Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.

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.

泡沫塑料动态快速分离富集金方法的研究

本文系统研究了泡沫塑料动态快速分离富集金的方法。对泡沫塑料柱的处理方法,再生及主要共存离子干扰的消除等均做了较详细的研究。提出了一种简便,不控速的金分离富集的方法。该法用于分析0.051～3.59g/t四种不同含量的金标样,结果与推荐值吻合,5次分析结果,相对标准偏差<5％,同时,可用泡沫塑料柱当天连续使用分析拿标样,回收率为93％—109％。

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.

乌江流域不同演化阶段水库汞的输入输出通量研究

北欧和北美的研究发现水库是典型的汞敏感生态系统，新建水库而引起的鱼体甲基汞污染问题已受到科学家的高度重视，而我国在这方面的研究比较薄弱。本论文选择乌江流域的6个水库作为研究对象，并根据年龄把这些水库划分为3个演化阶段，洪家渡、引子渡、索风营水库为初级演化阶段，普定、东风水库为中级演化阶段，乌江渡水库为高级演化阶段。对这6个水库总汞和甲基汞的输入和输出通量进行了研究，探讨了不同演化阶段的水库对总汞和甲基汞的“源/汇”作用，主要研究内容有以下三个方面：(1)各水库入出库河流中汞的分布特征；(2)大气降水中汞浓度及沉降通量的分布；(3)乌江流域不同水库汞的输入输出通量。通过本论文的研究，得出以下主要结论： 1. 乌江流域河流中总汞、颗粒态汞、溶解态汞、活性汞、总甲基汞、溶解态甲基汞的年均浓度分别为3.41±1.98、2.05±1.73、1.36±0.44、0.24±0.11、0.15±0.06、0.08±0.03 ng•L-1。与国内外其它河流的比较发现，总汞的浓度明显低于国外受污染的河流，略高于国外未受污染的河流。溶解态汞、活性汞、甲基汞的浓度略低于受污染的河流，与未受污染的河流基本相当。与同处在贵州喀斯特地区的阿哈湖、红枫湖、百花湖的入出库河流相比，总汞、溶解态汞、活性汞、甲基汞、溶解态甲基汞的浓度均明显偏低。 2. 水库的修建显著降低了出库河流中总汞、颗粒态汞的浓度，使总甲基汞和溶解态甲基汞的浓度升高，而且增加了出库河流中溶解态汞、活性汞、总甲基汞占总汞的比例。不同形态汞的沿程分布显示，梯级水库的修建改变了河流原有的汞的生物地球化学过程，使乌江多个河段的甲基汞升高，并且随着水库生态系统的不断演化，水库输出的甲基汞将增加，下游河流水体中甲基汞有继续升高的趋势。 3. 大气降雨中总汞、溶解态汞、颗粒态汞、活性汞、总甲基汞的浓度分别为7.49~149 ng•L-1、1.23~10.0 ng•L-1、5.76~142 ng•L-1、0.56~2.94 ng•L-1、0.08~0.82 ng•L-1，且以颗粒态汞为主，约占总汞比例的87%。总汞、溶解态汞、颗粒态汞、甲基汞的浓度有明显的季节变化趋势，冬春季高于夏秋季，而空间分布特征不明显。2006年总汞、甲基汞的年湿沉降通量为34.7±5.80 µg•m-2•yr-1、0.18±0.03 µg•m-2•yr-1，且主要受降雨量的影响。乌江流域降雨中总汞的浓度及其湿沉降通量远高于北美和日本，低于中国的一些城市地区（如长春和北京），而甲基汞的浓度和通量与其它地区相当。 4. 在乌江流域的不同水库中，降雨输入总汞和甲基汞的通量主要受降雨量和水库面积的影响，而与降雨的汞浓度间没有相关性。河流向水库输入总汞的量主要受河流流量的控制，而输入甲基汞和颗粒物的量受河流流量和浓度的影响。下泄水输出总汞、甲基汞、颗粒物的通量受浓度和流量的影响。由于流域面积/水面面积的比值较大，水库水量、总汞、甲基汞、颗粒物的输入以河流为主，分别占总输入的87%、80%、85%、86%。输出以下泄输出为主，下泄水输出的水量、总汞、甲基汞、颗粒物分别占总输出的80%、77%、86%、79%。 5. 从输入-输出通量的结果发现，各水库均表现为河流颗粒物输送的“汇”；除乌江渡水库外，其它水库均表现为总汞的“汇”；对甲基汞而言，引子渡、洪家渡、索风营水库表现为“汇”，而普定、东风、乌江渡水库则表现为“源”。 6. 普定和洪家渡水库中总汞的贮存率为56%和57%，明显高于其它水库，说明在上游有水库存在的情况下，水库对总汞“汇”的作用将降低。普定、东风、乌江渡水库中甲基汞的净通量分别为+69.4 g•yr-1、+368 g•yr-1、+857 g•yr-1，转化率为13%、73%、84%，说明甲基汞的净通量和转化率与水库的演化阶段有关，随着水库演化阶段的升高而增加，并且随着水库的不断演化，甲基汞将从“汇”变成“源”。

Indução à repelência à água em solo arenoso o partir de extratos naturais hidrofóbicos.

2008

Psilídeos no Brasil: 2- Ctenarytaina eucalypti (Maskell, 1980) (Psilídeo das ponteiras do eucalipto).

2008

Demonstração de diferentes protocolos para implantação de parcelas permanentes em Floresta Ombrófila Mista.

2008

Metodologia para obtenção de Antocianinas de frutos de juçara (Euterpe edulis).

2008

Método alternativo de extração dos componentes hidrofóbicos da matéria orgânica de solos florestais.

2008

Praga florestal exótica: Mycosphaerella dearnessii.

2008

Psilídeos no Brasil: 4 - Heteropsylla cubana (Psilídeo da leucena) Hemiptera: Psyllidae.

2008

Praga florestal exótica: Phytophthora meadii.

2008

Elaboração de um banco de dados climáticos para o Estado do Paraná.

2008

Manual de prática de coleta e herborização de material botânico.

2008