A new dinuclear molybdenum(V)-sulfur complex containing citrate ligand: synthesis and characterization of K2.5Na2NH4[Mo2O2S2(cit)(2)].5H(2)O

The complex, K2.5Na2NH4[Mo2O2S2(cit)(2)]. 5H(2)O (1), was obtained by crystallization from a solution of (NH4)(2)MoS4, potassium citrate (K(3)cit) and hydroxyl sodium in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The crystals are triclinic, space group , a = 7.376 (3)Angstrom, b = 14.620 (2) Angstrom, c = 14.661 (1) Angstrom, alpha = 71.10 (1)degrees, beta = 81.77 (1)degrees, gamma = 78.27(2)degrees, R = 0.0584 for 2545 observed (I > 2 sigma (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with two bridging sulfur atoms and a terminal oxygen atom completes distorted coordination octahedron around each molybdenum atom. Principal dimensions are: Mo = O-t, 1.707 Angstrom (av); Mo-S-b, 2.341 Angstrom (av); Mo-O-(hydroxyl), 2.021 Angstrom (av); Mo-O(alpha-carboxyl), 2.1290 Angstrom (av) and Mo-O(beta-carboxyl), 2.268(av) Angstrom. IR spectrum is in agreement with the structure.

Synthesis and polymerization of some macrocyclic (arylene ether sulfone) containing cardo groups and macrocyclic (arylene ether ketone sulfone) oligomers

Some novel macrocyclic (arylene ether sulfone) containing cardo groups and (arylene ether ketone sulfone) oligomers have been synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-difluorophenylsulfone with bisphenols in the presence of anhydrous potassium carbonate under a pseudo-high-dilution condition. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), fast atom bombardment mass spectrometry (f.a.b.-m.s.), nuclear magnetic resonance spectrometry (n.m.r.) and single-crystal X-ray structure analysis confirms their cyclic nature, and the composition of the oligomeric mixtures is provided by g.p.c. analysis. Ring polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 59.1 k was achieved by heating at 290 degrees C for 40 min in the presence of a nucleophilic initiator. (C) 1998 Elsevier Science Ltd. All rights reserved.

A new crystal modification of gutta percha

Single chain and pauci chain single crystals of gutta percha in nanometer size were prepared by a dilute solution spraying method. A new crystal modification of gutta percha was found. The unit cell of the new modification of gutta percha was determined by electron diffraction crystal structure analysis to be a hexagonal form with cell dimensions: a = b = 0.695 nm, c = 0.661 nm, alpha = beta = 90 degrees, gamma =120 degrees; the space group is P6. The molecular packing in the unit cell was determined by computer modelling with Cerius(2) 2.0 software. (C) 1998 Elsevier Science Ltd. All rights reserved.

Synthesis and structures of the complexes of beta-alkoxycarbonylethyltin trichlorides with N-aryl-2-hydroxyacetophenylideneimines

Sixteen novel beta-alkoxycarbonylethyltin trichlorides and the corresponding N-aryl-2-hydroxyacetophenylideneimines complexes have been synthesized and characterized. An X-ray crystal structure analysis of the complex of beta-methyloxycarbonylethyltin trichloride and N-4-methylphenyl-2-hydroxyacetophenylideneimine has been performed, The crystal belongs to space group , The cell parameters are: a = 1.0201(6) nm, b = 1.082 2(4) nm, c = 1.394 9(6) nm, alpha = 99.88(3)degrees, beta = 98.63(4)degrees, gamma = 97.86(4)degrees, Z = 2, The ligands coordinate to tin atom via phenolic oxygen atom. Coordination of carbonyl oxygen atom to tin atom still exists in the complexes, The coordination number of tin atom is 6.

SYNTHESES AND CRYSTAL-STRUCTURES OF (C8H8)ND(C5H9C5H4)(THF)(2) AND [(C8H8)GD(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)(2)]

LnCl(3) (Ln = Nd, Gd) reacts with C5H9C5H4Na (or K2C8H8) in THF (C5H9C5H4 = cyclopentylcyclopentadienyl) in the ratio of 1:1 to give (C5H9C5H4)LnCl(2)(THF)(n) (or (C8H8)LnCl(2)(THF)(n)], which further reacts with K2C8H8 (or C5H9C5H4Na) in THF to form the title complexes. If Ln = Nd the complex (C8H8)Nd(C5H9C5H4)(THF)(2) (a) was obtained: when Ln = Gd the 1:1 complex [(C8H8)Gd(C5H9C5H4)(THF)][(C5H8)Gd(C5H9C5H4)(THF)(2)] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)(2) (Ln = Nd or Gd), the Cyclopentylcyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp') in C5H9C5H4 group, cyclooctatetraenyl centroid (COT) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp', COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. - 0.0144 Angstrom).

PHOTOELECTROCHEMISTRY OF ELECTRODEPOSITED POLYCRYSTALLINE CUINSE2 THIN-FILMS .1. ELECTRODEPOSITION OF CUINSE2 FILMS

Electrodeposition of CuInSe2 was investigated in acidic solutions containing Cu2+, In3+ and HSeO2+ ions. The electrodeposition condition was optimized with the aim of obtaining uniform thin films on titanium substrate. The mechanism of the electrodeposition process is discussed. Structure analysis of the deposited film shows a typical polycrystalline chalcopyrite structure, good crystallinity and homogeneous dispersion. The photoelectrochemical cells made of these kinds of deposited films in polysulfide redox solution give distinct photoresponse.

The complete mitochondrial genome sequence of the cutlassfish Trichiurus japonicus (Perciformes: Trichiuridae) : Genome characterization and phylogenetic considerations

Mitochondrial genome sequence and structure analysis has become a powerful tool for studying molecular evolution and phylogenetic relationships. To understand the systematic status of Trichiurus japonicus in suborder Scombroidei, we determined the complete mitochondrial genome (mitogenome) sequence using the long-polymerase chain reaction (long-PCR) and shotgun sequencing method. The entire mitogenome is 16,796 by in length and has three unusual features, including (1) the absence of tRNA(Pro) gene, (2) the possibly nonfunctional light-strand replication origin (O-L) showing a shorter loop in secondary structure and no conserved motif (5'-GCCGG-3'), (3) two sets of the tandem repeats at the 5' and 3' ends of the control region. The three features seem common for Trichiurus mitogenomes, as we have confirmed them in other three T. japonicus individuals and in T nanhaiensis. Phylogenetic analysis does not support the monophyly of Trichiuridae, which is against the morphological result. T. japonicus is most closely related to those species of family Scombridae; they in turn have a sister relationship with Perciformes members including suborders Acanthuroidei, Caproidei, Notothenioidei, Zoarcoidei, Trachinoidei, and some species of Labroidei, based on the current dataset of complete mitogenome. T japonicus together with T. brevis, T lepturus and Aphanopus carbo form a clade distinct from Lepidopus caudatus in terms of the complete Cyt b sequences. T. japonicus mitogenome, as the first discovered complete mitogenome of Trichiuridae, should provide important information on both genomics and phylogenetics of Trichiuridae. (C) 2009 Elsevier B.V. All rights reserved.

Cloning and expression of tumor necrosis factor (TNF alpha) cDNA from red seabream Pagrus major

A fragment of TNFalpha cDNA sequence from red seabream was cloned by homology cloning approach with two degenerated primers which were designed based on the conserved regions of other animals' TNF sequences. The sequence was elongated by 3' and 5' RACE to get the full length CDS sequence. This sequence contained 1264 nucleotides that included a 5' UTR of 85 bp, a 3' UTR of 514 bp and an open reading frame (ORF) of 666 bp which could encode 222 amino acids propeptide. In 3' UTR, there were several mRNA instability motifs and three endotoxin-responsive sequences, but the sequence lacked the polyadenylation signal. The deduced peptide had a clear transmembrane domain, a TNFalpha family signature and a TNF2 family profile. The cell attachment sequence and the glycosaminoglycan attachment sites were also found in the sequence. The red seabream TNF sequence shared relatively high similarity with both mammalian TNFalpha and TNFbeta by multiple sequence alignments. Phylogenetic analysis showed that the piscine TNFalpha were located independently in a different branch compared with mammalian TNFalpha and TNFbeta. Based on the primary and secondary structure analysis and gene expression study, we could concluded that the red seabream TNF should be a TNFalpha, not TNFbeta. RT-PCR was used to study TNFa transcript expression. 24 h after the red seabream was challenged by Vibrio anguillarum, the RS TNFalpha transcript expression were detected in blood, brain, gill, heart, head kidney, kidney, Ever, muscle and spleen. Results showed that TNFalpha mRNA was constitutively expressed in parts of the tissues both in stimulated and unstimulated fish and the expression could be enhanced after the pathogen infection.

东海南部流-涡结构分析与动力机制研究

东海作为全球海洋变化中最为敏感的海区之一，其环流变异不仅直接影响东亚和我国的气候，还关系到海区内营养盐的输运和污染物的净化。鉴于东海环流在中国近海环境和海上工程、海洋活动所起的重要作用，其研究是我国海洋工作者工作的重点。 31N以南的东海南部海域是水文调查最为丰富的海域，目前已经积累了超过8 000 000个站点水文数据（温度、盐度）和12 000 000站点流数据（流速、流向），这些数据为该海域的物理海洋学研究提供了坚实的物质基础。本文以东海南部海域的流-涡结构为研究对象，以丰富的观测资料为基础，辅以MASNUM浪-潮-流耦合模式，通过数据分析、模式验证和动力机制分析相结合的方法，明确东海南部海域存在的各个海流系和涡旋结构。 本文研究内容主要包括东海黑潮的流速结构及其时间变化特征、黑潮分支和海温之间的关系、黑潮右侧逆流的季节特征、黑潮左侧逆流的存在性验证、东海黑潮环流子系统的构成、台湾海峡内海流的路径和流量、台湾暖流的水体来源和路径、涡旋和冷（暖）中心的季节分布特征。

Bromophenol derivatives from the red alga Rhodomela confervoides

Eight new bromophenol derivatives, 2,3-dibromo-4,5-dihydroxybenzyl methyl sulfoxide (1), 4-(2,3-dibromo-4,5-dihydroxyphenyl)-3-butene-2-one (2), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (3), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid methyl ester (4), 2-phenyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (5), 4'-methoxy-2",3',3"-tribromo-4",5',5"-trihydroxydiphenylacetic acid (6), and 3-bromo-5-hydroxy-4-methoxyphenylacetic acid (7) and its methyl ester (8), together with a known bromophenol, 3-bromo-5-hydroxy4-methoxybenzoic acid (9), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by spectroscopic methods including IR, EIMS, FABMS, ESIMS, HRFABMS, HRESIMS, 1D and 2D NMR, and single-crystal X-ray structure analysis. Compounds 1-4, 8, and 9 were found inactive against several human cancer cell lines and microorganisms.

Bromophenols coupled with derivatives of amino acids and nucleosides from the red alga Rhodomela confervoides

Three new bromophenols coupled with pyroglutamic acid derivatives and one bromophenol coupled with deoxyguanosine were obtained from the red alga Rhodomela confervoides. By spectroscopic methods including 2D NMR and single-crystal X-ray structure analysis their structures were elucidated as N-(2,3-dibromo-4,5-dihydroxybenzyl)methyl pyroglutamate (1), N-(2,3-dibromo-4,5-dihydroxybenzyl)pyroglutamic acid (2), N-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyllmethyl pyroglutamate (3), and 2-N-(2,3-dibromo-4,5-dihydroxybenzylamino)deoxyguanosine (4), respectively. Compounds 1-4 were evaluated against several microorganisms and human cancer cell lines, but found inactive. To our knowledge this is the first report of bromophenols coupled with amino acid or nucleoside derivatives through the C-N bond.

电离层参量M(3000)F2和hmF2的经验正交函数方法建模研究

The ionospheric parameter M(3000)F2 (the so-called transmission factor or the propagation factor) is important not only in practical applications such as frequency planning for radio-communication but also in ionospheric modeling. This parameter is strongly anti-correlated with the ionospheric F2-layer peak height hmF2，a parameter often used as a key anchor point in some widely used empirical models of the ionospheric electron density profile (e.g., in IRI and NeQuick models). Since hmF2 is not easy to obtain from measurements and M(3000)F2 can be routinely scaled from ionograms recorded by ionosonde/digisonde stations distributed globally and its data has been accumulated for a long history, usually the value of hmF2 is calculated from M(3000)F2 using the empirical formula connecting them. In practice, CCIR M(3000)F2 model is widely used to obtain M(3000)F2 value. However, recently some authors found that the CCIR M(3000)F2 model has remarkable discrepancies with the measured M(3000)F2, especially in low-latitude and equatorial regions. For this reason, the International Reference Ionosphere (IRI) research community proposes to improve or update the currently used CCIR M(3000)F2 model. Any efforts toward the improvement and updating of the current M(3000)F2 model or newly development of a global hmF2 model are encouraged. In this dissertation, an effort is made to construct the empirical models of M(3000)F2 and hmF2 based on the empirical orthogonal function (EOF) analysis combined with regression analysis method. The main results are as follows: 1. A single station model is constructed using monthly median hourly values of M(3000)F2 data observed at Wuhan Ionospheric Observatory during the years of 1957–1991 and compared with the IRI model. The result shows that EOF method is possible to use only a few orders of EOF components to represent most of the variance of the original data set. It is a powerful method for ionospheric modeling. 2. Using the values of M(3000)F2 observed by ionosondes distributed globally, data at grids uniformly distributed globally were obtained by using the Kriging interpolation method. Then the gridded data were decomposed into EOF components using two different coordinates: (1) geographical longitude and latitude; (2) modified dip (Modip) and local time. Based on the EOF decompositions of the gridded data under these two coordinates systems, two types of the global M(3000)F2 model are constructed. Statistical analysis showed that the two types of the constructed M(3000)F2 model have better agreement with the observational M(3000)F2 than the M(3000)F2 model currently used by IRI. The constructed models can represent the global variations of M(3000)F2 better. 3. The hmF2 data used to construct the hmF2 model were converted from the observed M(3000)F2 based on the empirical formula connecting them. We also constructed two types of the global hmF2 model using the similar method of modeling M(3000)F2. Statistical analysis showed that the prediction of our models is more accurate than the model of IRI. This demonstrated that using EOF analysis method to construct global model of hmF2 directly is feasible. The results in this thesis indicate that the modeling technique based on EOF expansion combined with regression analysis is very promising when used to construct the global models of M(3000)F2 and hmF2. It is worthwhile to investigate further and has the potential to be used to the global modeling of other ionospheric parameters.

面向决策支持的综合地质信息系统功能开发和GIS应用

Synthetic Geology Information System(SGIS) is a part of the theory of Engineering Geomechanics-mate-Synthetics(EGMS), is also a development of its technical methodology. SGIS includes ways of geology engineering investigation, design, and construction. Although SGIS has an integrate theory frame, and some parts of it have gained great progress, the completion of SGIS is a continuous and accumulative process. This paper analyses the ways and principle of building knowledge database and model database, summarizes the experts' experience on exploration methods selection and the characters of exploration models, combining with the application of Decision Support System(DSS) in Decision support of Synthetic Exploration Methods for Railway engineering Geology. By the analysis of hierarchy structure of the model database, the effects of geology engineering factors on the selection of exploration methods are expressed. By the usage of fuzzy patterns recognize, hierarchy structure analysis, fuzzy collection closement analysis etc, the software of DSS for engineering design and construction are developed. At same time, by the development of Monitoring Data Analysis System and experiment data management system of Hydro-power project, this paper discussed the data management of science experiment of Hydro-power project by the usage of synthetic database and the usage of Geography Information System(GIS) and DSS technics. The technic of visual operation of data process and project monitoring system are presented. The intelligence algorithm of self-adoption is carried out to improve the data process and analysis of monitoring. Items of the project theoretical analysis and data process are designed in detail. All the theory and technical methods presented in this paper are one part of SGIS, in which the application of DSS and GIS, is an important step of the progress and completion of SGIS.

河北寿王坟铜矿成矿定年及同位素地球化学特征

Samples from carbonate wall-rocks, skarn, ore of skarn type, later calcite vein, and ore of porphyry type in Shouwangfen copper deposit district were collected. Systematic study was carried out on carbon, oxygen, rubidium, strontium and sulfur isotope compositions of carbonates and sulfides in these samples. The first Isochron dating by the Rb-Sr isotopes in chalcopyrite of ore sub-sample was done as well. The following conclusions were obtained. The age (113.6±4.3Ma), obtained by Rb-Sr isotope isochron dating of chalcopyrite and pyrite from sub-sample of skarn ores, probably represents the true mineralization age of skarn ores. That demonstrates the genetic relationship between granodiorite in Shouwangfen complex and skarn copper ores. On the other hand, the Rb-Sr isochron age (73±15Ma) of chalcopyrite from porphyry ores is a little incredible because of bad synthesizing evaluation. But combined with other age data of igneous rocks, it implies the possibility of hydrothermal mineralization in connection with magma activity during the fourth period of Yanshanian in Hebei Province, even in the whole northern edge of Huabei continental block. Together from structure analysis of sulfide sub-samples, from pretreating preccedure of Rb-Sr isotope isochron and its' valuating, we found out that Rb-Sr isotope isochron of sulfide sub-samples is influenced by the crystal structure of sulfides. That is, sulfide ores with very big crystals are not suitable for sub-sample isochron. Carbon, oxygen, sulfur and strontium compositions, of different minerals in these two kinds of ores, imply that the ore-forming hydrothermal fluids were probably derived from magma deep under the crust. The calcite ~(87)Sr/~(86)Sr ratios from the porphyry are consistent to the initial 87Sr/86Sr ratio of the Rb-Sr isochron of chalcopyrite and pyrite in the skarn ore, indicating that these two kinds of ores have the same source characteristic, although the porphyry deposit was formed probably 40 million years later than the skarn one according to our dating results. Skarn and skarn ores are usually considered as interaction product between carbonate wall-rocks and magmatic fluids, but the carbon of the sedimentary carbonate seems not involved in the skarn ores. Considering the connection of magmatic processes and hydrothermal ore formation in the Shouwangfen district, particularly, the spatial distribution of skarn-type and porphyry-type ores, it is possible that the Shouwangfen ore district corresponds to a hydrothermal ore-forming system, which was promoted by high-intruding magmatic rocks. Systematic stable isotopic research can help to reveal the upper part of this hydrothermal ore-forming system, which mainly related to heated and circulating meteoric water, and the lower part principally related to ascending magmatic fluids. Both skarn and porphyry ore-bodies are formed by up-intruding magmatic fluids (even more deep mantle-derived fluids).

基于结构分析地震资料去噪方法研究

With the development of oil and gas exploration, the exploration of the continental oil and gas turns into the exploration of the subtle oil and gas reservoirs from the structural oil and gas reservoirs in China. The reserves of the found subtle oil and gas reservoirs account for more than 60 percent of the in the discovered oil and gas reserves. Exploration of the subtle oil and gas reservoirs is becoming more and more important and can be taken as the main orientation for the increase of the oil and gas reserves. The characteristics of the continental sedimentary facies determine the complexities of the lithological exploration. Most of the continental rift basins in East China have entered exploration stages of medium and high maturity. Although the quality of the seismic data is relatively good, this areas have the characteristics of the thin sand thickness, small faults, small range of the stratum. It requests that the seismic data have high resolution. It is a important task how to improve the signal/noise ratio of the high frequency of seismic data. In West China, there are the complex landforms, the deep embedding the targets of the prospecting, the complex geological constructs, many ruptures, small range of the traps, the low rock properties, many high pressure stratums and difficulties of boring well. Those represent low signal/noise ratio and complex kinds of noise in the seismic records. This needs to develop the method and technique of the noise attenuation in the data acquisition and processing. So that, oil and gas explorations need the high resolution technique of the geophysics in order to solve the implementation of the oil resources strategy for keep oil production and reserves stable in Ease China and developing the crude production and reserves in West China. High signal/noise ratio of seismic data is the basis. It is impossible to realize for the high resolution and high fidelity without the high signal/noise ratio. We play emphasis on many researches based on the structure analysis for improving signal/noise ratio of the complex areas. Several methods are put forward for noise attenuation to truly reflect the geological features. Those can reflect the geological structures, keep the edges of geological construction and improve the identifications of the oil and gas traps. The ideas of emphasize the foundation, give prominence to innovate, and pay attention to application runs through the paper. The dip-scanning method as the center of the scanned point inevitably blurs the edges of geological features, such as fault and fractures. We develop the new dip scanning method in the shap of end with two sides scanning to solve this problem. We bring forward the methods of signal estimation with the coherence, seismic wave characteristc with coherence, the most homogeneous dip-sanning for the noise attenuation using the new dip-scanning method. They can keep the geological characters, suppress the random noise and improve the s/n ratio and resolution. The rutine dip-scanning is in the time-space domain. Anew method of dip-scanning in the frequency-wavenumber domain for the noise attenuation is put forward. It use the quality of distinguishing between different dip events of the reflection in f-k domain. It can reduce the noise and gain the dip information. We describe a methodology for studying and developing filtering methods based on differential equations. It transforms the filtering equations in the frequency domain or the f-k domain into time or time-space domains, and uses a finite-difference algorithm to solve these equations. This method does not require that seismic data be stationary, so their parameters can vary at every temporal and spatial point. That enhances the adaptability of the filter. It is computationally efficient. We put forward a method of matching pursuits for the noise suppression. This method decomposes any signal into a linear expansion of waveforms that are selected from a redundant dictionary of functions. These waveforms are chosen in order to best match the signal structures. It can extract the effective signal from the noisy signal and reduce the noise. We introduce the beamforming filtering method for the noise elimination. Real seismic data processing shows that it is effective in attenuating multiples and internal multiples. The s/n ratio and resolution are improved. The effective signals have the high fidelity. Through calculating in the theoretic model and applying it to the real seismic data processing, it is proved that the methods in this paper can effectively suppress the random noise, eliminate the cohence noise, and improve the resolution of the seismic data. Their practicability is very better. And the effect is very obvious.