aliphatic ketone could be used as the substrate in this reaction. A second interesting type of reaction is the transformation of CH₃ ligands into μ-CH₂ ligands, which occurs during the treatment of MeLi or Me₃Al with molybdenum or tungsten chlorides (oxidation states VI and V, for Mo additionally IV) at low temperatures with liberation of CH₄. Here, the question arises as to whether the intermediate involved has a terminal CH₂ ligand (Schrock carbene complex) or a μ-CH₃ ligand (CH₃ bound by a two-electron three-center bond to two metal atoms). Of all the μ-CH₂ complexes obtained, those which were synthesized by the action of MeLi on molybdenum chlorides can be recommended as reagents for carbonylmethylenation of aldehydes and ketones. They display high selectivity, very low basicity, a surprising resistance to protons, they are readily available, can be easily modified and, as regards their selective behavior, they have been investigated more thoroughly than other readily accessible carbonylmethylenation reagents of comparable selectivity. The results of NMR spectroscopic investigations on the structure of the μ-CH₂ complexes, and associated reaction mechanisms are discussed. A survey of carbonylmethylenation reagents, which have been reported in the literature, permits comparisons to be made with carbonylmethylenating molybdenum and tungsten complexes.     

Fraktionierte Kristallisation von Ammonium- und Magnesiumdoppelnitraten der Ceriterden; Bestimmung der Trennfaktoren und Vergleich der Trennwirkung

Summary The Separation Factors for Pr/La, Nd/Pr, and Sm/Nd, characterizing the crystallization of ammonium and magnesium double nitrates under practical conditions, were determined analytically and are discussed. They confirm that La and Pr can be separated better by fractional crystallization of ammonium double nitrates, whereas in the presence of Sm the magnesium double nitrates are preferable.

     

CoMoK／γ—Al2O3水煤气变换催化剂的硫化及反硫化

以Ｈ２Ｓ和ＣＳ２作硫化剂，用ＰＰＳ和ＴＰＤＳ方法研究了水煤气变换催化剂ＣｏＭｏＫ／γ－Ａｌ２Ｏ３的硫化及反硫化过程。用Ｈ２Ｓ／Ｈ２硫化时，只发现Ｈ２Ｓ的消耗和Ｈ２Ｏ的生成，用ＣＳ２／Ｈ２硫化时，只发现Ｈ２Ｓ的消耗和Ｈ２Ｏ的生成。用ＣＳ２／Ｈ２硫化时，首先生成ＣＯ２，然后是ＣＨ４，Ｈ２Ｏ和Ｈ２Ｓ，ＴＰＧ实验表明催化剂表面上积炭，造成催化剂和活性降低，但积炭在水煤变换反应进行了逐渐除法。ＴＰＤＳ实验表     

[1-芳基甲羰基-2-(1,2,4-三唑-1-基)]乙基-N,N-二烷基二硫代氨基甲酸酯衍生物的合成、结构表征及生物活性研究

以芳香基三唑类杀菌剂三唑酮为先导物设计并合成了5个含N,N-二烷基二硫代氨基甲酸酯的芳香三唑类化合物, 通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征. 用X射线单晶衍射测定了[α-(4-甲氧基苯甲酰基)-2-(1,2,4-三唑-1-基)]乙基-N,N-二甲基二硫代氨基甲酸酯的晶体结构, 晶体属于三斜晶系, 空间群, 晶胞参数为: a＝0.73482(15) nm, b＝1.1051(2) nm, c＝1.1209(2) nm, α＝90.32(3)°, β＝101.97(3)°, γ＝105.13(3)°, V＝0.8578(3) nm³, Z＝2, D_c＝1.357 g/cm³, F(000)＝368, µ＝0.324 mm^－1. 生物测试结果显示这5种有机化合物都具有杀菌性和植物生长调节活性     

水热合成稀土氟化物材料YLiF4∶Yb,Tm的上转换发光特性

利用水热法合成了掺杂Tm3 和Yb3 的YLiF4材料, 并研究了Tm3 和Yb3 在材料中的光吸收, 以及980 nm红外光激发下不同Tm3 浓度掺杂下的上转换发光特性. 实验发现, 在980 nm激光激发下, 材料可发出可见光. 上转换发光光谱中包括蓝光和红光. 与蓝光相比, 红光强度要弱1～2个数量级. 上转换发光强度和浓度关系研究显示, 当Tm3 浓度为0.3% (摩尔分数)时上转换发光达到最强, 大于0.3% (摩尔分数)后发光开始减弱. 通过分析输出光强与泵浦功率的双对数曲线, 发现Tm3 的蓝光发射和红光发射均属于双光子过程.     

Chromatographic effect during the preparation of γ-Al2O3 supported Cu?Mn catalysts

A strong chromatographic effect has been established during copper-managenese formate impregnation of γ-Al₂O₃. The samples obtained have been characterized by adsorption, IR, X-ray and magnetochemistry methods.     

Reactions of Hydroxyazolidines with π-Donor Heterocycles. 3. Reaction of 1-Acetyl-5-hydroxypyrazolidines with Oxindoles

The reaction of oxindoles with 5-hydroxypyrazolidines on the surface of potassium fluoride-modified alumina leads to 3-(5-pyrazolidinyl)oxindoles. The structure of these products was studied.     

两个具有PTP1B抑制活性的4-羟基丁内酯化合物的全合成研究

Two new naturally 4-hydroxylated butenolides were concisely synthesized in excellent enantiomeric purities. An aldol condensation and a Suzuki reaction served successfully as the key steps in the synthesis.