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.

Benzaldehyde derivatives from Eurotium rubrum, an endophytic fungus derived from the mangrove plant Hibiscus tiliaceus

Four new (1-4) and seven known (5-11) benzaldehyde derivatives were characterized from the liquid fermentation cultures of Eurotium rubrum, an endophytic fungus that was isolated from the inner tissue of stems of the mangrove plant Hibiscus tiliaceus. The structures of these compounds were determined by extensive analysis of their spectroscopic data. Among these metabolites, compound 1, which was named as eurotirumin, possesses a new carbon skeleton with a cyclopentabenzopyran ring system.

Alkaloids from the Leaves of Daphniphyllum longeracemosum ROSENTH.

Four new Daphniphyllum alkaloids. daphlongamines E-H (1-4, resp.), along with 19 known alkaloids, were isolated front the leaves of Daphniphyllum longeracemosum. Their structures were characterized by spectroscopic methods, especially 2D-NMR techniques. It is noteworthy that aconitine- and veatchine-type diterpenoid alkaloids were also isolated from this species.

Triterpenoids from the mangrove plant Hibiscus tiliaceus

Three new triterpenoids with the rarely occurring nigrum skeleton, namely (20E)-22-hydroxynigrum-20-en-3-one (1), 21 beta-hydroxynigrum-22(29)-en-3-one (2), and 21 alpha-hydroxynigrum-22(29)-en-3-one (3), were isolated from the mangrove plant Hibiscus tiliaceus. Additionally, five known triterpenoids including friedelin (4),12-oleanen-3 beta-ol (5), 3 beta-hydroxy-12-oleanen-28-oic acid (6),20(29)-lupen-3 beta,28-diol (7). and cucurbita-5,23-dien-3 beta,25-diol (8) were also isolated and identified. The latter structures were elucidated by a detailed NMR and MS analyses, as well as by comparison with reported literature data.

海洋红藻多管藻和松节藻的化学成分及抗氧化活性研究

海洋生物具有产生丰富多样的次生代谢产物的能力，其中红藻门松节藻科海藻卤代次生代谢产物以其结构新颖、生物活性独特引起了天然产物化学家的重视。 本论文对海洋红藻多管藻和松节藻进行了化学成分研究，综合利用各种色谱学方法 (硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备高效液相色谱以及重结晶等) 和现代波谱学技术 (IR、UV、EI-MS、FAB-MS、HR-ESI-MS、CD、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)，共分离鉴定了100个化合物，发现25个新化合物。 从多管藻中分离鉴定38个化合物 (24个溴酚化合物)，其中7个新化合物 (均为溴酚化合物)，包括1个菲并呋喃结构溴酚 (P1), 2个二氢菲结构溴酚 (P2, P3)，1个含 5,7-dihydrodibenzo[c,e]oxepine 结构溴酚 (P4)和3个简单溴酚 (P5, P6, P7)。P1 (urceolatin) 属首例报道的具有菲并呋喃结构的天然产物，从该种中分离的化合物P12 和 P13 可能是其生源合成的前体。P2和P3为第二例报道的具有二氢菲结构的溴酚化合物。 从松节藻中分离并鉴定了62 个化合物，其中18 个为溴酚类新化合物，44 个为已知化合物。化合物具有多变的取代基团，包括2 个脲基吡咯烷酮溴酚化合物 (R1, R2), 4 个γ-脲基丁酸溴酚化合物 (R3-R6)，5 个酰胺溴酚化合物 (R7, R8, R9, R13, R14)，1 个溴酚砜化合物 (R12), 1 个Xanthene 溴酚化合物 (R10)和5 个简单溴酚化合物 (R11, R15, R16, R17, R18)。R1、R2 是首例报道的含有脲基吡咯烷酮片段的天然产物，R10 为首次报道的溴代Xanthene 类天然产物。 对分离到的化合物进行了清除DPPH 和ABTS两种自由基活性的筛选。结果发现溴酚类天然产物具有显著的DPPH自由基清除活性，其中R3 的IC50 仅为3.3 μM, 其活性强度约为阳性对照BHT (IC50 为82.1 μM) 的24倍。另外，溴酚类天然产物对ABTS自由基有较强的清除活性，R2 的TEAC（Trolox efficency activity capacity）值为5.2 mM，约为阳性对照 (ascorbic acid, 1.02 mM) 的 5 倍。初步的构效关系研究发现，稠环分子、多羟基和邻位甲氧基等结构特点能有效增强DPPH 自由基清除活性；特殊取代基如脲基、吡咯烷酮等含有氮原子的基团，能有效增强ABTS 自由基清除活性，多羟基、溴代等结构特点也使其活性有所增强。 本研究结果丰富了海藻卤代化合物的结构类型，为多管藻和松节藻的合理利用提供了一定的科学依据。

First record of the family Spengeliidae (Hemichordata : Enteropneusta) from Chinese waters, with description of a new species

Six species belonging to two families of Hemichordata have previously been recorded in Chinese waters. This paper records the discovery and description of a new species of the genus Glandiceps found in Jiaozhou Bay, Qingdao, Shandong Province, named Glandiceps qingdaoensis. The new species has a long proboscis with dorsal and ventral grooves, a stomochord with a long vermiform process, a proboscis cavity with a dorsal median, right and left glomeruli, right and left glomeruli very large and encircling the stomochord, a proboscis skeleton in the cavity extends into the median posterior of the collar, a well-developed dorsal ventral muscular septum in the proboscis cavity dividing the cavity completely into two separate parts. The collar cord is without giant nerve roots. The trunk with four distinct regions that can be recognized externally: branchial-genital region, genital region, hepatic region, and intestinal region. The dorsal pharynx is large and the gill pores are small. The tongue bars are encircled by vesicles, and the first gonad commences at the level of the second or third gill slit.

Minor sesquiterpenes with new carbon skeletons from the brown alga Dictyopteris divaricata

Five minor sesquiterpenes (1-5) with two novel carbon skeletons, together with a minor new oplopane sesquiterpene ( 6), have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR, and CD, their structures including absolute configurations were assigned as (+)-(1R, 5S, 6S, 9R)3- acetyl-1-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-3-ene ( 1), (+)-(1R, 3S, 4S, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6- isopropyl-9-methylbicyclo[4.3.0] nonane (2), (+)-(1R, 3R, 4R, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6-isopropyl-9-methylbicyclo[ ;4.3.0] nonane ( 3), (+)-(1S, 2R, 6S, 9R)-1-hydroxy-2-(1-hydroxyethyl)-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (4), (-)-( 5S, 6R, 9S)-2-acetyl-5-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-1-en-3-one ( 5), and (-)-( 1S, 6S, 9R)- 4-acetyl- 1-hydroxy-6-isopropyl-9-methylbicyclo[ 4.3.0] non-4-en-3-one ( 6). Biogenetically, the carbon skeletons of 1-6 may be derived from the co-occurring cadinane skeleton by different ring contraction rearrangements. Compounds 1-6 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines.

Norsesquiterpenes from the brown alga Dictyopteris divaricata

Three bisnorsesquiterpenes (1-3) with novel carbon skeletons and a norsesquiterpene (4) have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR techniques, single-crystal X-ray diffraction, and CD, their structures including absolute configurations were proposed as (+)-1R,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0]non-4-en3-one (1), (-)-(1S,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (2), (+)-(5S,6R,9S)5-hydroxyl-6-isopropyl-9-methylbicyclo [4.3.01 non-1-en-3-one (3), and (-)-(1R,7S,10R)-1-hydroxy-1lnorcadinan-5-en-4-one (4). Biogenetically, the carbon skeleton of 1-3 may be derived from the co-occurring cadinane skeleton by ring contraction and loss of two carbon units, and compound 4 from the oxidation of cadinane derivatives. Compounds 1-4 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), breast cancer (MCF-7), hepatoma (Bel7402), and colon cancer (HCT-8) cell lines.

Sesquiterpenes from the red alga Laurencia tristicha

Seven new sesquiterpenes (1-7), together with seven known sesquiterpenes, aplysin (8), aplysinol (9), gossonorol (10), 7,10-epoxy-ar-bisabol-11-ol (11), 10-epi-7,10-epoxy-ar-bisabol-11-ol (12), johnstonol (13), and laurebiphenyl (14), have been isolated from the red alga Laurencia tristicha. The structures of new compounds were established as laur-11-en-2,10-diol (1), laur-11-en-10-ol (2), laur-11-en-1,10-diol (3), 4-bromo-1,10-epoxylaur-11-ene (4), cyclolauren-2-ol (5), laurentristich-4-ol (6), and ar-bisabol-9-en-7,11-diol (7) by means of spectroscopic methods including IR, HRMS, and ID and 21) NMR techniques. Compound 6 possessed a novel rearranged skeleton. All compounds were tested against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), hepatoma (Bel 7402), colon cancer (HCT-8), and HELA cell lines. Laurebiphenyl (14) showed moderate cytotoxicity against all tested cell lines, with IC50 values of 1.68, 1.22, 1.91, 1.77, and 1.61 mu g/mL, respectively. Other compounds were inactive (IC50 > 10 mu g/mL).

陕北地区石家湾-李家岔探区三叠系延长组石油成藏条件分析

Shijiawan –Lijiacha area, lying on the northeastern part of the Shanbei Slope of Ordos Basin, was selected as studying area. The previous explorations proved that the 2nd segment and 6th segment of the Yanchang Formation are the most important oil-bearing formations. It is indicated that the sedimentary facies and reservoir characteristics restricted the hydrocarbon accumulation regularity. Therefore, with petrology methodologies, such as outcrop observation, core description, geophysical logging interpretation, thin section determination, scanning electron microscope, as well as rock property analysis, the reservoirs was were systematically studied and characterized. The sedimentary micro-facies, seals, reservoir-seal combines, migration pathways and entrapping modes were taken into account. The author tempted to establish a base for further studies on reservoirs and on petroleum geology, and to provide some reliably geological evidences for later prospect activities. It was found that the sediments in the 2nd and 3rd segments of the Yanchang Formation in Shijiawan –Lijiacha area were deposited in braided rivers, and most sandy-bodies were identified as channel sandbars. The 4+5th and 6th segments were principally deposited in deltaic-plain environment, consisting of corresponding sub-facies such as distributary channels, natural levee, crevasse-splay and marsh. The skeleton sandy-bodies were identified as sandy sediments of distributary channels. The sand grains in reservoir in studied area possess generally low mineralogical maturity and moderate structural maturity, and the form of pores may be classified into intergranular types and dissolved types. Most reservoirs of Yanchang Formation in Shijiawan –Lijiacha area belong to extreme low-porosity low-permeability ones (type III), and the 2nd sediments belongs to low permeability one (type II) and the 6th segment belong to super low-permeability one(type Ⅳ). The reservoirs in the 2nd segment behave more heterogeneous than those in the 6th segment. The statistic analysis results show that, for 6th and 4+5th segments, the high quality reservoir-seal combines may be found everywhere in the studied area except in the northwest and the southwest parts; and for 1st and 2nd segments, in the northeast, central and southwest parts Petroleum migration happened in the duration of the Early Cretaceous period in both lateral and vertical directions. The migration paths were mainly constructed by permeable sandy-bodies. The superimposed channel sandy-bodies consist of the principal part of the system of carriers. the vertical fractures, that may travel through the seals between reservoirs, offered the vertical paths for migrating oil. It may be synthesized that oil coming from south kitchens migrated first laterally in carriers in the 6th segment. When arrived at the studied area, oil will migration laterally or/and vertical within both the sandy-bodies and fractures, in a climbing-stair way. The results demonstrate that the oil was entrapped in traps structure-lithology and/or lithology traps. In some cases, the hydrodynamic force may help to trap oil. Accumulation of oil in the area was mainly controlled by sedimentary facies, seals, structure, and heterogeneity of reservoir in the 2nd, 4+5th and 6th segments. Especially, the oil distributions in both the 2nd and 6th segments were obviously influenced by seals in the 4+5th segment. The existence of seals in 1st segment seems important for accumulation in the 2nd segment.

南海沉积物中的放射虫及其古环境意义

In this paper a systematic study of radiolarian from surface sediments of all the South China Sea (SCS) has initially been done for its deposit ecology, biogeography and paleoenvironment significance. The paleoenvironment information obtained by radiolarian analysis and other sedimentary method for core samples is also made use as the synthesis proxy for revealing the paleoenvironment changes in the SCS and the relations of it with the past globe change during last 200ka. Some results come out of this study as: 1) Radiolarian skeleton chemistry composition and skeleton morphological features were analyzed, chiefly dividing them as 15 types of basic morphological features: 2) Analysis of biogeographical feature demonstrates that the fauna in SCS obviously belonging to a transitional type of west Pacific - Indian Ocean and has a particularity of itself: 3) Tendency of radiolarian population distribution is lower in shallow continental shelf area, increasing gradually toward the abyssal region; 4) Nine character boundaries of radiolarian depth distribution in the sediments from whole the South China Sea may be recognized; 5)Two radiolarian transfer functions for paleotemperature and paleo-primary productivity in the South China Sea have also been established respectively. The equation of transfer function for winter paleotemperature has only an average estimated error of 0.18678 ℃ and the equation for paleo-primary productivity has the calculation accuracy of 85.31%; 6) Changes of radiolarian individuals, numbers of species and H(S) values in core NS93-5 show the completely different oceanic geographical circumstance and ecology structure in the Last Maximum Glacial with present; 7) The abundance variation of some raiolarian warm species and cold species indicate the changes of water masse features along with the paleoenvironment evolution, showing that this sea area clearly is controlled in 6 issues of oxygen isotopes by the cold water masses; 8) By comparative analysis of δ ~(18)O curves with GISP2;s ice core can core 17940 of the northern SCS, the occurring characters of D/O's events 1-21 and Heinrich's events H1-H6 have been revealed in this sea area by core NS93-5, which prove the existence of paleoclimatic tele-connections between the southern SCS and Arctic region since about 200ka BP.

地质体科学计算可视化研究及其应用

Describing visually space-time properties of geological phenomena consists of one of the most important parts in geology research. Such visual images are of usually helpful for analyzing geological phenomena and for discovering the regulations behind geological phenomena. This report studies mainly three application problems of scientific visualization in geology: (Dvisualizing geological body A new geometric modeling technique with trimmed surface patches has been eveloped to visualize geological body. Constructional surfaces are represented as trimmed surfaces and a constructional solid is represented by the upper and lower surface composed of trimmed surface patches from constructional surfaces. The technique can completely and definitely represent the structure of geological body. It has been applied in visualization for the coal deposit in Huolinhe, the aquifer thermal energy storage in Tianjin and the structure of meteorite impact in Cangshan et al. (2)visualizing geological space field Efficient visualization methods have been discussed. Marching-Cube algorithm used has been improved and is used to extract iso~surface from 3D data set, iso-line from 2D data set and iso-point from ID data set. The improved method has been used to visualize distribution and evolution of the abnormal pressures in Zhungaer Basin. (3)visualizing porous space a novel way was proposed to define distance from any point to a convex set. Thus a convex set skeleton-based implicit surface modeling technique is developed and used to construct a simplified porous space model. A Buoyancy Percolation numerical simulation platform has been developed to simulate the process of migration of oil in the porous media saturated with water.

大港油田孔南地区孔一段储层流动单元研究

The main reservoir type in the south of Dagang Oilfield is alluvial reservoir. In this paper, the reservoir structure model and the distribution of connected body and flow barrier were built on base of the study of high-resolution sequential stratigraphic skeleton and fine sedimentary microfacies on level of single sandbody. Utilizing the static and dynamic data synthetically and carrying out the comparision of the classification method for reservoir flow unit in different reservoir, the criterion, which can be used to classify the flow unit in first section of Kongdian formation of Kongnan area, was defined. The qualitative method of well-to-well correlation and the quantitative method of conditional simulation using multiple data are adopted to disclose the oil and water moving regulation in different flow unit and the distribution rule of remaining oil by physical simulation measure. A set of flow unit study method was formed that is suit for the Dagang Oilfield on account of the remaining oil production according to the flow unit. Several outstanding progresses was obtained in the following aspects:It is considered that the reservoir structure of Zao V iow oil group- Zao Vup4 layerand are jigsaw-puzzled reservoir, while ZaoVup3-ZaoVupi layers are labyrinth reservoir,which are studied on base of high-resolution sequential stratigraphic skeleton on the levelof single sandbody in first section of Kongdian formation of Kongnan area and accordingto the study of fine sedimentary microfacies and fault sealeing.When classifying the flow unit, only permeability is the basic parameter using thestatic and dynamic data and, and also different parameters should be chose or deleted, suchas porosity, effective thickness, fluid viscosity and so on, because of the weak or stronginterlayer heterogeneous and the difference of interlayer crude oil character.The method of building predicting-model of flow unit was proposed. This methodis according to the theories of reservoir sedimentology and high-resolution sequencestratigraphic and adopts the quantitative method of well-to well correlation and the quantitative method of stochastic simulation using integrateddense well data. Finally the 3-D predicting-model of flow unit and the interlay er distribution model in flow unit were built which are for alluvial fan and fan delta fades in first section of Kongdian formation of Kongnan area, and nine genetic model of flow unit of alluvial environment that spread in the space were proposed.(4) Difference of reservoir microscopic pore configuration in various flow units and difference of flow capability and oil displacement effect were demonstrated through the physical experiments such as nuclear magnetic resonance (NMR), constant rate mercury penetration, flow simulation and so on. The distribution of remaining oil in this area was predicted combining the dynamic data and numerical modeling based on the flow unit. Remaining oil production measure was brought up by the clue of flow unit during the medium and late course of the oilfield development.

Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals

A silica-based monolithic capillary column was prepared via a sol-gel process. The continuous skeleton and large through-pore structure were characterized by scanning electron microscopy (SEM). The native silica monolith has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). Column efficiencies greater than 250000 plates/m for capillary electrochromatography (CEC) separation of basic compounds were obtained. It was observed that retention of basic pharmaceuticals on the silica monolith was mainly contributed by a cation-exchange mechanism. Other retention mechanisms including reversed-phase and normal-phase mechanisms and electrophoresis of basic compounds also played a role in separation. A comparison of the differences between CEC and capillary zone electrophoresis (CZE) separation was also discussed.