SYNTHESES OF BIS(TERT-BUTYLCYCLOPENTADIENYL)LANTHANOID CHLORIDE COMPLEXES AND CRYSTAL-STRUCTURES OF BIS(TERT-BUTYLCYCLOPENTADIENYL)CHLORO(BISTETRAHYDROFURAN)-PRASEODYMIUM AND BIS(TERT-BUTYLCYCLOPENTADIENYL)-CHLOROTETRAHYDROFURANYTTERBIUM

Reaction of lanthanoid trichloride with two equivalents of sodium t-butylcyclopentadienide in tetrahydrofuran affords bis(t-butylcyclopentadienyl)lanthanoid chloride complexes (t-BuCp)2LnCl. nTHF (Ln = Pr, Nd, n = 2; Ln = Gd, Yb, n = 1). The compound (t-BuCp)2PrCl.2THF (1) crystallizes from THF in monoclinic space group P2(1)/c with unit cell dimensions a = 15.080(3), b = 8.855(2), c = 21.196(5) angstrom, beta = 110.34(2)degrees, V = 2653.9 angstrom-3 and D(calcd) = 1.41 g/cm3 for Z = 4. The central metal Pr is coordinated to two t-BuCp ring centroids, one chlorine atom and two THF forming a distorted trigonal bipyramid. The crystal of (t-BuCp)2YbCl.THF (2) belongs to the monoclinic crystal system, space group P2(1)/n with a = 7.726(1), b = 12.554(2), c = 23.200(6) angstrom, beta = 97.77(2)degrees, V = 2229.56 angstrom-3, D(calcd) = 1.50 g/cm3 and Z = 4. The t-BuCp ring centroids, the chlorine atom and the oxygen atom of the THF describe a distorted tetrahedron around the central ion of ytterbium.

铕和铽与3,4-呋喃二甲酸双核配合物的合成、表征及其晶体结构

本文首次合成了铕(Ⅲ)和铽(Ⅲ)与3,4-呋喃二甲酸配合物,研究了它们的IR、DTA、TG、DTG和荧光光谱等性质,并完成了单晶的晶体分析。结果表明,配合物为〔Ln·HL_2(H_2O)_2〕_2·2H_2O(Ln=Eu(Ⅲ),Tb(Ⅲ);H_2L=3,4-呋喃二甲酸),属单斜晶系,P2/c空间群,Z=2,晶胞参数对铕和铽配合物分别为α=10.842(1),10.801(4);b=8.725(2),8.664(2);c=16.366(4),16.308(6)A;β=93.50(1),93.67(3)°;V=1545.3(5),1523.0(8)A~3。

维生素B_1-锌配合物的晶体结构

用X射线单晶衍射方法测定了ZnVB_1晶体结构。晶体属单斜晶系,空间群为C2/c;α=25.747(5),b=8.461(0),c=17.407(3)A;β=105.79(1)°,Z=8。晶体结构是用Patterson函数法与Fourier计算得到,最后的R=0.0283。金属锌离子与嘧啶环上的N(1)原子以及三个氯离子键合,形成四配位的络合物。配位多面体是稍有扭曲的四面体。Zn—Cl键的平均距离为2.266A,Zn—N键长为2.041(4)A。

Sesquiterpenes from Laurencia similis

One new sesquiterpene, (4E)-1-bromo-5-[(1'S*, 3'R*)-3'-bromo-2',2'-dimethyl-6'-methylenecyclohexyl]-3-methylpent-4-ene-2,3-diol (1), and fifteen known sesquiterpenes, isopalisol (2), luzonensol (3), palisadin B (4), aplysistatin (5), palisadin A (6), 4-hydroxyl-palisudin C (7), 5-acetoxypalisadin B (8), 10-hydroxyaristolan-9-one (9), aristol-8-en-1-one (10), aristolan-9-en-1-one (11), aristolan-1(10)-en-9-one (12), aristolan-1( 10)-en-9-ol (13), aristolan-1(10), 8-diene (14), aristolan-1,9-diene (15) and aristofone (16), were isolated from a sample of marine red alga Laurencia similis. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data. Compounds 2-9, and 16 were isolated for the first time from this species. All these metabolites were submitted for a cytotoxicity assay against the tumor cell line BEL7402 (human liver adenocarcinoma), but all of them were found inactive (IC50 > 10 mu g/mL).

海洋生物碳酸盐硼同位素技术研究及其应用

近些年来，利用海洋生物碳酸盐硼同位素重建古海水pH，计算当时大气CO2含量，进而推测古气候的变化已成为国际同位素地球化学界研究的热点问题，被称为δ11B-pH技术。古海水的δ11Bsw是否恒定、B(OH)4−和B(OH)3间理论的硼同位素分馏系数4/3是多少以及碳酸盐的δ11Bcarb是否等于海水B(OH)4−的δ11B4值是该技术成功的三个关键。但到目前为止以上三项问题还没得到完全证实。 为确定方解石的硼同位素组成与海水pH的依赖关系，已进行过大量实验研究。他们的结果与预期的假设一致，支持了B(OH)4-是掺入方解石结构主要形式的假设。但近期 Pagani(2005)指出B(OH)4-也许不是掺入方解石结构的主要形式，B(OH)3也可能同时掺入进碳酸盐。肖应凯等(2006)的无机碳酸盐沉积实验发现碳酸盐沉积和母液间的硼同位素分馏系数大于1的异常现象，认为碳酸钙中镁或其它微量元素的存在是重要原因，推断这是在高pH生成Mg(OH)2沉积后11B优先掺入的缘故，推断有B(OH)3掺入碳酸盐的可能。 以前进行的沉积实验，只考虑到碳酸钙本身，确实证明了硼只以或主要以B(OH)4-参与进生物碳酸钙。但天然的海洋生物碳酸盐含有镁、锶、铁等微量元素，这些微量元素的存在可能会改变硼的参与行为，从而对硼同位素分馏产生影响。现代珊瑚礁中水镁石普遍存在，这是否会影响珊瑚的硼同位素组成而导致δ11B-pH技术的误差还值得研究。 针对以上问题，主要对硼掺入进Mg(OH)2的形式及分馏机理，现代珊瑚中镁、锶等微量元素与硼浓度及硼同位素的关系进行研究，并用生物碳酸盐的硼同位素对陆相产出有孔虫的沉积环境进行判别。 通过研究，得到以下几点认识： 1. 在Mg(OH)2从pH9.5～13的含硼合成海水中沉积时，Mg(OH)2沉积11B的变化范围为-1.20‰～28.26‰，高于合成海水的11B (-7.00±0.07‰)，沉积和海水间的硼同位素分馏系数固/液变化范围为1.0177～1.0569，平均值为1.0329，这是H3BO3优先掺入的结果，造成11B在Mg(OH)2沉积中富集。 2. Mg(OH)2沉积的硼浓度和硼在Mg(OH)2沉积与滤液间的分配系数Kd的变化范围分别为228.61 g/g～937.79 g/g和9.31～494.20。高pH值时硼掺入Mg(OH)2的过程中吸附作用占有重要位置。 3. Mg(OH)2吸附实验表明，硼掺入Mg(OH)2非常迅速，4 h能达到平衡。平衡后Mg(OH)2中硼浓度[B]固和固相与溶液相间的分配系数Kd随pH设定的升高和固液比的降低而降低。而且最高的[B]固和Kd均远高于硼被金属氧化物或粘土矿物吸附时的对应值，表硼具有很强的掺入Mg(OH)2的能力。 4. 吸附平衡时溶液相的11B液f (-19.2‰～-17.8‰)均低于原始溶液的11B液i (-7.00±0.07‰)，计算的Mg(OH)2与平衡溶液间的硼同位素分馏系数固-液变化范围为1.0186～1.0220，平均值为1.0203。这充分表明，硼掺入Mg(OH)2时11B优先进入固相，这是B(OH)3优先掺入的结果。 5. 硼以B(OH)3和B(OH)4-两种形式同时掺入Mg(OH)2，并以B(OH)3优先掺入为主，pH设定越低掺入的B(OH)3比例越高。 6. 硼将通过吸附和与Mg(OH)2的沉淀反应而掺入Mg(OH)2，两者共同决定了Mg(OH)2中硼同位素分馏特征。 7. Ca、Sr、B和Na在珊瑚中均得到富集，而Mg在珊瑚中却是贫化的。珊瑚的B浓度主要不是由这几种元素决定的。 8. 珊瑚δ11Bcarb的变化范围为22.8‰～27.9‰，平均为25.2‰。除与B浓度相关性明显外，珊瑚δ11Bcarb与其它四种元素的相关性不强。北海涠洲岛、灯楼角和三亚三地珊瑚与海水间的分馏系数carb-sw分别为0.9839、0.9847和0.9850。珊瑚与海水B(OH)3间的分馏系数carb-3的变化范围为0.9772～0.9800，平均值为0.9788，随pH升高carb-3减小。珊瑚的平均δ11Bcarb基本位于采用=0.9772时理论计算的δ11B4曲线之上，而且都低于原始合成海水的δ11Bcarb，表明硼是以B(OH)3和B(OH)4-两种形式同时掺入进珊瑚中的，并以B(OH)4-优先掺入为主。 9. 由于B(OH)4- 和B(OH)3同时进入到珊瑚中，d11Bcarb=d11B4的假设不能成立，由所测定生物碳酸盐的δ11Bcarb值计算的海水pH值会产生误差，使δ11B-pH技术变得更为复杂。 10. 实验模拟与自然的真实情况是有差距的，不能完全用实验模拟来代替自然的真实情况。 11.杨户庄剖面的第四纪早期有孔虫的生存环境是非海相环境，不是“海侵”或“海泛”的结果；同时也表明有孔虫并非是特有的海洋生物，它完全可以在陆相环境中存在。

Ensayo con fitoterápicos para la erradicación del endófito Acremonium coenophilalum en semillas de festuca

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Central nervous system drugs: Low temperature X-ray structures of (I) the base 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine (4030W92) and (II) 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine methanesulphonic acid salt (227C89)

The X-ray crystal structures of (I), the base 4030W92, 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine, C11H9Cl2FN4, and (II) 227C89, the methanesulphonic acid salt of 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine, C11H11Cl2N4 center dot CH3O3S, have been carried out at low temperature. A detailed comparison of the two structures is given. Structure (I) is non-centrosymmetric, crystallizing in space group P2(1) with unit cell a = 10.821(3), b = 8.290(3), c = 13.819(4) angstrom, beta = 105.980(6)degrees, V = 1191.8(6) angstrom(3), Z = 4 (two molecules per asymmetric unit) and density (calculated) = 1.600 mg/m(3). Structure (II) crystallizes in the triclinic space group P (1) over bar with unit cell a = 7.686(2), b = 8.233(2), c = 12.234(2) angstrom, alpha = 78.379(4), beta = 87.195(4), gamma = 86.811(4)degrees, V = 756.6(2) angstrom(3), Z = 2, density (calculated) = 1.603 mg/m(3). Final R indices [I > 2sigma(I)] are R1 = 0.0572, wR2 = 0.1003 for (I) and R1 = 0.0558, wR2 = 0.0982 for (II). R indices (all data) are R1 = 0.0983, wR2 = 0.1116 for (I) and R1 = 0.1009, wR2 = 0.1117 for (II). 5- Phenyl-2,4 diaminopyrimidine and 6-phenyl-1,2,4 triazine derivatives, which include lamotrigine (3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine), have been investigated for some time for their effects on the central nervous system. The three dimensional structures reported here form part of a newly developed data base for the detailed investigation of members of this structural series and their biological activities.

Systematic study of visible transitions in Ti-like high Z ions

The magnetic dipole transitions between fine structure levels in the ground term of Ti-like ions, (3d(4)) D-5(2)-D-5(3), were investigated by observation of visible and near-UV light for several elements with atomic numbers from 51 to 78. The wavelengths are compared with theoretical values we recently calculated. The differences between the present calculations and measurements are less than 0.6%. The anomalous wavelength stability predicted by Feldman, Indelicato and Sugar [J. Opt. Soc. Am. B 8, 3 (1991)] was observed. We attribute this anomalous wavelength stability to the transition from LS to JJ coupling and the asymptotic behavior of the transition energies in the intermediate coupling regime.

Effect of composition, solvent exchange liquid and drying method on the porous structure of phenol-formaldehyde gels

Organic gels have been synthesized by sol–gel polycondensation of phenol (P) and formaldehyde (F) catalyzed by sodium carbonate (C). The effect of synthesis parameters such as phenol/catalyst ratio (P/C), solvent exchange liquid and drying method, on the porous structure of the gels have been investigated. The total and mesopore volumes of the PF gels increased with increasing P/C ratio in the range of P/C B 8, after this both properties started to decrease with P/C ratio for P/C[8 and the gel with P/C = 8 showed the highest total and mesopore volumes of 1.281 and 1.279 cm3 g-1 respectively. The gels prepared by freeze drying possessed significantly higher porosities than the vacuum dried gels. The pore volume and average pore diameter of the freeze dried gels were significantly higher than those of the vacuum dried gels. T-butanol emerged as the preferred solvent for the removal of water from the PF hydrogel prior to drying, as significantly higher pore volumes and specific surface areas were obtained in the corresponding dried gels. The results showed that freeze drying with t-butanol and lower P/C ratios were favourable conditions for the synthesis of highly mesoporous phenol–formaldehyde gels.

Moralité nouvelle du mauvais riche et du ladre : à douze personnages

[La vie et l'histoire du Mauvais riche (français moyen). 1823]

[Portrait de garçon en uniforme de collégien à mi-jambes, debout portant un brassard de communiant] : [photographie] / Pierre Eugène Fixon

Ancien possesseur : Gilles, Albert (1873-1959)

[Portrait de jeune fille, en pied, assise, à la droite d'une balustrade et d'une draperie] : [photographie] / Derussy

Ancien possesseur : Gilles, Albert (1873-1959)

[Jeune garçon au papillon, à mi-jambes, assis, de trois-quarts à gauche] : [photographie] / Non identifié

Ancien possesseur : Gilles, Albert (1873-1959)