镧系金属有机配合物Gd(2,4-C_7H_(11))_3的晶体和分子结构

2,4-二甲基戊二烯基的金属配合物在一些性质上可与相应的环戊二烯配合物相比拟。已报道了许多d过渡金属以及碱金属钾的配合物的晶体结构。对于镧系金属,仅Ernst等得到了2,4-二甲基戊二烯钕的配合物并测定了晶体结构,其晶格中含有无序的乙醚溶剂分子。本文报道了不含溶剂分子的Gd(2,4-C_7H_(11))_3,配合物在低温下的晶体结构。

11-钨硼酸钾的结构和振动光谱研究

标题化合物K_8H〔BW_(11)O_(39)〕·13H_2O属立方晶系,空间群P43m,a=10.710(1)A,V=1228.58A~3,Z=1;D_O=4.39g·cm~(-3),D_c=4.42g·cm~(-3)。(BW_(11)O_(3.9)~(9-)离子属于不饱和α-Keggin型结构,B原子位于O_a四面体的中心。测定并研究了化合物的IR和Raman光谱性质。

Molecular cloning and expression of interleukin 1beta (IL-1 beta) from red seabream (Pagrus major)

The interleukin 1beta (IL-1beta) cDNA was cloned from the red seabream (Pagrus major) by homology cloning strategy. A cDNA fragment was amplified by PCR using two degenerated primers, which were designed according to the conserved regions of other known IL-1beta sequences, and elongated by 3' ends and 5' ends RACE PCR to get the full length coding sequence of red seabream IL-1beta (RS IL-1beta). The sequence contained 1252 nucleotides that included a 5' untranslated region (UTR) of 84 bp, a 3' UTR of 410 bp and an open reading frame (ORF) of 759 nucleotides which could be translated into a putative peptide of 253 amino acids with molecular weight of 28.6 kD and putative isoelectric point pI of 5.29. The deduced peptide contained two potential N-glycosylation sites and an identifiable IL1 family signature, but lacked the signal peptide and the clear ICE cut site, which were common in other nonmammalian IL-1beta genes. The RS IL-1beta had the highest homology with piscine IL-1beta according to phylogenetic tree analysis. The transcript expression was detected in blood, brain, gill, heart, head kidney, kidney, liver, muscle and spleen in the pathogen challenged and healthy red seabream by RTPCR. Results showed that the RS IL-1beta mRNA was constitutively expressed in most of the tissues both in stimulated and un-stimulated fish, and the expression could be enhanced by pathogen challenging.

Characterization of amphioxus GDF8/11 gene, an archetype of vertebrate MSTN and GDF11

MSTN, also known as growth and differentiation factor 8 (GDF8), and GDF11 are members of the transforming growth factor-beta (TGF-beta) subfamily. They have been thought to be derived from one ancestral gene. In the present study, we report the isolation and characterization of an invertebrate GDF8/11 homolog from the amphioxus (Branchiostoma belcheri tsingtauense). The amphioxus GDF8/11 gene consists of five exons flanked by four introns, which have two more exons and introns than that of other species. In intron III, a possible transposable element was identified. This suggested that this intron might be derived from transposon. The amphioxus GDF8/11 cDNA encodes a polypeptide of 419 amino acid residues. Phologenetic analysis shows that the GDF8/11 is at the base of vertebrate MSTNs and GDF11s. This result might prove that the GDF8/11 derived from one ancestral gene and the amphioxus GDF8/11 may be the common ancestral gene, and also the gene duplication event generating MSTN and GDF11 occurred before the divergence of vertebrates and after or at the divergence of amphioxus from vertebrates. Reverse transcriptase polymerase chain reaction results showed that the GDF8/11 gene was expressed in new fertilized cell, early gastrulation, and knife-shaped embryo, which was different from that in mammals. It suggested that the GDF8/11 gene might possess additional functions other than regulating muscle growth in amphioxus.

文昌鱼发育相关基因GDF8/11、ACTIVIN和NM23-Bbt2的克隆、表达及分子进化分析

文昌鱼是头索动物，被认为是现存的与脊椎动物最接近的无脊椎动物，经常被看作是分析从无脊椎动物到脊椎动物进化过程的一种重要的模式动物。在本研究中，我们克隆了青岛文昌鱼的GDF8/11、ACTIVIN和NM23-Bbt2基因，并对这些基因在不同胚胎发育时期和不同成体组织中的表达情况进行了分析，同时分析了这些基因的进化情况。 文昌鱼GDF8/11的基因组全长为9.9 kb，包括五个外显子和四个内含子，比其他物种多出两个外显子和两个内含子。在多出的第三个内含子中，我们分离出一个可能的转座因子，这表明这个内含子可能来源于转座子。文昌鱼GDF8/11 cDNA编码一个419个氨基酸的前体多肽，这个前体多肽与软体动物、硬骨鱼类、鸟类和哺乳动物的MSTN以及哺乳动物和斑马鱼的GDF11具有高同源性。系统分析表明文昌鱼GDF8/11位于脊椎动物MSTN和GDF11的根部，这个结果证实MSTN/GDF11来源于同一个祖先基因，并且文昌鱼GDF8/11可能就是他们的共同祖先，产生MSTN和GDF11的基因复制事件发生在脊椎动物分离之前和文昌鱼与脊椎动物分离之后或者分离时。RT-PCR结果表明GDF8/11基因在新受精的细胞、早原肠胚和刀形胚胎中表达，这与哺乳动物中的情况不同。这表明GDF8/11在文昌鱼中除了调节肌肉生长外还可能拥有其他的功能。 文昌鱼ACTIVIN的基因组序列长为6.1 kb，启动子大约长为447 bp，其基因组包括两个外显子和一个内含子，外显子/内含子边界严格遵守GT…AG的原则。文昌鱼ACTIVIN基因编码一个410个氨基酸的前体蛋白，前体蛋白包括信号肽、N-末端结构域和C-末端结构域。文昌鱼ACTIVIN基因演绎的氨基酸序列与脊椎动物比较发现ACTIVIN基因比较保守，特别是C-末端生物活性区。系统进化分析表明脊椎动物和无脊椎动物的ACTIVIN基因分别聚在一起，文昌鱼的ACTIVIN则位于脊椎动物ACTIVIN分支的根部，这表明文昌鱼ACTIVIN基因可能是脊椎动物ACTIVIN同源基因的祖先基因。 文昌鱼NM23-Bbt2 cDNA包括一个编码171个氨基酸的开放阅读框，序列分析表明文昌鱼NM23-Bbt2与其他物种高度保守，他们都包含高度保守的基元，并且这些基元在NM23的功能中扮演着重要的角色。RT-PCR分析表明文昌鱼NM23-Bbt2在所检测的组织和胚胎发育时期中的非特异性的表达模式。系统分析表明脊椎动物和无脊椎动物NM23-H2分别聚在一起，而文昌鱼NM23-Bbt2位于脊椎动物NM23-H2分支的根部，这表明文昌鱼NM23-Bbt2可能是脊椎动物NM23-H2同源基因的祖先基因。从无脊椎动物到脊椎动物的基因组结构比较表明五个外显子和四个内含子的基因组结构可能产生在文昌鱼与脊椎动物分离之前。

Immunomodulation and antitumor activity of kappa-carrageenan oligosaccharides

The modulation of carrageenan oligosaccharides from Kappaphycus striatum on the immune system in S 180-bearing mice was investigated. The mice inoculated with S180 cell suspension were treated p.o. with carrageenan oligosaccharides (50, 100 and 200 mu g/g) for 14 days. The effects of carrageenan oligosaccharides on transplantable tumors and macrophage phagocytosis, quantitative hemolysis of sheep red blood cells (QHS),. lymphocyte proliferation, the activity of natural killer cells (NK), production of interleukin-2 (IL-2) and tumor necrosis factor-alpha (TNF-alpha) were studied. Carrageenan oligosaccharides could significantly inhibit the growth of transplantable sarcoma S180 and increase macrophage phagocytosis, the form of antibody secreted by spleen cells, spleen lymphocyte proliferation, NK cells activity, serumal IL-2 and TNF-alpha level in S 180-bearing mice. Considering all these results, it is suggested that carrageenan oligosaccharides exert their antitumor effect by promoting the immune system. (c) 2005 Elsevier Ireland Ltd. All rights reserved.

Application of 2-(11H-benzo[a] carbazol-11-yl) Ethyl Carbonochloridate as a Pro-column Derivatization Reagent of Amino Acid by High Performance Liquid Chromatography with Fluorescence Detection

On a reversed phase Hypersil BDS C-18 (200 mm x 4. 6 mm, 5 mu m) column, 20 amino acids, which were derivatized using 2-(11H-benzo [a] carbazol-11-yl) ethyl carbonochloridate (BCEC-Cl) as pre-column derivatization reagent, were separated in conjunction with a gradient elution. Optimum derivatization was obtained by reacting of amino acids with BCEC-Cl at room temperature for 5 min in the presence of sodium borate catalyst in acetonitrile solvent. The fluorescence excitation and emission wavelengths were 279 nm and 380 nm respectively. The identification of amino acid derivatives from hydrolyzed bovine serum albumin and bee pollen was carried out by post-column mass spectrometry with electrospray ion source in positive ion mode. Linear correlation coefficients of the amino acid derivatives were > 0.9990, and detection limits (at signal to noise of 3:1) were 1.49 - 19.74 fmol for the labeled amino acids.

Determination of amines using 2-(11H-benzo[a]carbazol-11-yl) ethyl chloroformate (BCEC-Cl) as labeling reagent by HPLC with fluorescence detection and identification with APCI/MS

A pre-column derivatization method for the sensitive determination of amines using a labeling reagent 2-(11H-benzo[a]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) followed by high-performance, liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by LC/APCI/MS in positive-ion mode. The chromophore of 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC-Cl) reagent was replaced by 2-(11H-benzo[a]-carbazol-11-yl) ethyl functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEC-Cl. BCEC-Cl could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M+ H](+) under APCI/MS in positive-ion mode. The collision-induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 261.8 and m/z 243.8 corresponding to the cleavages of CH2O-CO and CH2-OCO bonds. Studies on derivatization demonstrated excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% were observed with three- to four-fold molar reagent excess. In addition, the detection responses for BCEC-derivatives were compared to those obtained using 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC-Cl) and 9-fluorenyl methylchloroformate, (FMOC-Cl) as labeling reagents. The ratios I-BCEC/I-BCEOC = 1.94-2.17 and I-BCEC/I-FMOC = 1.04-2.19 for fluorescent (FL) responses (here, I was relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits calculated from 0.50 pmol injection, at a signal-to-noise ratio of 3, were 1.77-14.4 fmol. The relative standard deviations for within-day determination (n = 11) were 1.84-2.89% for the tested amines. The mean intra- and inter-assay precision for all amines levels were < 3.64% and 2.52%, respectively. The mean recoveries ranged from 96.6% to 107.1% with their standard deviations in the range of 0.8-2.7. Excellent linear responses were observed with coefficients of > 0.9996. (C) 2006 Elsevier B.V. All rights reserved.

珠江口盆地流花11-1油田储层非均质性及流体分布规律研究

In order to discover the distribution law of the remaining oil, the paper focuses on the quantitative characterization of the reservoir heterogeneity and the distribution law of the fluid barrier and interbed, based on fine geological study of the reservoir in Liuhuall-1 oil field. The refined quantitative reservoir geological model has been established by means of the study of core analysis, logging evaluation on vertical well and parallel well, and seismic interpretation and prediction. Utilizing a comprehensive technology combining dynamic data with static data, the distribution characteristics, formation condition and controlling factors of remaining oil in Liuhuall-1 oil field have been illustrated. The study plays an important role in the enrichment regions of the remaining oil and gives scientific direction for the next development of the remaining oil. Several achievements have been obtained as follows: l.On the basis of the study of reservoir division and correlation,eight lithohorizons (layer A, B_1, B_2, B_3, C, D, E, and F) from the top to the bottom of the reservoir are discriminated. The reef facies is subdivided into reef-core facies, fore-reef facies and backreef facies. These three subfacies are further subdivided into five microfacies: coral algal limestone, coralgal micrite, coral algal clastic limestone, bioclastic limestone and foraminiferal limestone. In order to illustrate the distribution law of remaining oil in high watercut period, the stratigraphic structure model and sedimentary model are reconstructed. 2.1n order to research intra-layer, inter-layer and plane reservoir heterogeneity, a new method to characterize reservoir heterogeneity by using IRH (Index of Reservoir Heterogeneity) is introduced. The result indicates that reservoir heterogeneity is medium in layer B_1 and B_3, hard in layer A, B_2, C, E, poor in layer D. 3.Based on the study of the distribution law of fluid barrier and interbed, the effect of fluid battier and interbed on fluid seepage is revealed. Fluid barrier and interbed is abundant in layer A, which control the distribution of crude oil in reservoir. Fluid barrier and interbed is abundant relatively in layer B_2,C and E, which control the spill movement of the bottom water. Layer B_1, B_3 and D tend to be waterflooded due to fluid barrier and interbed is poor. 4.Based on the analysis of reservoir heterogeneity, fluid barrier and interbed and the distribution of bottom water, four contributing regions are discovered. The main lies on the north of well LH11-1A. Two minors lie on the east of well LH11-1-3 and between well LH11-1-3 and well LH11-1-5. The last one lies in layer E in which the interbed is discontinuous. 5.The parameters of reservoir and fluid are obtained recurring to core analysis, logging evaluation on vertical well and parallel well, and seismic interpretation and prediction. Theses parameters provide data for the quantitative characterization of the reservoir heterogeneity and the distribution law of the fluid barrier and interbed. 6.1n the paper, an integrated method about the distribution prediction of remaining oil is put forward on basis of refined reservoir geological model and reservoir numerical simulation. The precision in history match and prediction of remaining oil is improved greatly. The integrated study embodies latest trend in this research field. 7.It is shown that the enrichment of the remaining oil with high watercut in Liuhua 11-1 oil field is influenced by reservoir heterogeneity, fluid barrier and interbed, sealing property of fault, driving manner of bottom water and exploitation manner of parallel well. 8.Using microfacies, IRH, reservoir structure, effective thickness, physical property of reservoir, distribution of fluid barrier and interbed, the analysis of oil and water movement and production data, twelve new sidetracked holes are proposed and demonstrated. The result is favorable to instruct oil field development and have gotten a good effect.

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。

7-11岁正常儿童和ADHD儿童故事重述能力及策略的发展

儿童的故事重述涉及工作记忆和抽象表征能力，是与儿童的日常学业任务密切联系。儿童能否把握时间线索来组织故事重述，反映的是儿童抽象出故事事件内在时间关系的能力，因此对儿童故事重述的探查可以揭示儿童抽象思维发展的一般规律和特点。本研究在前人研究的基础上，系统探查了7－11岁儿童故事重述能力及其策略的发展过程，探讨了时间线索对儿童故事重述的影响，并对ADHD儿童和正常儿童的故事重述及策略进行了比较。 主要研究结果如下： (1)7－11岁儿童故事重述能力总体上随年龄增长而提高，按正确顺序重述的事件数量增多，重述过程中提取和使用的时间线索也增加。其中7－9岁有较快速的发展。 (2)随故事中包含的事件数量的增加，故事难度增大，儿童的故事重述成绩有所下降，故事长度对7岁和9岁儿童的影响大于对11岁儿童的影响。 (3)有、无时间线索语词会影响儿童的故事重述。故事中包含时间语词线索有助于儿童的故事重述。11岁儿童的故事重述已不受有、无时间线索的影响，他们在无时间线索的条件下，更多地主动使用表示因果关系的语词来表征事件关系。 (4)ADHD儿童的故事重述能力在9岁到11岁有较快的发展。但总体而言，ADHD儿童对含有时间线索故事的重述能力显著差于正常儿童。 (5)故事再学习对ADHD儿童和正常儿童的故事重述都存在促进作用。但ADHD儿童故事再学习效果不如正常儿童，低龄儿童中差距尤其明显，随着年龄的增加，ADHD儿童与正常儿童故事再学习效果的差距逐渐缩小。 (6)不同年龄的儿童主要采用四种策略解决问题。随年龄增长，正常儿童和ADHD儿童中使用水平较高的内容主线和逻辑关系策略的人数都有所增加。但ADHD儿童中高水平策略使用人数比例仍低于正常儿童。