Syntheses and crystal structures of [(C6H5CH2C5H4)(2)GdCl center dot THF](2) and (C6H5CH2C5H4)(2)ErCl center dot THF

[(C6H5CH2C5H4)(2)GdCl . THF](2) (1) and (C6H5CH2C5H4)(2)ErCl . THF (2) were prepared by the reaction of LnCl(3) (Ln=Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, H-1 NMR, C-13 NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2(1)/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, beta=108.75(2), V=2.4732(9) nm(3), Z=2(four monomers), D-c=1.54 g . cm(-3). R=0.0342 and R(w)=0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2(1)2(1)2(1) space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm(3), Z=4, D-c=1.56 g . cm(-3). R=0.0514, R(w)=0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd3+ are located in the opposite direction (139 degrees); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er3+ are located in the same direction (6.5 degrees).

Synthesis and molecular structures of di- and trinuclear molybdenum complexes containing pyridine-2-thiolato (pyS) ligand

Dinuclear complexes [Mo-2(mu-pyS)(2)(CO)(4)(PPh(3))(2)] (1), [Mo-2(mu-pyS)(2)(CO)(5)(PPh(3))] (2) and a trace quality of trinuclear complex [Mo-3(mu-pyS)(2)(mu(3)-pyS)(2)(CO)(6)] (3) were obtained from the reaction of [Mo(CO)(3)(MeCN)(3)] with pyridine-2-thione (pySH) and PPh(3) in THF. The crystal structures of 1.2C(7)H(8) and 3.7 C7H8 have been determined by X-ray diffraction studies. Crystals of 1.2C(7)H(8) are monoclinic, space group C2/c and Z = 4, with a = 18.797(3), b = 11.143(4), c = 28.157(7) Angstrom, beta = 101.23(2)degrees. The structure was refined to R = 0.050 and Rw = 0.057 for 3146 observed reflections, Crystals of 3.7 C7H8 are monoclinic, space group P2(1)/a and Z = 4, with a = 13.912(2), b = 17.161(2), c = 15.577(3) Angstrom, beta = 101.17(1)degrees. The structure was refined to R = 0.046 and Rw = 0.051 for 4357 observed reflections. The molecule of 1 consists of two Mo(CO)(2)(PPh(3)) fragments linked by an Mo-Mo bond (2.974(2)Angstrom) and by two doubly-bridging pyS ligands. The compound 3 contains a bent open geometry of three molybdenum atoms (Mo(1)-Mo(2)-Mo(3) angle 122.99(3)degrees) linked by two Mo-Mo bonds (2.943(1) and 2.950(1) Angstrom) and by two doubly- and two triply-bridging pyS ligands.

DICHLORO(ETA(5)-CYCLOPENTADIENYL)([1-(4-METHOXYPHENYL)CYCLOHEXYL]-ETA(5)-CYCLOPENTADIENYL)TITANIUM(IV)

The title molecule, [TiCl2(C5H5)(C18H21O)], has a pseudotetrahedral bent metallocene structure in which the cyclopentadienyl ring is symmetrically bonded to Ti [range of Ti-C distances 2.36(1)-2.41(1)Angstrom], but the substituted cyclopentadienyl ring adopts asymmetrical bonding [Ti-C 2.33(1)-2.48(1)Angstrom] due to the interaction of the large substituent with the Cl(2) atom. The angle C(11)-C(1)-C(21) is 111.1(8)degrees with the large substituent occupying a cis position with respect to the substituted ring.

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.

SYNTHESIS AND CRYSTAL-STRUCTURE OF NEODYMIUM COMPLEX OF 1-METHYL-1, 4, 7, 10-TETRAAZACYCLODODECANE

The complex [Nd(L)(CH3CN)(CF3SO3)3] has been synthesized. Where L = 1-methyl-1, 4, 7, 10-tetraazacycldodecane. The crystal structure of the complex has been determined by a four-circle X-ray diffractometer to a final deviation factor B value of 0.0370 and R(w) value of 0.0385 respectively. The crystal is triclinic system, space group P1BAR with a = 0.8738(2), b = 1.2870(3), c = 1.2900(3) nm, alpha = 85.63(2), beta = 87.25(2), gamma = 78.30(2)-degrees, V = 1.41571 (60) nm3, Z = 2, D(c) = 1.92 g/cm3. The neodymium ion is eight-coordinated to forming a distorted square antiprism.

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

Sm_xLa_(1-x)P_5O_(14)和Dy_xY_(1-x)P_5O_(14)晶体的荧光寿命研究

本文用脉冲衰减法和时间分辨荧光光谱法测量了六种不同稀土离子浓度的Sm_xLa_(1-x)P_5O_4晶体的~4G_(5/2)→~6H_J(J=5/2,7/2,9/2,11/2)四个能级和七种不同稀土离子浓度的Dy_xY_(1-x)P_5O_(14)晶体的~4F_(9/2)→~6H_J(J=15/2,13/2,11/2,9/2)四个能级的荧光寿命和荧光强度。结果指出,在这类晶体中,Sm~(3+)和Dy~(3+)的荧光寿命随着离子的浓度增加而变短,存在着严重的荧光浓度猝灭现象。最后还讨论了浓度与寿命,寿命与荧光强度的关系。

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.

Palaeoenvironmental changes from pollen record in deep sea core PC-1 from northern Okinawa Trough, East China Sea during the past 24 ka

A pollen record of core PC-1 from the northern Okinawa Trough, East China Sea (ECS), provides information on vegetation and climate changes since 24 cal. kaBP. A total of 103 samples were palynologically analyzed at 8 cm intervals with a time resolution of 230 a. Four pollen zones are recognized: zone I (812-715 cm, 24.2-21.1 cal. kaBP), zone II (715-451 cm, 21.1-15.2 cal. kaBP), zone III (451-251 cm, 15.2-10.8 cal. kaBP), zone IV (251-0 cm, 10.8-0.3 cal. kaBP), corresponding to Late MIS 3, Last Glacial Maximum (LGM), deglaciation and Holocene, respectively. The LGM is characterized by the dominance of herbs, mainly Artemisia, and high pollen influx, implying an open vegetation on the exposed continental shelf and a cool and dry climate. The deglaciation is a climate warming stage with Pinus percentage increased and Artemisia percentage decreased and a rapid sea-level rise. The Holocene is characterized by predominance of tree pollen with rapid increase in Castanea-Castanopsis indicating the development of mixed evergreen and deciduous broad-leaved forest and a warm, humid climate. Low pollen influx during the Holocene probably implies submergence of the continental shelf and retreat of the pollen source area. The vegetation indicated by pollen assemblage found in this upper zone is consistent with the present vegetation found in Kyushu, Japan. Originating from the humid mountain area of North Luzon of the Philippines, Tasmania and New Zealand, Phyllocladus with sporadic occurrence throughout PC-1 core probably suggests the influence of Palaeo-Kuroshio Current or intense summer monsoon. The observed changes in Pinus and Herbs percentage indicate fluctuations of the sea level, and high Pinus percentage corresponds to high sea level. Spectrum analysis of the pollen percentage record reveals many millennial-scale periodicities, such as periodicities of 6.8, 3.85 2.2, 1.6 ka.

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.