STUDIES ON OLEFIN-COORDINATING TRANSITION-METAL CARBENE COMPLEXES .20. SYNTHESIS OF 1,3-CYCLOHEXADIENE(DICARBONYL) [ETHOXY(ARYL)-CARBENE]IRON COMPLEXES AND THEIR PHOSPHINE ADDUCTS - CRYSTAL-STRUCTURE OF C6H8(CO)2FEC(OC2H5)C6H4CH3-O

Reaction of 1,3-cyclohexadiene(tricarbonyl)iron (1) with ortho-substituted aryllithium reagents ArLi (Ar=o-CH3C6H4, o-CH3OC6H4, o-CF3C6H4) in ether at low temperature, and subsequent alkylation of the acylmetalates formed with Et3OBF4 in aqueous solution at 0-degrees-C or in CH2Cl2 at -60-degrees-C gave the 1,3-cyclohexadiene(dicarbonyl)[ethoxy(aryl)carbene]iron complexes (eta4-C6H8)(CO)2FeC(OC2H5)Ar (3, Ar = o-CH3C6H4; 4, Ar = o-CH3OC6H4), and the isomerized product (eta3-C6H8)(CO)2FeC(OC2H5)C6H4CF3-o (5), respectively, among which the structure of 3 has been established by an X-ray diffraction study. Complex 3 is monoclinic, space group P2(1) with a = 8.118(4), b = 7.367(4), c = 14.002(6) angstrom, beta = 104.09(3)-degrees, V = 812.2(6) angstrom3, Z = 2, D(c) = 1.39 g cm-3, R = 0.056, and R(w) = 0.062 for 976 observed reflections. Complexes 3 and 5 were converted into the chelated allyliron phosphine adducts(eta3-C6H8)(CO)2(PR31)FeC(OC2H5)Ar (6, Ar = o-CH3C6H4, R1 = Ph; 7, Ar = o-CH3C6H4, R1 = OPh; 9, Ar = o-CF3C6H4, R1 = Ph), by reaction with phosphines in petroleum ether at low temperatures.

PREPARATION AND STRUCTURE OF HALF-OPEN VANADOCENE, V[2,4-(CH3)2C5H5](C5H5)CO

The half-open vanadocene, V[2,4-(CH3)2C5H5](C5H5)CO, was obtained by the reaction of V[2,4-(CH3)2C5H5](C5H5)PMe3 with CO in petroleum ether at room temperature. Its crystal structure was determined by X-ray diffraction technique. The crystal was monoclinic with space group P2(1)/n, a = 16.614(3), b = 7.636(1), c = 19.128(6) angstrom, beta = 99.92(2)-degrees, V = 2390.5(9) angstrom3, and Z = 8. The final R value was 0.043. The V(1)-CPD(1) (half) (PD = 2,4-(CH3)2C5H5) bonds were shorter (0.038 angstrom) than the V(1)-CCP(1) (half) (CP = C5H5) bonds, averaging 2.224(4) versus 2.262(4) angstrom, respectively. 4V[2,4-(CH3)2C5H5](C5H5)CO has been characterized by IR and EPR methods.

WATER-SOLUBLE AND AMPHIPHILIC POLYMERS .6. A STUDY ON THE SURFACE-COMPOSITION OF CAST FILMS OF PST/PMAA AND PEO-PST-PEO BLOCK POLYMERS BY XPS

Thin films of PSt/PMAA and PEO-PSt-PEO block polymers were deposited on a polystyrene substrate by solution adsorption (with or without solvent treatment), and the film surfaces were characterized by means of XPS. Direct solvent - casting of PEO-PSt-PEO from benzene solutions resulted in PSt-rich surfaces, whereas PMAA richer surfaces were obtained for PSt/PMAA films cast from DMF solutions. Moreover, solvent treatment after casting had profound effect on the film surface composition. Treatment with water markedly increased the surface concentration of polar PEO segments. In the case of PSt-PMAA block polymers, the PSt content on the surface increased in the order of water < ethanol < cyclohexane < petroleum ether, the last-named giving films with almost pure PSt surface. It is well worth noticing that the bulk composition had little to do with the surface composition for both PSt/PMAA and PEO-PSt-PEO block polymers within the composition range investigated when subsequent solvent treatment was applied.

Features of Late Cenozoic Deepwater Sedimentation in Southern Qiongdongnan Basin, Northwestern South China Sea

Based on high resolution 2D and 3D seismic data acquired in recent years, using sequence stratigraphy analysis and geophysical methods, we discuss the features of Late Cenozoic deepwater sedimentation in the southern Qiongdongnan (sic) basin. The study area entered a bathyal slope environment in the Miocene. The channel developed in the Sanya (sic) Formation was controlled by a fault break, and its shingled seismic characteristics represent multiple erosion and fill, which may indicate that turbidite current developed in the slope environment. The polygon faults found in mudstone of the Meishan (sic) Formation represent the deepwater hungry sedimentary environment. The large-scale channels developed on the top of Huangliu (sic) Formation could be the result of a big sea level drop and an increase of sediment supply. The fantastic turbidite channel developed in Late Quaternary in the slope environment has "fan-like" body and long frontal tiny avulsion channel. The analysis of these features suggests that the sediment supply of the study area in the post-rifting period was dominant from the Vietnam uplift in the southwest. These deepwater sedimentary features could be potential reservoirs or migration pathways for deepwater petroleum systems.

Characteristics and Formation Mechanism of Polygonal Faults in Qiongdongnan Basin, Northern South China Sea

Based on high-resolution 3D seismic data, we document the polygonal faults within the Miocene Meishan (sic) Formation and Huangliu (sic) Formation of the Qiongdongnan (sic) basin, northern South China Sea. Within the seismic section and time coherent slice, densely distributed extensional faults with small throw and polygonal shape were identified in map view. The orientation of the polygonal faults is almost isotropic, indicating a non-tectonic origin. The deformation is clearly layer-bounded, with horizontal extension of 11.2% to 16%, and 13.2% on average. The distribution of polygonal faults shows a negative correlation with that of gas chimneys. The development of polygonal faults may be triggered by over-pressure pore fluid which is restricted in the fine-grained sediments of bathyal facies when the sediments is compacted by the burden above. The polygonal faults developed to balance the volumetric contraction and restricted extension. The product of hydrocarbon in the Meishan Formation may have contributed to the development of the polygonal faults. In the study area, it was thought that the petroleum system of the Neogene post-rift sequence is disadvantageous because of poor migration pathway. However, the discovery of polygonal faults in the Miocene strata, which may play an important role on the fluid migration, may change this view. A new model of the petroleum system for the study area is proposed.

Seismic characteristics of a reef carbonate reservoir and implications for hydrocarbon exploration in deepwater of the Qiongdongnan Basin, northern South China Sea

Our analysis of approximately 40,000 km of multichannel 2-D seismic data, reef oil-field seismic data, and data from several boreholes led to the identification of two areas of reef carbonate reservoirs in deepwater areas (water depth >= 500 in) of the Qiongdongnan Basin (QDNB), northern South China Sea. High-resolution sequence stratigraphic analysis revealed that the transgressive and highstand system tracts of the mid-Miocene Meishan Formation in the Beijiao and Ledong-Lingshui Depressions developed reef carbonates. The seismic features of the reef carbonates in these two areas include chaotic bedding, intermittent internal reflections, chaotic or blank reflections, mounded reflections, and apparent amplitude anomalies, similar to the seismic characteristics of the LH11-1 reef reservoir in the Dongsha Uplift and Island Reef of the Salawati Basin, Indonesia, which house large oil fields. The impedance values of reefs in the Beijiao and Ledong-Lingshui Depressions are 8000-9000 g/cc x m/s. Impedance sections reveal that the impedance of the LH11-1 reef reservoir in the northern South China Sea is 800010000 g/cc x m/s, whereas that of pure limestone in BD23-1-1 is > 10000 g/cc x m/s. The mid-Miocene paleogeography of the Beijiao Depression was dominated by offshore and neritic environments, with only part of the southern Beijiao uplift emergent at that time. The input of terrigenous sediments was relatively minor in this area, meaning that terrigenous source areas were insignificant in terms of the Beijiao Depression: reef carbonates were probably widely distributed throughout the depression, as with the Ledong-Lingshui Depression. The combined geological and geophysical data indicate that shelf margin atolls were well developed in the Beijiao Depression, as in the Ledong-Lingshui Depression where small-scale patch or pinnacle reefs developed. These reef carbonates are promising reservoirs, representing important targets for deepwater hydrocarbon exploration. (C) 2008 Elsevier Ltd. All rights reserved.

Gas hydrate associated with mud diapirs in southern Okinawa Trough

Many mud diapirs have been recognized in southern Okinawa Trough by a multi-channel seismic surveying on R/V KEXUE I in 2001. Gas hydrates have been identified, by the seismic reflection characteristics, the velocity analysis and the impedance inversion. Geothermal heat flow around the central of the mud diapir has been determined theoretically by the Bottom Simulating Reflectors (BSRs). Comparing the BSR derived and the measured heat flow values, we infer that the BSR immediately at the top of the mud diapirs indicate the base of the saturated gas hydrate formation zone (BSGHFZ), but not, as we ordinarily know, the base of the gas hydrate stability zone (BGHSZ), which could be explained by the abnormal regional background heat flow and free gas flux associated with mud diapirs. As a result, it helps us to better understand the generation mechanism of the gas hydrates associated with mud diapirs and to predict the gas hydrate potential in the southern Okinawa Trough. (C) 2008 Elsevier Ltd. All rights reserved.

Fine-grained Pleistocene deepwater turbidite channel system on the slope of Qiongdongnan Basin, northern South China Sea

Recently, as oil exploitation has become focused on deepwater slope areas. more multi-channel high resolution 2D and 3D seismic data were acquired in the deepwater part of the Qiongdongnan Basin, northern South China Sea. Based on 3D seismic data and coherence time slice, RMS and 3D visualization, a series of deepwater channels were recognized on the slope that probably developed in the late Quaternary period. These channels trend SW-NE to W-E and show bifurcations, levees, meander loops and avulsions. High Amplitude Reflections (HARs), typical for channel-levee complexes, are of only minor importance and were observed in one of the channel systems. Most of the detected channels are characterized by low-amplitude reflections, and so are different from the typical coarse-grained turbidite channels that had been discovered worldwide. The absence of well data in the study area made it difficult to determine the age and lithology of these channels. Using a neighboring drill hole and published data about such depositional systems worldwide, the lithology of these channels is likely to be dominated by mudstones with interbedded thin sandstones. These channels are formed by turbidity currents originated from the little scale mountain river of mid-Vietnam in SW direction and were probably accompanied by a relative sea level drop in the last glacial age. These channels discovered on the northern South China Sea slope are likely to be fine-grained, mud-dominant and low N:G deposits in a deepwater paleogeographic setting. (C) 2009 Elsevier Ltd. All rights reserved.

Gas hydrate occurrence on the continental slope of the northern South China Sea

High-resolution multi-channel seismic data and geological samples were collected during two research cruises of the R/V FENDOU 4 in 1999 and 2000. Studies on these data and samples together with results from sites 1143-1145 and 1148 of ODP Leg 184 suggest that the geological structure on the continental slope of the northern South China Sea is favorable for the formation of gas hydrates. Bottom simulating reflectors (BSRs) and geochemical anomalies which indicate the existence of gas hydrates have been recognized in sediments of the Xisha Trough, the Dongsha Rise and the accretionary wedge of the Manila subduction zone. These gas hydrates are generated by two different mechanisms depending on the tectonic regime and the seismic and geochemical characteristics. The first applies to the passive continental margin of the nor-them South China Sea on the Dongsha Rise and in the Xisha Trough. The gas hydrates are associated with diapiric structures, active faults, slumps and gravity flows as well as high Late Cenozoic sedimentation rates. Their seismic expression includes BSRs, seismic blanking zones and velocity anomalies. The second mechanism is operative on the active continental margin along the Manila subduction zone, especially in the accretionary wedge. Here, gas hydrate occurrence is marked by widespread BSRs and acoustic 'pull-down' possibly related to the existence of free gas in the sediments beneath the BSR. The thickness of the seismic blanking zones averages 250 m, suggesting that the stable gas hydrate zone has about the same thickness. (c) 2005 Elsevier Ltd. All rights reserved.

Mesozoic-Cenozoic tectonic evolution of the Zhuanghai area, Bohai-Bay Basin, east China: the application of balanced cross-sections

The technique of balancing cross-sections, an important method for studying the tectonic history of sedimentary basins, has many applications. It enables one to compile charts for petroleum exploration and development, and growth sections of ancient structures can be restored so that the structural growth history can be studied. In order to study tectonic evolution in the Zhuanghai area of the Bohai-Bay basin, we selected two seismic profiles and compiled two structural growth sections. Based on the two balanced cross-sections, the evolution can be divided into four phases: the Triassic-Middle Jurassic phase, Late Jurassic - Cretaceous phase, Palaeogene extension phase, and Late Palaeogene-to-present phase. The whole area was uplifted during the Triassic-Middle Jurassic phase because of intense extrusion stress related to the Indo-China movement. During the Late Jurassic and Early Cretaceous, intense extension occurred in east China, and the whole area rifted, leading to the deposition of a thick sedimentary sequence. In the Late Cretaceous, the area suffered uplift and compression associated with the sinistral strike slip of the Tanlu fault. In the Palaeogene, a rifting basin developed in the area. Finally, it became stable and was placed in its present position by dextral strike-slip motion. In addition, some problems associated with compiling balanced cross-sections are discussed.

东海沿岸贝类体内石油烃和有机氯农药的分布特征及评价

本研究分别于2006、2007年5月在东海沿岸海域22个站位采集牡蛎、贻贝、四角蛤蜊、文蛤、花蛤5种贝类样品，采用荧光分光光度法和气相色谱法检测贝类体内的石油烃（TPHs）和有机氯农药(HCHs和DDTs) 含量，分析东海沿岸海域贝类体内的TPHs、HCHs和DDTs的时空分布特征和HCHs、DDTs的组分特征，比较不同贝类体内污染物含量的差异，探讨HCHs和DDTs的来源，并对贝类进行初步海洋生物质量评价和人体健康风险评价。研究结果表明： （1）东海沿岸海域贝类体内TPHs含量范围为0.40 74.40 mg kg-1，平均含量为9.42 mg kg-1；HCHs含量为ND～5.42×10-3mg kg-1，平均含量为1.47×10-3 mg kg-1；DDTs含量为2.09×10-3～197.66×10-3mg kg-1，平均含量为38.05×10-3 mg kg-1。其中，TPHs含量在长江口及邻近海域较高， HCHs和DDTs含量在江苏省的如东、海门和浙江省的各海域含量较高。与2006年相比，2007年贝类体内TPHs含量与2006年基本持平，HCHs含量有稍微降低，但是DDTs含量有明显升高趋势。 （2）HCHs和DDTs组分分析表明，α-HCH和β-HCH占HCHs总量的绝大多数，γ-HCH和δ-HCH仅有极少量检出，大多数区域的α-HCH/γ-HCH比值在4-7之间，说明研究区域内有新的HCHs污染源； DDTs 中O,P’-DDT/P,P'-DDT的比值远高于工业DDTs中O,P’-DDT/P,P'-DDT的比值，分析认为其与周围区域使用三氯杀螨醇密切有关。 （3）贝类体内的TPHs、HCHs和DDTs与水体、沉积物中的相应有机物存在正相关性。相对于TPHs和HCHs，DDTs更容易在贝类体内富集；牡蛎对TPHs和HCHs、DDTs的累积能力明显高于四角蛤蜊和贻贝。 （4）质量评价显示TPHs在局部海域超标，HCHs未超标，DDTs含量超标严重。人体健康风险评估结果显示，东海沿岸海域贝类体内HCHs和DDTs的致癌风险和暴露风险均在可接受的范围之内，消费者因食用监测海域的贝类而受到HCHs和DDTs危害的可能性不大。 （5）与世界其他海域比较表明，东海海域贝类TPHs和HCHs含量处于中等水平， DDTs含量处于比较高的水平。

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments of Jiaozhou Bay, Qingdao, China

The composition and distribution of aliphatic (n-alkanes) and polyaromatic hydrocarbons (PAHs) were measured for the surface sediments collected at 25 sites from Jiaozhou Bay, Qingdao, China. Total n-alkanes and PAH concentrations ranged from 0.5 to 8.2 mu g/gdw and 0.02 to 2.2 mu g/gdw, respectively, and the distribution of both n-alkanes and PAHs showed large spatial variations in the bay. The distribution of PAHs in the sediments was predominated by the three or more ring compounds. High hydrocarbon levels were generally found in the areas associated with high anthropogenic impact and port activities in the bay. The calculated hydrocarbon indexes suggest that petroleum contamination was the main source of n-alkanes, while both pyrolytic and petrogenic sources contributed PAHs to the surface sediments of Jiaozhou Bay. In comparison to other polluted coastal sediments, the level of contamination from both aliphatic hydrocarbons and PAHs in Jiaozhou Bay sediments is relatively low at the present time. (c) 2005 Elsevier Ltd. All rights reserved.

Prediction of marine sediment corrosion by fuzzy clustering analysis

Along with the development of marine industries, especially marine petroleum exploitation, more and more pipelines are buried in the marine sediment. It is necessary and useful to know the corrosion environment and corrosiveness of marine sediment. In this paper, field corrosion environmental factors were investigated in Liaodong Bay marine sediment containing sulfate-reducing bacteria (SRB) and corrosion rate of steel in the partly sediment specimens were determined by the transplanting burying method. Based on the data, the fuzzy clustering analysis (FCA) was applied to evaluate and predict the corrosiveness of marine sediment. On that basis, the influence factors of corrosion damage were discussed.

可重构模块机器人倾翻稳定性研究

介绍了一种可重构模块机器人,它可以通过构形的变化来提高系统的稳定性和抗倾翻能力.该机器人由3个模块组成,采用履带驱动,具有直线、三角、并排3种对称构形.在对移动机器人的倾翻因素和倾翻对策等问题进行分析的基础上,提出稳定锥方法,用倾翻性能指数对移动机器人的静、动态稳定性进行综合判定.讨论了变形机器人3种对称构形在仰俯、偏转、倾斜等干扰组合作用下的倾翻性能指数和综合稳定性,并进行了仿真实验和非结构环境实验.

链式可重构机器人单模块结构设计与运动实验

提出了一种新型模块化链式移动机器人机构,它具有可重构、自动变形的特点。单个标准模块主要由中间通孔式连接手臂、履带驱动链传动装置、模块偏转锥齿轮传动装置、模块俯仰链传动装置、连接柄等组成。模块间由偏转关节、连接柄、连接臂和仰俯关节进行连接组合。为提高单个模块的机动性和实现运动自主功能,对标准模块进行了适当改进,单模块机器人采用了履带、轮、臂、腿组合的移动机构,具有三维空间的运动能力。最后对单模块机器人样机在垂直壁障碍、平地支腿、平地转弯、斜坡、楼梯等情况下的运动能力进行了实验,为进一步实现多模块机器人的自重构和环境应用打下了基础。