Hydrothermal synthesis and crystal structure of a novel compound: [Ni(phen)(3)](2)[(SiMo10V2O40)-O-IV((VO)-O-IV)2]center dot 2H(2)O

A novel compound [Ni(phen)(3)](2)[(SiMo10V1/2O40)-O-V((VO)-O-IV)(2)] . 2H(2)O has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the triclinic, system, space group P-1, a = 12.378(4) Angstrom, b = 14.148(5) Angstrom, c = 14.316(2) Angstrom, alpha = 105.91(2)degrees, beta = 95.31(2)degrees, gamma = 96.89(3)degrees, V = 2373.0(12) Angstrom(3), Z = 1, (lambdaMo(Kalpha)) = 0.71073 Angstrom, R1 (wR2) = 0.0869(0.2174). Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range of 1.51 < theta < 22.50degrees using the omega-scan technique. Empirical absorption correction (psi scan) was applied. The structure was solved by the direct method and refined by the Full-matrix least-squares on F-2 using the SHELXL-97 software. X-ray crystallographic study showed that the title compound contained a bi-capped alpha-Kegin-type [(SiMo10V2O40)-O-IV((VO)-O-IV)(2)](4-) polyoxoanion.

Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates

Two novel dibenzo-18-crown-6 sodium isopolytungstates, [(DB18C6)(CH3OH)Na](2)W(6)O(19)(.)DB18C6(.)H(2)O 1 and [(DB18C6)(DMF)(2)Na](4)W(10)O(32)(.)2DMF(.)2H(2)O 2, have been synthesized in mixed methanol and acetonitrile solvents and characterized by elemental analysis, TGA, IR and single crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic space group C2/c with a = 23.182(8), b = 19.527(2), c = 18.737(3) Angstrom, beta = 115.15(2)degrees, V = 7678(3) Angstrom(3), Z = 4, and R1(wR2) = 0.0611(0.1504). The compound 2 crystallizes in the monoclinic space group P21/n with a = 16.516(2), b = 22.325(6), c = 20.425(7) Angstrom, beta = 91.78(2)degrees, V = 7528(3) Angstrom(3), Z = 2, and R1(wR2) = 0.0397(0.0773). The compound 1 exhibits a novel organic-inorganic sandwich-type structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of W6O192-. In compound 2, all Na+ ions are thoroughly enveloped into the organic moieties of crown ether and DMF molecules and are connected with the 'naked' polyanions W10O324- via the electrostatic attraction.

Synthesis and crystal structure of a new supermolecular compound: [C12H24O6][H3PMo12O40]center dot 22H(2)O (C12H24O6=18-crown-6)

The title compound, [C12H24O6][H3PMo12O40]. 22H(2)O, was synthesized by the self-assembly of 18-crown-6 (abbreviated as C12H24O6 or 18C6) and H3PMo12O40 in the mixed solvent of CH3OH and CH3CN, and was characterized by IR, H-1 NMR and Xray diffraction for the first time. Crystal data: Triclinic, P (1) over bar, a = 13.428(3) Angstrom, b = 13.557(3)A, c = 14.642(3) Angstrom, a = 105.39(3)degrees, beta = 90.06(3)degrees, gamma = 119.56(5)degrees, V = 2207.5(8) Angstrom(3), Z = 1, R1 = 0.0719, wR2 = 0.1990. It has a disordered alpha-Keggin PMo12O403- anion, which contains the strong alternating short (mean 1.844 Angstrom) and long (mean 1.958 Angstrom) Mo-O-Mo bonds. In the unit cell, crown ethers and molybdophosphates are alternatively arranged in good order along c-axis. An oxonium ion is located at the center of a crown ether molecule., Oxonium ion interacts with 18C6 by the means of hydrogen bonds (mean 2.7771 Angstrom), which are electrostatic or resonant. The observations show the existence of [H3O(C12H24O6)](+) (C) 2000 Elsevier Science B.V. All rights reserved.

长链烷氧基取代苯基卟啉衍生物的解吸电子离子化质谱

长链烷氧基取代苯基卟啉化合物是一类性能良好的充电膜材料及照相感光材料.本文对合成一系列四-(对-烷氧基笨基)卟啉(取代基如式(1)R1=R2=R3=R4=H;(2)R1=C16H33,R2=R3=R4=H;(3)R1=R2=C16H33,R3=R4=H;(4)R1=R2=R3=C16H33,R4=H;(5)R1=R2=R3=R4=C16H33)进行质谱分进,结果表明,当用DEI电离方式时,不仅能给出较大丰度的分子离子峰,而且其EDIMS谱还清楚地反映出卟啉苯环羟基氢取代基团的丢失规律.然而其他电离方式却难以达到这样的效果.2 样品与仪器 部分所用样品承吉林大学王永祥博士赠送.质谱实验在 VG公司生产的 Quattro三级四极串联质谱仪上进行,采用DCI方式进样,但不通反应气故称DEI,离子源温度为100℃,发射电流260μA,用IBM386数据系统采集数据.

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.

海洋红藻多管藻和松节藻的化学成分及抗氧化活性研究

海洋生物具有产生丰富多样的次生代谢产物的能力，其中红藻门松节藻科海藻卤代次生代谢产物以其结构新颖、生物活性独特引起了天然产物化学家的重视。 本论文对海洋红藻多管藻和松节藻进行了化学成分研究，综合利用各种色谱学方法 (硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备高效液相色谱以及重结晶等) 和现代波谱学技术 (IR、UV、EI-MS、FAB-MS、HR-ESI-MS、CD、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)，共分离鉴定了100个化合物，发现25个新化合物。 从多管藻中分离鉴定38个化合物 (24个溴酚化合物)，其中7个新化合物 (均为溴酚化合物)，包括1个菲并呋喃结构溴酚 (P1), 2个二氢菲结构溴酚 (P2, P3)，1个含 5,7-dihydrodibenzo[c,e]oxepine 结构溴酚 (P4)和3个简单溴酚 (P5, P6, P7)。P1 (urceolatin) 属首例报道的具有菲并呋喃结构的天然产物，从该种中分离的化合物P12 和 P13 可能是其生源合成的前体。P2和P3为第二例报道的具有二氢菲结构的溴酚化合物。 从松节藻中分离并鉴定了62 个化合物，其中18 个为溴酚类新化合物，44 个为已知化合物。化合物具有多变的取代基团，包括2 个脲基吡咯烷酮溴酚化合物 (R1, R2), 4 个γ-脲基丁酸溴酚化合物 (R3-R6)，5 个酰胺溴酚化合物 (R7, R8, R9, R13, R14)，1 个溴酚砜化合物 (R12), 1 个Xanthene 溴酚化合物 (R10)和5 个简单溴酚化合物 (R11, R15, R16, R17, R18)。R1、R2 是首例报道的含有脲基吡咯烷酮片段的天然产物，R10 为首次报道的溴代Xanthene 类天然产物。 对分离到的化合物进行了清除DPPH 和ABTS两种自由基活性的筛选。结果发现溴酚类天然产物具有显著的DPPH自由基清除活性，其中R3 的IC50 仅为3.3 μM, 其活性强度约为阳性对照BHT (IC50 为82.1 μM) 的24倍。另外，溴酚类天然产物对ABTS自由基有较强的清除活性，R2 的TEAC（Trolox efficency activity capacity）值为5.2 mM，约为阳性对照 (ascorbic acid, 1.02 mM) 的 5 倍。初步的构效关系研究发现，稠环分子、多羟基和邻位甲氧基等结构特点能有效增强DPPH 自由基清除活性；特殊取代基如脲基、吡咯烷酮等含有氮原子的基团，能有效增强ABTS 自由基清除活性，多羟基、溴代等结构特点也使其活性有所增强。 本研究结果丰富了海藻卤代化合物的结构类型，为多管藻和松节藻的合理利用提供了一定的科学依据。

青海湖区东部沙地植被及其特征研究

根据野外样地调查资料,对青海湖区东部沙地植被从区系特征及其物种多样性进行了研究,结果表明:①青海湖东部沙地植被种类组成简单,共有27科58属71种.其中禾本科比重最高为22.535%,其次为菊科占12.676%;再次为豆科占9.8592%;桔梗科等14科比重较小均占1.4085%.②地理成分上,湖东沙地植物区系以世界分布为主,共有16科,湖区植物区系中的优势科均为世界广布科;其次是温带成分10科;热带亚热带成分仅有1科.③生活型以多年生地面芽植物和地下芽植物为主,两者种类系数之和达到76.06%,一年生植物所占种类比重最小.④湖东沙地植被群丛多以单一优势种为主,物种多样性指数H、丰富度指数R1和均匀度指数Jsw三者的变化趋势大致是一致的,即随物种的增多,他们的指数趋向增大;生态优势度C的变化趋势则正好相反.⑤湖东沙地群丛物种相似性差异较大.固定沙地之间植被群丛相似性较高,流动半流动沙地与流动沙地之间则较低.

青海湖地区芨芨草草地土壤种子库的初步研究

选择青海湖地区的次生芨芨草草地为研究对象,以围栏内封育和围栏外自由放牧的草地做对照,研究了围栏内外土壤种子库的萌发状况、密度和数量、物种多样性,以及土壤种子库与地上植被的关系。结果表明,围栏内外土壤种子库的萌发趋势非常相似,但是萌发种子累计数量不同;围栏内外土壤种子库中萌发种子的平均密度分别为3660和2460粒·m-2,围栏内萌发种子数比围栏外提高了48.8%;围栏内外土壤种子库的物种多样性指数差异较大,围栏内外丰富度指数R1分别为17和13,R2为3.693和2.832,丰富度围栏内大于围栏外,多样性指数和丰富度指数具有相同的规律,均匀度指数围栏内外分别为0.812和0.857,则是围栏外大于围栏内。围栏内外地上植被群落组成存在显著差异,围栏内的封育草地的物种丰富度和多样性指数均大于围栏外的放牧草地,而均匀度指数则呈相反趋势。

甘肃临夏盆地龙担剖面晚新生代磁性地层与古环境

Linxia Basin, situated in the northeast belt of the Tibetan Plateau, is a late Cenozoic depression basin bounded by the Tibetan Plateau and the Chinese Loess Plateau. The Cenozoic deposition, spanning over 30Ma, in which very abundant mammal fossils were discovered, is very suitable for study of uplift processes and geo-morphological evolution of the Tibetan Plateau. The Longdan section (35°31′31.6″N，103°29′0.6″E) is famous for the middle Miocene Platybelodon fauna and the late Miocene Hipparion fauna for a long time and is also one of the earliest known places for wooly rhino, which lies on the east slope of Longdan, a small village of township Nalesi in the south of the Dongxiang Autonomous County, Linxia Hui Nationallity Autonomous Prefecture. The Longdan mammal fauna was discovered at the base of the Early Pleistocene loess deposits at Dongxiang, where the lithology is different from the typical Wucheng Loess on the Chinese Loess Plateau. The rich fossils contain many new species and the major two layers of fossils are in the loess beds. Geologically the fossiliferous area is located in the central part of the Linxia Cenozoic sedimentary basin. Tectonically the Linxia Basin is an intermountain fault basin, bordered by the Leijishan major fault in the south and the north Qinling and Qilianshan major faults in the north. The section is 51.6m thick above the gravel layer, including the 1.6m Late Pleistocene Malan Loess on the top and the other loess-paleosol sequences in the middle of the section. The base of the section is the Jishi Formation, consisting of gravel layer of 13 ~ 17m thick. In this study, 972 bulk samples were collected with an interval of 5cm and other 401 orientied samples were taken with a magnetic compass. In the laboratory, the paleomagnetism, medium grain size, susceptibility, color, micromorphology, anisotropy of magnetic susceptibility were analyzed. From the stratigraphic analysis, the Longdan section from the top 0.3m to the bottom 51.6m, containing 5 normal polarities (N1-N5) and 5 reversal polarities (R1-R5). The paleomagnetic results show N3 is the Olduvai subchron in the middle of the Matuyama chron, and then the chronology of the Longdan mammal fauna is constructed along the section. The Matuyama-Gauss boundary is 45m and N5 enters Gauss chron. The Olduvai subchron with the age of 1.77 ~ 1.95Ma is found just in the upper fossiliferous level of Longdan mammal fauna. Taking the deposit rate of the section into account, the geological age of the upper fossiliferous level of Longdan mammal fauna is estimated to be about 1.9Ma. The lower fossiliferous level is just below the Reunion subchron and its age is estimated to be 2.25Ma. In addition, anisotropy of magnetic susceptibility of the loess-paleosol and other climatic indexes were used for discussing the late Cenozoic paleoenvironmental changes at Longdan, from which the Longdan area should have been an area of predominantly steppe the same as the Longdan mammal fauna.