Syntheses and Crystal Structures of Fused Thiophenes: [7]Helicene and Double Helicene, a D-2-Symmetric Dimer of 3,3 '-Bis(dithieno[2,3-b:3 ',2 '-d]thiophene)

The efficient synthesis of (TMS)(2)-[7]helicene (rac-3) and double helicene, a D-2-symmetric dimer of 3,3'-bis(dithieno-[2,3-b:3',2'-d]thiophene) (rac-4) was developed. The crystal structures of 3 and 4 show both strong intermolecular pi-pi interactions and S center dot center dot center dot S interactions. UV/vis spectra reveal that both 3 and 4 show significant pi-electron delocalization.

Efficient synthesis of substituted tetrahydrothiopyrano[2,3-b]thiopyran-4,5-diones by a double annulation strategy from dialkenoylketene dithioacetals

An efficient synthetic procedure for substituted 2,3,6,7tetrahydrothiopyrano [2,3-b] thiopyran-4,5 -diones by a double annulation strategy is described. The ring systems are made in good yields from readily available dialkenoylketene dithioacetals in the presence of either sodium sulfide nonahydrate/N,N-dimethylformamide (DMF) or a sodium hydride/DMF/amine system.

Efficient synthesis of trimethylsilyl-substituted dithieno[2,3-b:3',2'-d]thiophene,tetra[2,3-thienylene] and hexa[2,3-thienylene] from substituted [3,3']Bithiophenyl

Efficient synthetic procedures for the preparation of beta-trithiophenes (dithieno[2,3-b:3',2'-d]thiophene) and two macrocyclic compounds, tetra[2,3-thienylene] and hexa[2,3-thienylene] bearing trimethylsilyl (TMS) groups from 2,2'-dibromo-5,5'-bistrimethylsilanyl[3,3']bithiophenyl are reported. The UV-Vis spectra property and crystal structures of these macrocyclic oligothiophenes are described.

6,7,8,9-Tetrahydro-5H-pyrido[2,3-b]azepine-5,8-dione: a hydrogen-bonded dimer structure

In the title compound, C9H8N2O2, two crystallographically independent molecules form a dimer structure, in which two N-H center dot center dot center dot N hydrogen bonds generate an intermolecular R-2(2)( 8) ring.

VUV excitation properties of LnAl(3)B(4)O(12): Re (Ln = Y, Gd; Re=Eu, Tb)

Vacuum ultraviolet excitation spectra of LnAl(3)B(4)O(12):Re (Ln = Y, Gd; Re = Eu, To), along with X-ray photoelectron spectra, were measured. The spectra are tentatively interpreted in terms of the optical properties of the rare earth ions and the band structure. It was found that there is an energy transfer from the hosts to the rare earth ions. It was also found that the top of the valence band in the Gd compound is mainly formed by the 2p levels of O2- and the 4f levels of Gd3+, and in the Y compound mainly by the 2p levels of O2-. (C) 2000 Elsevier Science Ltd. All rights reserved.

中国株丙型肝炎病毒实验感染3种猕猴的初步结果

选用无各型肝炎病毒感染、体质良好的6只食蟹猴、3只恒河猴和3只熊猴,按人感染HCV的主要途径——输血,经静脉输注含HCV的中国献血员血浆,观察临床一般指标,血清ALT,抗HCV各种抗体和HCV-RNA,肝组织普通病理,超微病理。从肝组织中找病毒颗粒及免疫组化查HCV NS3抗原,观察14周,结果9例猕猴出现不同程度的肝炎症状,12例血清ALT升高,2例出现黄疸;5例抗HCVC22 IgG抗体阳性,4例抗HCV E2-24 IgG抗体阳性,10例抗HCV C33c IgG抗体阳性,2例抗HCVNS4-40 IgG抗体阳性,11例抗HCV NS5-A IgG抗体阳性,无1例抗HCVNS5-B IgG抗体阳性;9例HCV-RNA阳性。6例肝活检或肝小部切除作肝组织普通光镜镜检,5例肝细胞气球样变,点状坏死及少许纤维组织增生。另一例相应损害较重,呈碎片坏死,界板破坏,纤维组织增生明显,汇管区炎性细胞浸润,超微病理除普通炎症所具有的特征外,以滑面内质网大量增生扩张为其主要特征,3例从内质网里看到约30nm的类病毒颗粒。免疫组化显示3只动物肝组织内HCVNS3抗原阳性,以膜型为主少量周边型及散在胞浆内分布,因此我们认为已...

The effect of substrate orientation on the morphology of InAs nanostructures on (001) and (11n)A/B(n=1-5) InP substrates

Strained InAs nanostructures have been grown by solid-source molecular beam epitaxy in In0.52Al0.48As matrix on different InP substrate surfaces ((0 0 1) and (1 1 n)A/B (n = 1 - 5)). The morphology of the nanostructures was characterized using atomic force microscopy (AFM). The AFM results reveal interesting differences in the size, shape, and alignment of the nanostructures between different oriented surfaces. It was found that some faceted nanostructures tend to form on A-type surfaces, the shape and the alignment of these nanostructures show clear dependence on the substrate orientation. Samples grown on (0 0 1) and B-type surfaces showed preferentially dense round dots. Dots formed on (1 1 3)B, (1 1 3)B and (1 1 5)B surfaces have a higher dot density and size homogeneity, which shows a potential for the production of high-quality and customized self-assembled quantum dots for photonics applications. (C) 2000 Elsevier Science B.V. All rights reserved.

Ce~(3+)在稀土取代的卤磷酸盐中的发光与能量传递的研究

本工作用固相反方法、以炭保护或在N_2-H_2还原气氛中，两次灼烧，合成了一系列烯土取代的卤磷酸盐发光体，其反应是M_2~ICO_3 + M_3~(II)(PO_4)_2 + M_2~(III)O_3 + (NH_4)_2HPO_4 + M~(II)F_2 → M_x~IM_(10-2x)~(II)M_x~(III)(PO_4)_6F_2 + NH_3 + H_2O式中：M~I = Li~+, Na~+, K~+; M~(II) = Ca~(2+), Sr~(2+); M~(III) = Y~(3+), La~(3+), Gd~(3+); X = 0.5, 1, 2, 3。通过X－射线分析法和以Eu~(3+)作为荧光离子探针方法确定了样品的物相和晶体结构，表明它与M_(10)~(II)(PO_4)_6F_2同属六方晶系(Pb_3/m)。并用图解外推法求得样品的晶胞参数a和c分别为9.41和6.89 A。在研究了M~I, M~(II)和M~(III)为不同阳离子，X为不同值时，取代物的物相和结构变化以及对Ce~(3+)发光和能量传递影响规律的基础上，以Na_2Ca_6La_2(PO_4)_6F_2为基本体系比较详细地研究了Ce~(3+)的发光，Ce~(3+)-Mn~(2+), Ce~(3+)-Re~(3+) (Re~(3+) = Pr~(3+)、Nd~(3+)、Sm~(3+)、Tb~(3+)、Dy~(3+)、Tm~(3+)、Ho~(3+)、Er~(3+))以及Ce~(3+)-Mn~(2+)-Re~(3+) (Re~(3+) = Dy~(3+), Nd~(3+))的能量传递。实验发现，Na_2Ca_6La_2(PO_4)_6F_2:Ce~(3+)是较强的紫外光发射体，发射谱带是由338和358nm两个宽带峰组成的，相应于~2D-~2F_(5/2)和~2D-~2F_(1/2)跃迁。发射强度和~2D-~2F_(6/2)，~2D-~2F_(7/2)两种辐射跃迁几率相对大小与温度，Ce~(3+)的浓度有关；F~-含量对发射强度也有强烈的影响。我们认为，浓度和温度的影响是由于Ce~(3+)-Ce~(3+)的能量迁移作用。实验发现，Ce~(3+)能有效地敏化Mn~(2+)的发光，得到高效的黄色荧光发射体。Ce~(3+)对Re~(3+)的作用可以分为三类：A）. Ce~(3+)-Sm~(3+)、Tb~(3+)、Dy~(3+)、Tm~(3+)；B）．Ce~(3+)-Nd~(3+)，Pr~(3+)；C）. Ce~(3+)-Ho~(3+), Er~(3+)。在A，B类型中，Ce~(3+)能有效地敏化这些稀土离子，但能量传递效率(η_T)_A > (η_T)_B。在Ce~(3+)-Ho~(3+)、Ce~(3+)-Er~(3+)类型中，Ho~(3+)、Er~(3+)不产生可见辐射，Ce~(3+)的发射强度也显著降低。在Ce~(3+)-Mn~(2+)-Re~(3+)三元中心体系中，Ce~(3+)的能量可直接传递给Mn~(2+)和Re~(3+)中心，还可通过Ce~(3+)-Mn~(2+)-Re~(3+)的途径传递。通过研究中心离子的浓度效应，温度效应、测定激发光谱、荧光光谱、荧光衰减曲线的荧光寿命，能够证实：在Ce~(3+)-Mn~(2+)、Ce~(3+)-Re~(3+)、Ce~(3+)-Mn~(2+)-Re~(3+)的能量传递属于无辐射共振传递相互作用类型。符合M. Yokata等人提出的偶极－偶极相互作用扩散限制传递历程。我们还利用Ce~(3+)、Ce~(3+)-Mn~(2+)、Ce~(3+)-Re、Ce~(3+)-Mn~(2+))-Re~(3+)激活体系中Ce~(3+)的发射强度和荧光寿命等数据计算了Ce~(3+)的能量传递效率。发现两种结果相差较大，为了准确地表达Ce~(3+)的敏化效果，在分析上了产生这种误差的原因后，提出了两种传递效率表示式(η_f, η_R)。

青稞B组醇溶蛋白基因与上游调控区的克隆及基因表达

高等植物种子胚乳贮藏蛋白是种子发芽时的主要氮源，也是人类和动物食用植物蛋白的主要来源。大麦种子胚乳贮藏蛋白主要是醇溶蛋白（hordeins），占大麦胚乳总蛋白的50–60%。根据大麦醇溶蛋白的大小和组成特点，大麦醇溶蛋白被划分为三种类型：富硫蛋白亚类(B，γ-hordeins)、贫硫蛋白亚类（C-hordeins)以及高分子量蛋白亚类(D-hordeins)。B组和C组醇溶蛋白是大麦胚乳的两类主要贮藏蛋白，它们分别占大麦总醇溶蛋白成分的70–80%和10–12%。遗传分析表明，大麦B、C、D和γ-组醇溶蛋白分别是由位于大麦第五染色体1H（5）上的Hor2、Hor1、Hor3和Hor5位点编码。Hor2位点编码大量分子量相同但组成不同的B组醇溶蛋白（B-hordein）。B-hordein的种类、数量和分布是影响大麦酿造、食用及饲养品质的重要因素之一。为深入了解B-hordein基因家族的结构和染色体组织，探明Hor2位点基因表达的发育调控机制，最终达到改良禾谷类作物籽粒品质的目的，本研究以青藏高原青稞为材料，采用同源克隆法，分别克隆B-hordein基因和启动子，通过原核生物表达验证B-hordein基因功能，并利用实时定量PCR探索B-hordein基因表达时空关系，取得如下研究结果： 1. 以具有特殊B组醇溶蛋白亚基组成的9份青藏高原青稞为材料，根据GenBank中三个B-hordein基因序列（GenBank No. X03103, X53690和X53691）设计一对引物，通过PCR扩增，获得23个B-hordein基因克隆并对其进行了序列分析。核苷酸序列分析表明，所有克隆均包含完整的开放阅读框。有11个克隆都存在一个框内终止密码子，推测这11个克隆可能是假基因。推测的氨基酸序列分析表明，所有大麦B-hordein具有相似的蛋白质基本结构，均包括一个高度保守的信号肽、中间重复区以及C-端结构域。不同大麦种重复区内重复基元的数目有较大差异。青稞材料Z07–2和Z26的B-hordeins仅具有12个重复基元结构，更接近于野生大麦。这些重复基元数目的差异导致了重复区序列长度和结构的变异。这种现象极可能是由于醇溶谷蛋白基因在进化过程中染色体的不平衡交换或复制滑动所造成的。对所克隆基因和禾本科代表性醇溶谷蛋白基因进行聚类分析，结果表明所有来自栽培大麦的B-hordeins聚类成一个亚家族，来自野生大麦的B-hordeins以及普通小麦的LMW-GS聚类成另外一个亚家族，表明这两个亚家族的成员存在显著差异。此外，我们发现B-hordein基因推测的C-末端序列具有一些有规律的特征：即具有相同C-末端序列的B-hordein基因在系统发生树中聚类为同一个亚组（除BXQ053，BZ09-1，BZ26-5分别单独聚为一类外）。这个特征将有助于我们对所有B组醇溶蛋白基因家族成员进行分类，避免了在SDS-PAGE电泳图谱上仅依靠大小分类的局限性。 2. 根据上述克隆的青稞B-hordein基因的5’端序列设计三条基因特异的反向引物，以青稞Z09和Z26的基因组DNA为模板，采用SON-PCR和TAIL-PCR技术分离克隆出8个B-hordein基因的上游调控序列（命名为Z09P和Z26P）。序列分析表明，推测的TATA box位于–80 bp，CAAT–like box位于–140 bp处。此外，Z09P和Z26P中有六个序列在–300 bp处均存在一个由高度保守的EM基序和类GCN4基序构成的胚乳盒(Endosperm Box，EB)，在约–560 bp处存在一个胚乳盒类似结构。而Z09P-2和Z26P-3不存在保守的胚乳盒或其类似结构，预示着这两个启动子所调控的基因表达可能受不同类型反式作用因子的调节，推测该启动子对基因的表达调控具有多样性。 3. 将B-hordein基因的开放阅读框定向克隆到表达载体pET-30a中，将其导入大肠杆菌表达菌株BL21中进行外源基因的诱导表达以验证所克隆基因的功能。结果表明仅含重组子pET-BZ07-2和pET-BZ26-5的BL21细菌有目的表达蛋白产生。在诱导3 h时的蛋白表达量最高；3 mM IPTG诱导的蛋白表达量要高于1 mM IPTG诱导的表达量。这为分离纯化B-hordein蛋白以及进一步研究其对大麦籽粒品质的影响奠定基础。 4. 根据从青稞Z09和Z26中分离克隆的B-hordein基因序列设计一对基因特异的引物，同时，选择大麦α-微管蛋白基因（GenBank no. U40042）为看家基因并设计特异引物，利用实时荧光定量PCR检测了青稞籽粒4个胚乳发育时间段的B-hordein基因表达，荧光定量结果显示：两份材料中B-hordein基因的表达量均随发育过程的进行而逐渐升高。Z09中B-hordein基因在开花后7天开始转录，而Z26开花4天后就有低水平B-hordein的表达，这表明Z26中B-hordein基因可能比Z09表达的较早或者Z09中B-hordein基因表达水平较低以致于不能被检测到。此外，在4个不同的胚乳发育时期中，Z26中B-hordein基因的表达量均高于Z09材料。在开花12天到18天的过程中，Z09和Z26中B-hordein基因的表达水平有一个急剧性的升高。这说明在不同胚乳发育时期，Hor2位点的B-hordein等位基因变异体存在mRNA的差异表达。 Seed endosperm storage proteins in higher plants are the main resources of nitrogen for germinating and plant proteins for human and animals. Barley prolamins (also called hordeins) are the major storage proteins in the endosperm and account for 50–60% of total proteins. Hordeins are classically divided into three groups: sulphur-rich (B, γ-hordeins), sulphur-poor (C-hordeins) and high molecular weight (HMW, D-hordeins) hordeins based on the size and composition. B-hordeins and C-hordeins are two major groups and each respectively account for about 70-80% and 10-12% of the total hordein fraction in barley endosperm. Genetic analysis showed that B-, C-, C-, γ-hordeins are encoded by Hor2, Hor1, Hor3 and Hor5 locus on the chromosome 1H (5). Hor2 locus is rich in alleles that encode numerous heterogeneous B-hordein polypeptides. It is reported that B-hordein species, quantity and distribution are significant factors affecting malting, food and feed quality of barley. To understand comprehensively the structure and organization of B-hordein gene family in hull-less barley and explore the developmental control mechanisms of Hor2 locus gene expression and eventually to better exploitation in crop grain quality improvement, we isolated and cloned B-hordein genes and promotors of hull-less barley from Qinghai-Tibet Plateau by PCR, and testified their expression founction in bacteria expression system and explore their spatial and temporal expression pattern by quantitative real time PCR. Our results are as followed, 1. Twenty-three copies of B-hordein gene were cloned from nine hull-less barley cultivars of Qinghai-Tibet Plateau with special B-hordein subunits and molecularly characterized by PCR, based on three B-hordein genes published previously (GenBank No. X03103, X53690 and X53691). DNA sequences analyses confirmed that the six clones all contained a full-length coding region of the barley B-hordein genes. Eleven clones all contain an in-frame stop codon and they are probably pseudogenes. The analysis of deduced amino acid sequences of the genes shows that they have similar structures including signal peptide domain, central repetitive domain, and C-terminal domain. The number of the repeats was largerly variable and resulted in polypeptides in different sizes or structures among the genes. Twelve such repeated motifs were found in Z07–2 and Z26, and they are close to those of the wild barleys, and it is most probably caused by unequal crossing-over and/or slippage during replication as suggested for the evolution of other prolamins. The relatedness of prolamin genes of barley and wheat was assessed in the phylogenetic tree based on their polypeptides comparison. Our phylogenetic analysis suggested that the predicted B-hordeins of cultivated barley formed a subfamily, while the B-hordeins of wild barleys and the two most similar sequences of LMW-GS of T. aestivum formed another subfamily. This result indicated that the members of the two subfamilys have a distinctive difference. In addition, we found the B-hordeins with identical C-terminal end sequences were clustered into a same subgroup (except BXQ053，BZ09-1 and BZ26-5 as a sole group, respectively), so we believe that B-hordein gene subfamilies possibly can be classified on the basis of the conserved C-terminal end sequences of predicted polypeptide and without the limit of SDS-PAGE protein banding patterns. 2. The specific primers were designed according to the published sequences of barley B-hordein genes from Z09 and Z26. Using total DNA isolated from them as the templates, eight clones (designated Z09Pand Z26P) of upstream sequences of the known B-hordein genes was obtained by TAIL-PCR and SON-PCR. Sequences analysis shows that the putative TATA box was present at position –80 bp and CAAT-like box at position –140 bp. Besides, a putative Endosperm Box including an Endosperm Motif (EM) and a GCN4-Like Motif was found at position –300 bp in six clones, and another Endosperm-like box was found at positon –560 bp. While the Endosperm Box or Endosperm-like box was not found in Z09P-2 and Z26P-3. This may indicate that gene expression drived by the two promtors was probably controlled by different trans-acting factors and the genetic control mechanism of corresponding gene expression may be diverse. 3. The B-hordein genic region coding for the mature peptide was cloned into expression vector pET-30a and transformed into bacterial strain BL21 for identifying gene expression fountion. Protein SDS–PAGE analysis showed that only the transformed lysate with the pET-BZ07-2 and pET-BZ26-5 constructs produced proteins related to B-group hordeins of barley, and the mounts of proteins induced by 3 mM IPTG and 3 h were higher than other conditions. This established a base for isolating and putifying B-hordein and further exploring their effects on barley grain quality. 4. The gene-specific primers of B-hordein genes from Z09 and Z26 were used for the quantification of B-hordein gene expression. The α-tubulin gene from Hordeum vulgare subsp. vulgare (GenBank accession number U40042) was used as a control gene. The result shows the transcription of the B-hordein genes in Z09 was found 7 days after flowering, while the transcription of the B-hordein genes in Z26 was found 4 days after flowering, but at a very low level, and it suggested that the B-hordein genes in Z26 probably expressed earlier than those in Z09, or the B-hordein genes in Z09 expressed at so a lower level than Z26 that it can not detected. In addition, B-hordein genes in Z26 accession showed higher expression levels than those in Z09 in four developing stages. Furthermore, a progressive increase in the expression levels of the B-hordein genes between 12 and 18 days after anthesis was observed in both Z09 and Z26. It implies that the B-hordein allelic variants encoded by Hor2 locus exist the differential expression in mRNA levels of during barley endosperm development.

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

Synthesis, characterization and crystal structure of a charge transfer salt based on 1.3-cyclopentadiene tetrabutylammoniumdodecamolybdosilicoate

A charge transfer salt, (Bu4N)(4) (C5H6)[(HSiMo11MoO40)-Mo-VI-O-V] has been photochemically synthesized from (Bu4N)(4)SiMo12O40 and 1.3-cyclopentadiene and Characterized, by elemental analysis, IR spectra, solid diffusion reflectance electronic spectra, CV and ESR. The X-ray crystal structure revealed that the title complex crystal data are as follows: triclinic, space group P (1) over bar, a = 14.347(3), b = 14.423(3), c = 27.158(5) Angstrom, alpha = 96.90(3), beta = 104.18(3), gamma = 98.20(3)degrees, V = 5322(2) Angstrom (3), Z = 2, M-r = 2855. 30, D-c = 1.782g.cm(-3), F(000) = 2860, R = 0.0719, wR = 0.198. The title compound is composed of 1.3-cyclopentadiene, four tetrabutylammonium and [(SiMo11MoO40)-Mo-VI-O-V](4-) anion.

THE CLEAVAGE REACTION OF THE MO-MO TRIPLE BOND - THE CRYSTAL-STRUCTURES OF MOLYBDENUM COMPLEXES [CPMO(CO)(2)(C(5)H(4)NS)], [CPMO(CO)(2)(C(9)H(6)NS)]O=PPH(3) AND [CPMO(CO)(2)(S(2)CNME(2)]

The reactions of [Cp2Mo2(CO)4] (1) with 2,2'-dipyridyl disulphide (C5H4NS-)2, 8,8'-diquinolyl disulphide (C9H6NS-)2 and tetramethyl thiuram disulphide (Me2NC(S)S-)2 in toluene solution resulted in the cleavage of the Mo-Mo triple bond to yield molybdenum complexes [CpMo(CO)2(C5H4NS)] (2), [CpMo(CO)2(C9H6NS)] (3) and [CpMo(CO)2(S2CNMe2)] (4), respectively. The molecular structures of 2, 3 . O=PPh3 and 4 were determined by X-ray diffraction studies. Crystals of 2 are monoclinic, space group P2(1)/n, with Z = 4, in a unit cell of dimensions a = 6.448(1), b = 12.616(2), c = 14.772(2) angstrom, beta = 92.85(1)-degrees. The structure was refined to R = 0.028 and R(w) = 0.039 for 1357 observed reflections. Crystals of 3 . O=PPh3 are triclinic, space group P1BAR, with Z = 2, in a unit cell of dimensions a = 11.351(3), b = 13.409(3), c = 9.895(2) angstrom, alpha = 94.59(2), beta = 90.35(2), gamma = 78.07(2)-degrees. The structure was refined to R = 0.033 and R(w) = 0.037 for 3260 observed reflections. Crystals of 4 are monoclinic, space group P2(1)/a and Z = 4 with a = 12.468(5), b = 7.637(2), c = 13.135(4) angstrom, beta = 96.62(3). The structure was refined to R = 0.032 and R(w) = 0.042 for 1698 observed reflections. Each of complexes 2-4 contains a cyclopentadienyl ligand, a cis pair of carbonyls and a chelate ligand (S,N donor or S,S donor). All the compounds have distorted square-pyramid structures.

SYNTHESIS AND MOLECULAR-STRUCTURE OF NBU2[(MEO)3C6H2C(O)N2CHC6H4O]SN FORMED IN THE REACTION OF DI-N-BUTYLTIN(IV) OXIDE WITH 3,4,5-TRIMETHOXY-BENZOYL SALICYLAHYDRAZONE

The title complex was synthesized and characterized by H-1, C-13, Sn-119 NMR and IR spectra. A single crystal X-ray diffraction study confirmed its molecular structure and revealed that 3,4,5-trimethoxy-benzoyl salicylahydrazone was a tridentate and approximately planar ligand. The complex crystallizes in the triclinic space group P1BAR with a = 9.208(3), b = 12.536(2), c = 12.187(4) angstrom, alpha = 113.12(2), beta = 90.58(2), gamma = 81.42(2), V = 1277.5(6) angstrom, Z = 2. The structure was refined to R = 0.033 and R(w) = 0.041 for 3944 observed independent reflections. The tin atom has a distorted trigonal bipyramidal coordination. The Sn-C bond lengths are 2.129(5) and 2.113(5) angstrom (av. 2.121(5) angstrom), the C-Sn-C angle is 123.3(2); the bond length between the tin atom and the chelating nitrogen is 2.173(3) angstrom. Two chain carbon atoms and the chelating nitrogen atom occupy the basal plane. The skeleton of two erect oxygen atoms and the tin atom is bent (O-Sn-O angle = 153.5(1)). In the complex, the ligand exists in the enol-form.

YV_(1-x)B_xO_(4-x):Eu~(3+)(或Dy~(3+),Bi~(3+))的合成及光谱性质的研究

本文报道了Eu~(3+)、D~(3+)在YV_(1-x)B_xO_(4-x)中的光谱性质。实验表明:B~(3+)取代V~(5+)时,可使基质和Dy~(3+)的发射强度及黄兰比下降,并使基质的吸收带短移。而B~(3+)取代Y~(3+)时,则可提高Dy~(3+)的黄兰比。同时我们还研究了Bi~(3+)和温度对YV_(0.69)B_(0.31)O_(3.69):Dy~(3+)中Dy~(3+)发射强度的影响。

岩浆－热液过渡阶段体系中不相容元素地球化学行为及其机制－以新疆阿尔泰3号伟晶岩脉研究为例

伟晶岩形成和演化中岩浆-热液过渡阶段物理化学性质、过铝质富挥发分岩浆体系岩浆液相不混溶、流体相出溶事件的相对时间尺度以及在岩浆-热液过渡阶段体系中稀土和其它微量元素地球化学行为(稀土“四重效应”机制和微量元素分异及控制因素等)是目前过铝质岩浆体系研究的焦点问题。对上述问题的研究和探讨，将有助于了解伟晶岩形成和演化的全过程，有助于了解挥发分(H_20、F、B、P)对过铝质岩浆体系物理性质以及对REE和其它微量元素地球化学行为影响，这对于理解过铝质岩浆体系成岩、成矿作用过程具有重大的理论和实际意义。本论文选择著名的新疆阿尔泰3号伟晶岩脉为研究对象，由于它具有完美的分带特征，使我们有可能通过各结构带矿物学、地球化学的研究揭示伟晶岩成因和演化过程以及讨论岩浆-热液过渡阶段体系中的稀土和微量元素地球化学行为。由于LCT型伟晶岩具有明显的分带性、矿物颗粒大小不均匀性等特点，因此利用全岩样品研究伟晶岩往往因取样没有代表性而被大多数岩石学家和地球化学家所否定。考虑到这点，本文系统采集阿尔泰3号伟晶岩脉各结构带磷灰石、电气石、碱性长石、石英矿物，部分结构带的石榴石、绿柱石、锂辉石矿物以及伟晶岩冷凝边和蚀变围岩的全岩样品，通过各结构带磷灰石矿物化学组成和~(87)Sr／~(86)Sr比值测定，电气石矿物的化学组成和硼同位素组成分析，碱性长石中磷含量的电子探针分析和碱性长石-石英矿物对的氧同位素体系研究以及蚀变围岩和冷凝边的化学组成分析，本文较为详尽系统地探讨以上所有的问题。通过本次多年的研究，我们获得了以下几点新的认识：f1) 富挥发分过铝质岩浆体系的样品存在稀土“四重效应”和Y-Ho、Zr-Hf、Nb-Ta、Sr-Eu元素对的显著分异，表明在过铝质岩浆演化过程中含氟流体相起着重要的作用；目前，稀土“四重效应”机制被认为是含水流体相与过铝质岩浆熔体相互作用的结果(Irber 1999；Bau 1997)，而不是独居石、磷钇矿、石榴石矿物等矿物的早期结晶引起的残余熔体稀土含量的异常变化。由于阿尔泰3号伟晶岩脉各带磷灰石以及与其共生的石榴石、绿柱石、碱性长石、锂辉石矿物均存存明显的稀土“四重效应”以及相同电价、相似离子半径的不相容元素间存在显著的分异，并结合最近赵振华等(1999)和Sba and Chappell(1999)报道S型花岗岩全岩和单矿物(磷灰石、独居石、长石、黄玉等)均存在稀土“四重效应”这一现象，本文研究提出，稀土“四重效应”是富挥发分过铝质岩浆体系的一个基本特征，其机制既不可能由含稀土的副矿物早期结晶引起残余熔体相中REE含量变化的结果，也不能定性地归因于流体相与熔体相相互作用过程中稀土元素在流体／熔体之间分异的结果，而很可能与伟晶岩岩浆形成之前某些过程密切相关，S型花岗岩岩浆在液相线以上存在硅酸盐熔体与高盐熔体(或卤水相)的不混溶液相分离有可能是过铝质岩浆体系产生稀土“四重效应”的主要原因。(2) 由于Sr~(2+)与Eu~(2+)具有相同的电价、相似的离子半径，根据经典的地球化学原理，它们具有相似的地球化学行为，在各种地质过程中其它们具有紧密的一致性。阿尔泰3号伟晶岩磷灰石中Sr／Eu比值具有二歧变化现象，其中I、Il、III和IV带磷灰石具有低的Sr／Eu比值(16:0～111.2)，而V、VI、VII带、核部带和IV带中的一个磷灰石则显示较大的Sr／Eu比值(主要在246．6～514:9范围，其中IV带的一个磷灰石该比值在10000以上)。对世界范围内的过铝质花岗岩统计表明，过铝质岩浆岩的全岩样品中的Sr／Eu也呈现二歧变化，由此本文提出Sr／Eu比值是指示过铝质岩浆体系中岩浆流体相出溶的有效地球化学参数，大于300的Sr／Eu比值是Eu~(2+)强烈分配进入流体相的地球化学标志。(3) 阿尔泰3号伟晶岩I、II、III带电气石矿物的硼同位素组成(δ~(11)B)分布在-41.11‰～-30.90‰之间，V、VI、VII带电气石矿物硼同位素组成(δ~(11)B)在-15.23‰～-9.20‰范围，IV带电气石硼同位素分布于-39.19～13.10‰范围，如此大的硼同位素分馏无法根据实验研究获得的熔体／流体相间的分馏系数进行合理解释。我们的研究表明岩浆成因电气石的B同位素组成与电气石化学组成具相关性，随电气石Y位上AI、Li阳离子数的增大，δ~(11)B值显示明显增大的趋势。阿尔泰3号伟晶岩最初形成的结构带中电气石的B同位素组成是目前所发现的最低值之一(-41.1l～39.01‰)，指示形成伟晶岩脉的初始岩浆可能由含非海相蒸发岩的泥质岩经变质深熔作用形成，或是伟晶岩岩浆在上侵定位过程中同化了含非海相蒸发岩地层的结果。本次研究利用电气石-白云母和电气石-四硼酸盐矿物间的同位索分馏以及熔体相-流体相间的同位索分馏，合理解释了阿尔泰3号伟晶岩脉电气石B同位素分馏过程，并首次获得伟晶岩形成、演化过程中B同位素组成演化的全程图谱。(4)伟晶岩岩浆形成和演化过程是否存在由过磷引起的液相不混溶现象未见确凿的岩石学和实验地球化学证据。阿尔泰3号伟晶岩脉糖粒状钠长石带(II带)明显由两种不同组构的岩性组成，而且该带是3号脉主要的Be矿化带，也是P、REE最重要的沉淀场所。阿尔泰3号伟晶岩脉梳状结构带和I带的碱性长石具较高P含量(平均值分别为0.42 wt％和0.22 wt％)，随着岩浆的演化进行，从III带到核部带，碱性长石中P含量逐渐增大(平均值由0.21 wt％增至0.50 wt％)，而II带碱性长石中异常低的P含量(平均值为0.08、wt％)是该带大量磷灰石矿物饱和结晶，导致残余熔体相中P极度亏损所造成的，而不是晚期出溶的岩浆热液交代形成的。根据Watson (1978)、Ryerson and Hess(1980)在液相线以上温度下实验研究获得的微量元素在不混溶的基性和酸性液相中分配特征，以及Webster et a1．(1997）对德国Ehrenfriedersdorf矿区伟晶岩石英中熔体包裹体的研究成果，我们推断在富磷岩浆体系中，在其演化的早期将出现由磷引起的液相不混溶作用，它对伟晶岩成岩和Be的成矿具有重大的影响。