SYNTHESIS AND CRYSTAL-STRUCTURE OF [ME4C2CP2SMCL-CENTER-DOT-THF]2

Me4C2(C5H4MgCl)2(THF) (THF = tetrahydrofuran) reacts with anhydrous SmCl3 in THF to give [Me4C2CP2SMCl.THF]2. The molecule is a dimer. Sm1 and Sm2 are bridged unsymmetrically by two chlorine atoms [Sm(1)-CI(1) 2.787(2), Sm(1)-Cl(2) 2.848(2), Sm(2)-Cl(1) 2

STRUCTURE OF AN ERBIUM COORDINATION COMPOUND WITH L-PROLINE, ([ER(PRO)2(H2O)5]CL3)(N)

catena-Poly[{pentaaqua(L-proline-O)-erbium-mu-(L-proline-O:O')} trichloride], {[Er(C5H9-NO2)2(H2O)5]Cl3}n, M(r) = 594.0, monoclinic, P2(1), a = 8.294 (1), b = 10.981 (3), c = 11.934 (3) angstrom, beta = 107.04 (2)degrees, V = 1039.2 (4) angstrom3, Z = 2, D(x) = 1.90 g cm-3, lambda(Mo Kalpha) = 0.71069 angstrom, mu = 45.2 cm-1, F(000) = 586, T = 298 K, R = 0.0244 for 1711 unique reflections [I > 3 sigma(I(o))]. The crystal consists of one-dimensional chains of infinite length in which one L-proline ligand bridges two neighboring Er ions, the other L-proline ligand being monodentate.

STUDIES ON ORGANOLANTHANIDE COMPLEXES .40. SYNTHESIS AND X-RAY STRUCTURE OF BIS (2-METHOXYETHYLCYCLOPENTADIENYL) YTTRIUM AND YTTERBIUM TETRAHYDROBORATES

New bis (2-methoxyethylcyclopentadienyl) yttrium and ytterbium tetrahydroborates (Ln = Y, 1; Yb, 2) have been synthesized in good yield by the reaction of bis (2-methoxyethylcyclopentadienyl) lanthanide chlorides (Ln = Y, Yb) with sodium borohydride in THF at room temperature. The title complexes were characterized by elemental analyses, MS, H-1 NMR and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. 1 crystallizes from THF-n-Hexane in space group Pna2(1) with unit cell parametert: a = 1.2390(3), b = 1.1339(2), c = 1.1919 (2) nm and V = 1.6745(6) nm3 with z = 4 for D(c) = 1.39 g.cm-3.The structure was solved by direct method and refined to final R = 0.061 (for 1730 observed reflections). The Space group of 2 is Pna2(1) with unit cell parameters: a = 1.2399(6), b = 1.1371(5), c = 1.1897(2) nm and V = 1.6773(1) nm3 with z = 4 for D(c) = 1.72 g.cm-3, R = 0.038 (for 2157 observed reflections). The X ray structures and IR reveal the bidentate yttrium and ytterbium tetrahydroborate complexes with the intramolecular coordination bonds between lanthanide metal and ligand oxygen atoms.

SYNTHESES OF METHYLCYCLOPENTADIENYL DERIVATIVES OF LANTHANIDES (LN = LA-ND) AND CRYSTAL-STRUCTURES OF [(THF)2LI(MU-CL)2]2[MECPND(THF)] AND [LI(DME)3][MECPLA(NPH2)3]

The reaction of LnCl3.2LiCl with 1 equiv of MeCpNa in THF gives the complexes [(THF)2Li(mu-Cl)2]2[MeCpLn(THF)] (Ln = Nd (1), La (2)) in good yield. These precursors react further with 2 equiv of LiNPh2 to produce the new complexes [Li(DME)3][MeCpLn(NPh2)3] (Ln = La (3), Pr (4), Nd (5)). They have been characterized by elemental analyses and IR and NMR spectra, as well as by structural analyses of 1 and 3. The chloride 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.130 (5) angstrom, b = 17.343 (5) angstrom, c = 17.016 (5) angstrom, beta = 108.54 (3)-degrees, V = 3393.87 angstrom3, Z = 4, and D(c) = 1.45 g/cm3. Least-squares refinement led to a final R value of 0.051 (I greater-than-or-equal-to 3-sigma(I(o))) for 2004 independent reflections. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 18.335 (6) angstrom, b = 16.576 (5) angstrom, c = 17.461 (6) angstrom, beta = 96.04 (3)-degrees, V = 5277.17 angstrom3, D(c) = 1.26 g/cm3, Z = 4, and R = 0.057 (I greater-than-or-equal-to 2.5-sigma(I(o))) for 3378 reflections. The structure of 3 consists of discrete ion pairs [Li(DME)3]+ and [MeCpLa(NPh2)3]- with average La-N and La-C(ring) distances of 2.459 (8) and 2.84 (1) angstrom, respectively.

镧系金属有机配合物的研究 XL.双(2-甲氧乙基环戊二烯基)钇和镱的硼氢配合物的合成及晶体结构

双(2-甲氧乙基环戊二烯基>氯化钇和镱,在THF中,室温与硼氢化钠发生置换反应,生成双(2-甲氧乙基环戊二烯基)硼氢化钇(1)和镱(2),产率分别为70和59%.它们都经红外光谱,质谱,~1HNMR和元素分析鉴定.将l和2在THF-已烷中重结晶,得到适用于X射线衍射分析的单晶.1的空间群为Pna2_1,晶胞参数:a=1.2390(3),b=1.1339(2),c=1.1919(2)nm,晶胞体积,1.6745(6)nm~3.D_o=1.39g·om~3,z=4,R=0.061;2的空间群为Pna2_1,晶胞参数:a=1.2399(6),b=1.1371(5),c=1.1897(2)nm,晶胞体积,1.6773(1)nm~3,D_c=1.72g·cm~(-3),z=4,R=0.038,1与2都是含有两个内配位键(Ln—O)的双齿型的单体结构.

[2,4-(CH_3)_2C_5H_5]NdCl_2·3THF-AlEt_3体系引发丁二烯聚合的活性

戊二烯稀土配合物化学目前尚处于萌芽时期,只报道有几个配合物的合成,戊二烯稀土氯化物的合成则至今未见报道.最近,东德专利报道了[2,4-(CH_3)_2C_5-H_5]_3Nd在双烯烃定向聚合上的应用.我们合成了2,4-二甲基戊二烯基稀土二氯化物,并考察了其对双烯烃的聚合催化活性. 1.试剂和分析方法:聚合用溶剂经纯化,活性氧化铝浸泡后使用.稀土含量分析用二甲酚橙为指示剂以EDTA标准溶液滴定;氯含量分析用硫酸铁铵为指示剂,加过量

电活性质点Fe~(2+)离子在六氰亚铁钒薄膜中的传输

电活性质点Fe~(2+)可穿透六氰亚铁钒薄膜在玻璃碳基体电极表面于较负电位处直接氧化,也可经VHF膜中氧化还原点位的媒介在较正电位处于膜-溶液界面及膜内部发生催化氧化.两个过程分别在用VHF修饰过的旋转GC电极上的伏安曲线中产生,可明确分辨的第一波和第二波.第一波的极限电流受Fe~(2+)离子在溶液中和膜中的扩散速率控制.VHF薄膜对Fe~(2+)离子的透过能力,kD_m/d,为10~(-3)-10~(-2)cm·s~(-1)数量级,随膜厚度增大而减小,不随溶液中Fe~(2+)离子浓度改变.

栉孔扇贝C型凝集素-2(CfLec-2)基因的克隆和分析

栉孔扇贝是我国北方一种重要的贝类养殖品种。自1997年以来爆发的栉孔扇贝大规模死亡，给地区经济造成了重大损失并且已经严重威胁着扇贝养殖业的健康发展。然而，到目前为止，对扇贝免疫防御分子机理的了解还很少，深入研究扇贝免疫应答的分子机制是认识和了解病害发生和实现病害控制的重要途径。本研究采用了EST大规模测序和3’RACE的方法，从栉孔扇贝cDNA文库中克隆到一个凝集素基因CfLec-2，并对功能进行了研究。 CfLec-2 cDNA全长708bp，5’非翻译区(Untranslated Region, UTR)含有59bp，3’非翻译区含有163bp，具有典型的多聚腺苷酸加尾信号序列AATAAA和多聚腺苷酸尾巴，开放阅读框(Open Reading Frame, ORF )含有486bp，编码162个氨基酸残基，该多肽的理论分子量为16.8 kDa，等电点为4.54。利用SignalP分析，发现其信号肽的剪切位置在VEA-QSL之间。经BLASTP比对分析可知，CfLec-2基因编码的蛋白与人的Brevican，Anguilla japonica的C-type lectin-1和C-type lectin-2， Rattus norvegicus的CD23有较高的相似性，其中与Brevican的一致性有37%。Clustal W多序列比对发现该多肽具有标准长型C型凝集素所必须的6个保守半胱氨酸和相对保守的糖识别位点。用SMART(Small Modular Architecture Research Tool)软件分析发现其具有一个保守的糖识别结构域(Carbohydrate-recognition Domain, CRD)，氨基酸序列上第49、125、141、149位置上的半胱氨酸参与形成糖识别结构域，而位于N末端的第21和32位上的两个半胱胺酸形成额外的一个二硫键，位于115、116和117上的Glu、Pro、Asp则构成了糖识别位点。 将编码CfLec-2成熟肽段的cDNA序列克隆进pET32a(+)载体中，并在大肠杆菌Rosetta-gami(DE3)中重组表达CfLec-2。重组蛋白利用其具有的His tag纯化并复性后发现CfLec-2可以凝集溶血葡萄球菌，且凝集过程不需要钙离子的参与。并且，CfLec-2对大肠杆菌TOP10F’有微弱的抑菌活性，对溶壁微球菌、溶血葡萄球菌和鳗弧菌则没有抑菌活性。这一结果说明，CfLec-2可能不仅参与对入侵微生物的识别过程，而且可能作为效应分子起到了直接杀灭入侵微生物的作用。 本研究发现CfLec-2具有和以前在栉孔扇贝报道的CFLec-1完全不同的功 能，说明栉孔扇贝利用不同的凝集素来识别不同的病原，同时也暗示栉孔扇贝中可能有更多不同功能的凝集素有待发现。研究结果丰富和发展了海水无脊椎动物免疫学的内容，对进一步了解扇贝固有免疫的机制，实现养殖扇贝疾病防治具有重要参考价值。

pCO(2) and carbon fluxes across sea-air interface in the Changjiang Estuary and Hangzhou Bay

Partial pressure of CO2 (pCO(2)) was investigated in the Changjiang (Yangtze River) Estuary, Hangzhou Bay and their adjacent areas during a cruise in August 2004, China. The data show that pCO(2) in surface waters of the studied area was higher than that in the atmosphere with only exception of a patch east of Zhoushan Archipelago. The pCO(2) varied from 168 to 2 264 mu atm, which fell in the low range compared with those of other estuaries in the world. The calculated sea-air CO2 fluxes decreased offshore and varied from -10.0 to 88.1 mmol m(-2) d(-1) in average of 24.4 +/- 16.5 mmol m(-2) d(-1). Although the area studied was estimated only 2 x 10(4) km(2), it emitted (5.9 +/- 4.0) x 10(3) tons of carbon to the atmosphere every day. The estuaries and their plumes must be further studied for better understanding the role of coastal seas playing in the global oceanic carbon cycle.

Light energy conversion into H-2 by Anabaena variabilis mutant PK84 dense cultures exposed to nitrogen limitations

Concentrated cultures (25-86 mg Chl a l(-1)) of Anabaena variabilis PK84 were incubated under 99% Ar+1% CO2 atmosphere in the photobioreactor made of coaxial cylinders. Under illumination equal to 353 mu E m(-2) s(-1) they produced hydrogen with the rate more than 20 ml l(-1) h(-1) for several days. The efficiency of light energy conversion into H-2 was approx. 1% and did not depend significantly on initial Chl a concentration. H-2/O-2 ratio reached 41.5% of theoretical value for water photolysis. Data indicate that dense cultures might be used for outdoor systems under direct sun light. Supra-optimal temperatures 36 degrees C were not harmful for cultures even for 2 days period. Short-term incubation of cultures under 36 degrees C even increased H2 production rate and efficiency of light energy bioconversion by 1.25 times. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Studies on two coordination polymers [M(mu(4)-pz25dc)](n) (M = Cd or Zn, pz25dc=pyrazine-2,5-dicarboxylato) with three-dimensional pillared-layer three-nodal framework: Synthesis, structural characterization, strong optical non-linearities and optical limiting properties

Two isomorphous new candidates [M(mu(4)-pz25dc)](n) (M = Cd, 1; Zn, 2; pz25dc = pyrazine-2,5-dicarboxylato)for nonlinear optical (NLO) materials have been synthesized hydrothermally and characterized crystallographically as pillared-layer three-nodal frameworks with one four-connected metal nodes and two crystallographically different four-connected ligand nodes. Their optical non-linearities are measured by the Z-Scan technique with an 8 ns pulsed laser at 532 nm. These two coordination polymers both exhibit strong NLO absorptive abilities [alpha(2) = (63 +/- 6) x 10 (12) mW (1) 1, ( 46 +/- 6) x 10 (11) mW (1) 2] and effective self-focusing performance [n(2) = (67 +/- 5) x 10 (18) 1, (13 +/- 3) x 10 (18) m(2) W (1) 2] in 1.02 x 10 (4) 1 and 1.05 x 10 (4) mol dm (3) 2 DMF solution separately. The values of the limiting threshold are also measured from the optical limiting experimental data. The heavy atom effect plays important role in the enhancement of optical non-linearities and optical limiting properties. (C) 2009 Elsevier B. V. All rights reserved.

Unprecedented 5,5-connected (4(7)center dot 6(3)) (4(8)center dot 6(2)) structural topology: A lead biphosphonate with double layered structure

A new lead(II) phosphonate, Pb[(PO3)(2)C(OH)CH3]center dot H2O (1) was hydrothermally synthesized and characterized by IR, elemental analysis, UV, TGA, SEM, and single crystal X-ray diffraction analysis. X-ray crystallographic study showed that complex 1 has a two-dimensional double layered hybrid structure containing interconnected 4- and 12-membered rings and shows an unusual (5,5)-connected (4(7) . 6(3)) (4(8) .6(2)) topology. (C) 2008 Elsevier B.V. All rights reserved.

Synthetic studies on optically active Schiff-base ligands derived from condensation of 2-hydroxyacetophenone and chiral diamines

Three optically active Schiff-base ligands have been prepared by condensation of 2-hydroxyacetophenone with (IR,2R)-(-)-1,2-diaminocyclohexane, (1S,2S)-(-)1,2-diphenylethylenediamine or R-(+)-2,2'-diamino-1,1'-binaphthalene, respectively. The products have been characterized by their IR, H-1- and C-13-NMR spectra.

LOCALIZED ENHANCEMENTS OF Fe+10 DENSITY IN THE CORONA AS OBSERVED IN Fe xi 789.2 nm DURING THE 2006 MARCH 29 TOTAL SOLAR ECLIPSE

Habbal, Shadia Rifai; Morgan, Huw; Johnson, Judd; Arndt, Martina Belz; Daw, Adrian; Jaeggli, Sarah; Kuhn, Jeff; Mickey, Don, LOCALIZED ENHANCEMENTS OF Fe+10 DENSITY IN THE CORONA AS OBSERVED IN Fe xi 789.2 nm DURING THE 2006 MARCH 29 TOTAL SOLAR ECLIPSE, The Astrophysical Journal, Volume 663, Issue 1, pp. 598-609

Plankton Of The Fladen Ground During Flex-76 .2. Population-Dynamics And Production Of Thysanoessa-Inermis (Crustacea Euphausiacea)

Samples taken in the northern North Sea with the Continuous Plankton Recorder (CPR), the Undulating Oceanographic Recorder (UOR) and the Longhurst-Hardy Plankton Recorder (LHPR) during the Fladen Ground Experiment in 1976 (FLEX 76) are used to describe the vertical distribution and population dynamics of Thysanoessa inermis (Krøyer) and to provide estimates of the production and carbon budget of the population from 19th March to 3 June 1976. Spawning occurred in late April and early May, in near synchronisation with the start of the spring bloom of phytoplankton. Eggs, nauplii and calyptopes reached maximum abundance in succession, and furciliae were numerous when sampling ceased in early June. Adults increased in length from a mean of 12.1 mm in mid-March to 17.5 mm in early June and the estimated production was 2.40 mg m-3 over the 74 d period. Total carbon ingested by the population of T. inermis was estimated to be 10 mg C m-2 d-1 in the upper 100m which was only 1.5% of the daily primary production of 0.68 gC m-2 measured over the FLEX period 26 March to 4 June 1976. The grazing by T. inermis on the phytoplankton population was assumed to have little effect on the control and depletion of the spring phytoplankton bloom during FLEX 77.