Synthesis and electrochemical characteristics of lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate

Four lanthanide complexes with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate were prepared and characterized by elemental analyses, LR, UV-Visible,H-1 NMR, XPS and molar conductance. The redox properties of the lutetium complex with 2-nitro-5,10,15,20-tetraphenylporphyrin and acetylacetonate in dichloromethane were studied by cyclic voltammetry.

20世纪稀土科技发展的回顾与前瞻

本文对20世纪各个时期稀土科技的重大发展作了回顾,并对21世纪初期稀土可能取得的重大应用作了展望。

Synthesis, crystal structure and properties of H-8[P4W14O58Na4 (H2O)(20)] center dot 16H(2)O

A novel heteropoly tungstophosphates, H-8[P4W14O58Na4(H2O)(20)] . 16H(2)O, was synthesized by hydrothermal method and characterized by elemental analysis, IR spectrum and single-crystal X-ray structure analysis. The thermal stability of the compound was investigated by using TG-DTA. The crystal is triclinic system with space group P (1) over bar, a = 1. 137 9(2) nm, b=1. 363 2(3) nm, c=1. 627 1(3) nm; alpha=78. 20(3)degrees, beta=71, 20(3)degrees, gamma= 71. 62(3)degrees; V = 2. 252 5(8) nm(3), Z=1, M-r= 4 374. 38, D-c = 3. 225 mg/cm(3), mu = 18. 007 mm(-1), F(000)=1 972, R=0. 074 2, R-w=0. 200 4. The result of structure analysis shows that the anion of the compound consists of two PW7O29Na2(H2O)(10) subunits and two linked phosphorous atoms. A kind of microporous with size of 0. 661 4 nm X 0. 318 9 nm was formed in the crystal structure.

H_8[P_4W_(14)O_(58)Na_4(H_2O)_(20)]·16H_2O的合成、晶体结构与性质

用水热法合成了 H8[P4 W14 O58Na4 (H2 O) 2 0 ]· 16 H2 O,通过 X射线单晶衍射、元素分析和IR进行了结构表征 ,用 TG- DTA研究了热稳定性 .晶体属三斜晶系 ,P1空间群 ,a=1.1379(2 )nm,b=1.36 32 (3) nm,c=1.6 2 71(3) nm;α=78.2 0 (3)°,β=71.2 0 (3)°,γ=71.6 2 (3)°;V=2 .2 52 5(8) nm3 ,Z=1,Mr=4 374 .38,Dc=3.2 2 5mg/ cm3 ,μ=18.0 0 7mm-1,F(0 0 0 ) =1972 ,R=0 .0 74 2 ,Rw=0 .2 0 0 4 .标题化合物的阴离子是由两个 PW7O2 9Na2 (H2 O) 10 亚单元通过与两个磷原子上键合的氧连接而成 ,分子内形成了一个 0 .6 6 14nm× 0 .3189nm的微孔.

5，10，15，20－四（对－山嵛酸乙酯－α－氧代苯基）卟啉LB膜结构研究

５，１０，１５，２０－四（对－山嵛酸乙酯－α－氧代苯基）卟啉ＬＢ膜结构研究王海水，曾广赋，谷淑珍，席时权（中国科学院长春应用化学研究所长春１３００２２）利用ＬＢ膜技术将分子组装成有序的分子单层或多层体系，研究膜内分子间相互作用和分子的结构，对了解结构...

STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

5,10,15,20-四(对-乙酯苯基)卟啉LB膜的结构

对卟啉类化合物LB膜的结构、电性质和气敏性的研究已见报道。本文利用膜天平和UV-Vis分光光度计研究了标题化合物在气-液界面上的成膜特性、分子间相互作用和LB膜的结构。5,10,15,20-四(对-乙酯苯基)卟啉(TPEPP)由5,10,15,20-四(对-氰苯基)卟啉和乙醇酯化得到。元素分析测定值与计算值相符。λ(CHCl_3,nm):421,515,550,590,645;ν(KBr压

New sphingolipids with a previously unreported 9-Methyl-C-20-sphingosine moiety from a marine algous endophytic fungus Aspergillus niger EN-13

Asperamides A (1) and B (2), a sphingolipid and their corresponding glycosphingolipid possessing a hitherto unreported 9-methyl-C-20-sphingosine moiety, were characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from marine brown alga Colpomenia sinuosa. The structures were elucidated by spectroscopic and chemical methods as (2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (1) and 1-O-beta-D-glucopyranosyl-(2S,2'R,3R,3'E,4E,8E)-N-(2'-hydroxy-3'-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (2). In the antifungal assay, asperamide A (1) displayed moderate activity against Candida albicans.

Development of the East Asian monsoon: Mineralogical and sedimentologic records in the northern South China Sea since 20 Ma

We here reconstruct the past change of the East Asian monsoon since 20 Ma using samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea based On a multi-proxy approach including a monomineralic quartz isolation procedure, identification of clay minerals by X-ray Diffraction (XRD) and grain-size analysis of isolated terrigenous materials. Terrigenous supply to ODP Site 1146 was dominated by changes in the strength of multiple sources and transport processes. Grain-size data modeled by an end-member modeling algorithm indicate that eolian dust from the and Asian inland and fluvial input have contributed on average 20% and 80% of total terrigenous material to ODP Site 1146, respectively. Specifically, about 40-53% of the total (quartz+feldspar) and only 6-11% of the total clay is related to eolian supply at the study site. Detailed analysis of the sedimentary environment, and clay minerals combined with previous studies shows that smectite originates mainly from Luzon, kaolinite from the Pearl River and illite and chlorite from the Pearl River, Taiwan and/or the Yangtze River. The proportion and mass accumulation rate (MAR) of the coarsest end-member EM1 (interpreted as eolian dust), ratios of (illite+chlorite)/smectite, (quartz+feldspar)% and mean grain-size of terrigenous materials at ODP Site 1146 were adopted as proxies for East Asian monsoon evolution. The consistent variation of these independent proxies since 20 Ma shows three profound shifts in the intensity of East Asian winter monsoon relative to summer monsoon, as well as aridity of the Asian continent, occurred at similar to 15 Ma, similar to 8 Ma and the youngest at about 3 Ma. In comparison, the summer monsoon intensified contemporaneously with the winter monsoon at 3 Ma. The phased uplift of the Himalaya-Tibetan plateau may have played a significant role in strengthening the Asian monsoon at similar to 15 Ma, 8 Ma and 3 Ma. (C) 2007 Elsevier B.V. All rights reserved.

Grain-size records at ODP site 1146 from the northern South China sea: Implications on the east Asian monsoon evolution since 20 Ma

273 samples from Ocean Drilling Program (ODP) Site 1146 in the northern South China Sea (SCS) were analyzed for grain-size distributions using grain-size class vs. standard deviation method and end-member modeling algorithm (EMMA) in order to investigate the evolution of the East Asian mon-soon since about 20 Ma. 10-19 mu m/1.3-2.4 mu m, the ratio of two grain-size populations with the highest variability through time was used to indicate East Asian winter monsoon intensity relative to summer monsoon. The mass accumulation rate of the coarsest end member EM1 (eolian), resulting from EMMA, can be used as a proxy of winter monsoon strength and Asian inland aridity, and the ratio of EM1/(EM2+EM3) as a proxy of winter monsoon intensity relative to summer monsoon. The combined proxies show that a profound enhancement of East Asian winter monsoon strength and winter monsoon intensity relative to summer monsoon occurred at about 8 Ma, and it is possible that the summer monsoon simultaneously intensified with winter monsoon at 3 Ma. Our results are well consistent with the previous studies in loess, eolian deposion in the Pacifc, radiolarians and planktonic foraminifera in the SCS. The phased uplift of the Himalaya-Tibetan Plateau may have played a significant role in strengthening the Asian monsoon at 8 Ma and 3 Ma.

焦脱镁叶绿酸-a甲酯20-meso-1-位的亲电取代反应

利用焦脱镁叶绿酸-a甲酯与亲电试剂发生的取代反应，在焦脱镁叶绿酸-a甲酯的20-meso-位上分别引进硝基和卤原子，得到了20-meso位取代的焦脱镁叶绿酸衍生物．所合成的新叶绿素-a衍生物均经UV，IR，~1H NMR及元素分析证明其结构．另外，对叶绿素-a卟吩环上的芳香性和相应的化学反应活性也进行了讨论，提出了可能的亲电取代反应机理．

20世纪运动稳定性研究的三个重要结果

本文论述 2 0世纪运动稳定性理论研究的三个重要结果 :李雅普诺夫函数、谢聂稳定判据、卡利托洛夫定理 .这三个结果都是对一般的连续系统作出的 ,结论明确 ,简单实用 ,因而具有广泛的应用性

准噶尔盆地侏罗系层序格架和油气成藏条件研究

Jurassic is an important hydrocarbon-bearing formation in Junggar Basin. Analyzing in strata sequence stratigraphy and hydrocarbon formation has both theoretical and practical values. First of all, strata sequence stratigraphy of continental facies is a new development and supplement in the theory of stratigraphic geology. Stratum of continental facies, unlike sea facies, has rich sup-plements, rapid facies changes, and was influenced slightly by sea level changes. The structural background and sedimentary environment of the basin in west China are greatly different from those of the basins in east China. So it is important to build the patterns of strata sequence stratigraphy in west China basins. Secondly, it is also of significance to find out all kinds of traps, for the dominant types are structural ones so far. After 50 years exploration, the stratigraphic or litholigic traps have become the main concern. This desertation is mainly focused on establishing the isochronal strtaum frame for Junggar Basin to show the evolvement characters of the basin sediment system and the regionalstuctrue background. By analyzing the conditions and patterns of the regional oil and gas bearing formations with typical cross-sections, we have established the patterns of sedimentary conditions for different reserviors. By authur's study, several fruitful results have been obtained in the following: Strata sequence frame and evolvement characteristics of Jurassic: By studing strata sequence, Jurassic has been divided into 2 second rank strata sequences and 3 third rank strata sequences based on the interface unconformities. Only 2 fourth rank strata sequences were grouped in BaDaoWan group. Also different seismic facies and sediment units have been recognized with the establishment of the of sediment system model. The oil-gas system characteristics in Jurassic: We conclude that hydrocar bon resources have the best oil potential. Potential of coal, carbonaceous and dark mudstone were reduced in turn. In this thesis we have made the evaluation of three hydrocarbon sources and the distribution oil-gas resource, and studied the potentials of hydrocarbon and evolvement for each kind of micro-component of the two main resource rocks. Prediction of paleo-temperature: In Junggar basin the evolvement of paleo-ground temperature can be divided into three stages. From Carboniferous to early Permian grads of ancient ground temperature was 8-5 ℃/100m, 5-3 ℃/100m from later period of Permian to end Trias, 3-2 ℃/100m from Jurassic to early Tertiary. Patterns of Jurassic hydrocarbon-bearing reserviors: There were two kinds of hydrocarbon source of Permian and Jurassic. They form different hydrocarbon - bearing systems. Six fundamental hydrocarbon - bearing trap modeS have been established. Directions for later exploration: There were two kinds of regional belts in Jurassic, One is structural belt caused by Yanshan and Ximalaya process, and the other was the stratum one caused by paleostructural rises.