Three New Serratane Triterpenoids from Phlegmariurus squarrosus

Three new serratane triterpenoids, (3α,14α,15α,21α)‐3,14,15,21,29‐pentahydroxyserratan‐24‐oic acid ( 1 ), (3α,21β)‐serrat‐14‐ene‐3,21,24,30‐tetraol ( 2 ), and (3α,21α)‐serrat‐14‐ene‐3,21,24,29‐tetraol ( 3 ), were isolated from Phlegmariurus squarrosus, together with eight known compounds. Their chemical structures were elucidated on the basis of in‐depth spectroscopic analyses.     

Synthesis and Crystal Structure of Two One—dimensional Chain Copper Complexes [Cu（TTA）2（4,4‘’—azpy）] and [Cu（TTA）2（3,3‘’—azpy）

Two copper complexes [Cu(TTA)₂(4,4′‐azpy)] (1) and [Cu‐(TTA)₂(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm³, D_c = 3.425 g/cm³, γ = 2.113 mm^?1, F(000) = 694, R₁ = 0.0594, wR₂ = 0.1499. The crystal 2 belongs to monoclinic with space group P2₁/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm³, Z = 2, D_c = 1.646 g/ cm³, μ = 1.015 mm^?1, F(000) = 694, R₁, = 0.0535, wR₂ = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands.     

Configuration of MFI-type zeolite interacting with the probe molecule P(CH<Subscript>3</Subscript>)<Subscript>3</Subscript> – a theoretical study

With P(CH₃)₃ as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH₃)₃]⁺ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH₃)₃]⁺ species from the first to the second Brönsted acidic site.     

Selective Inversion of the Proximal or Distal Hydroxyl Groups in syn,syn-3-[N-(Alkoxycarbonyl)amino] 1,2-Diols via Cyclic Sulfates

The formation of cyclic sulfates (4) from syn,syn-3-[N-(benzyloxycarbonyl)amino] 1,2-diols provides a common intermediate to access other diastereomers via two inversion procedures. Thermolysis of the cyclic sulfates in acetonitrile normally leads to inversion of the distal hydroxyl group to form a 1,3-oxazin-2-one (6). Catalytic hydrogenation of the cyclic sulfates under basic conditions (NEt(3)) results in inversion at the proximal hydroxyl group to form a 1,3-oxazolidin-2-one (5).     

Selection of Anodic Material Used in Electrolytic Process for Producing Hypophosphorous Acid

Black lead, Ti-Ru and Ti-PbO2 were used as anode and stainless steel was used as cathode The electrolytic process of producing hypophosphorous acid with four-compartment electrodialytic cell was studied. The comparison of some factors, such as anodic voltage, product concentration and current efficiency, of black lead, Ti-Ru, and Ti-PbO2 electrodes was conducted. As a result, theTi-PbO2 electrode is the optimal anode material used, it can be in electrolytic process for producing hypophosphorous acid.     

Distinct chemoselectivity in the reaction of N-(thio)phosphoryl imines with diethylzinc

This report describes the reaction of N-(thio)phosphoryl imines with diethylzinc under different conditions. An interesting and distinct chemoselectivity between hydrogen-addition and ethyl-addition to imine double bond is disclosed: in weakly polar solvent, e.g. toluene, N-(thio)phosphoryl imines were exclusively reduced in excellent yields via a β-H transfer from diethylzinc to imine double bond; in polar solvents like THF, the reduction product was competitively formed as a major product together with the minor product resulting from ethyl-addition to imine double bond; in sharp contrast, in the presence of strong coordinative additive N,N,N′,N′-tetramethylethylenediamine (TMEDA), the ethylation product was formed exclusively from the reaction of N-(thio)phosphoryl imine with diethylzinc. These results are discussed and explained in terms of the coordination interactions between the imine, solvent, and additive with diethylzinc.     

有害杂草的微量元素分析

紫茎泽兰和水葫芦均属有害杂草，大规模防治的有效方法还未找到，本文分析研究了采自昆明郊区的紫茎泽兰和滇池水域的水葫芦中微量元素的含量，为进一步开发利用这两种杂草提供科学依据。     

K/Ru(10ī0)表面上的CO-4a1轨道对称性确定

用同步辐射角分辨偏振紫外光电子谱对Ｋ／Ｒｕ（１０１０）面上吸附分子轨道的对称性测量发现：结合能在１１、．２ｅＶ的ＣＯ－４ａ１（４σ）分子轨道对ｓ偏振光（在沿〈１２１０〉的人射面）是禁戒的。结果表明由于Ｋ的强烈影响,ＣＯ的分子轨道重新排列（ｓＰ＾２杂化）。依据选择定则和分子轨道的对称性６说明,ｓｐ＾２再杂化的ＣＯ分子吸附的桥位取向是〈１２１０〉晶向。     

TEOS-MTES基SiO2溶胶微结构的SAXS研究

正硅酸乙酯(TEOS)为前驱体,在碱性条件下制备含有无定形SiO2颗粒的溶胶,以甲基三乙氧基硅烷(MTES)在酸性条件下获得聚甲基硅氧链,二者混合后应用同步辐射X射线进行混合溶胶的SAXS散射强度测定,计算了溶胶的平均回转半径、平均粒径、两相界面层厚度、散射体体积分数、两相间比表面积等参数,辅以光子相关光谱法(PCS)和透射电子显微镜(TEM)观测溶胶粒度,证实SiO2颗粒被MTES混合物连接成族团.实验发现所测混合溶胶样品均表现出对Porod定理的负偏离,说明溶胶中颗粒与溶剂之间存在很明显的两相间界面层.     

聚酰亚胺中空纤维膜用于甲醇/甲基叔丁基醚的分离

甲醇／甲基叔丁基醚混合物的膜法分离，大多采用渗透汽化方法，少有采用蒸汽渗透法。用聚酰亚胺中空纤维膜，对以蒸汽渗透和渗透汽化两种方式分离甲醇／甲基叔丁基醚混合物（甲醇质量分数为0．01－0．30）的效果进行了对比。结果显示，在甲醇质量分数低于0．05时，蒸汽渗透较渗透汽化法的分离性能优越。