吲哚生物碱Desbromoarborescidine A 的全合成及烯胺C-亚磺酰化反应研究

从新几内亚核桃木的树皮中分离得到的吲哚类喹诺里西定生物碱10-Desbromoarborescidine A，因发现其具有阻滞钙离子通道的活性而倍受关注。10-Desbromoarborescidine A由A、B、C、D四个环组成，只有一个手性中心，是吲哚生物碱中结构较简单的一种，常作为此类生物碱全合成方法的模型化合物。但迄今为止，能高效而简便的实现手性10-Desbromoarborescidine A不对称全合成方法线路不多，大多数以不对称诱导的方式建立其手性中心，手性催化的方式仅有一例金属催化。从逆合成分析可知，Desbromoarborescidine A的全合成可以通过亚胺不对称催化还原进行关键的手性中心构建，而本课题组在之前的研究中通过手性有机小分子催化剂的发展，已将三氯硅烷氢转移还原亚胺发展成了一类简便实用、高效、高对映选择性并具有优良底物适应范围的不对称催化反应，我们希望以这一反应作为关键手段，发展一条Desbromoarborescidine A及其类似物不对称合成新路线。 根据我们设计的新路线，首先成功合成了其关键中间体，然后我们进行了关键的不对称催化尝试。用本实验室已有的高性能有机小分子催化剂虽得到了较好的对应选择性，但是产率很低。同时，为了验证整条线路的可行性，我们也用消旋的中间体进行拉通线路的尝试。但不幸的是，在脱除保护基时遇到了很大困难。尝试换不同的保护基，或改变脱保护基的顺序，都未能成功合成目标产物。究其原因可能是由于吲哚的特殊性造成的，吲哚类亚胺与常规的芳香亚胺有较大的差异，其NH基团无论保护还是不保护，对与其2位相联接的C=N双键均有很大的影响，导致其不对称催化还原难以进行。另外，由于所设计的还原产物含有处在吲哚苄位的胺基，稳定性较差，造成保护基脱除困难。 烯胺C-亚磺酰化反应是本课题组最近发现的一个新反应，之前未见文献报道。本研究对该反应进行了反应条件优化和底物扩展，发现带Cbz，Ac，COt-Bu，CO2Et，Bz等保护基的一系列环状和非环状烯胺在亚磺酸钠、DMAc和MeSiCl3的共同作用下能高效高产率生成β-胺基烯基亚砜类新化合物，为合成多官能团化的烯基亚砜新化合物提供了一条简便实用的途径。 The main constituent of Dracontomelum mangiferum B1, indoloquinolizidine alkaloid 10-Desbromoarborescidine A, has drawn great attention due to its calcium channel blocking activity. Its molecular structure is relatively simple compared with the other alkaloids of the same type, which has only one chiral center, albeit with four cycles A, B, C, and D. This compound is often used as a model target for exploring different strategies for the total synthesis of indole alkaloids. Nevertheless, so far there still lack practical and highly efficient methods for the asymmetric total synthesis of 10-Desbromoarborescidine A. Most of the current available methods rely on stoichiometric asymmetric synthesis for the construction of the chiral center. There is only one example reporting utilization of asymmetric catalysis, but with transition metal complex as the catalyst. Our retrosynthetic analysis shows that catalytic asymmetric reduction of imine could be used as the key step for the construction of the chiral center of Desbromoarborescidine A. Since in the previous studies our group has developed the asymmetric reduction of imines by trichlorosilane into a practical and highly efficient and enantioselective method using newly designed chiral organocatalysts, we hope to apply this method to develop a novel synthetic route for the total synthesis of Desbromoarborescidine A and its analogues in this study. According to the newly designed synthetic route, we first accomplished the synthesis of the key intermediates which was then examined for the critical asymmetric catalysis. The asymmetric reduction using the highly efficient organocatalysts, developed in our lab afforded high ee but poor yield. We tried different reaction conditions to improve the yield, but failed to get any good results. Simultaneously, to vertify the feasibility of the synthetic route we designed, we also tired to go through the route toward the racemic synthesis of Desbromoarborescidine A. But unfortunately, protection and deprotection proved to be big hurdles. All the different protection groups and different sequences of protection and deprotection we tried failed to get us through the designed synthetic sequence and furnish the final product. Most likely, the indole part is the culprit behind the failures.The NH group of the indole, no matter protected or not, may impact the catalytic asymmetric reduction of C-N double bond connected with 2-C. Additionally, the reduction product we designed contains an amino group in the β-position of the indole, which may cause problems due to its instability. C-sulfenylation of enamines is a novel reaction discovered recently by our group, which has not been seen before in the literature. In this study, optimization of the reaction conditions and exploration of the substrate scope were further undertaken for this reaction, which reveal that a series of enamines with N-Cbz, Ac, COt-Bu, CO2Et protection groups could all undergo smooth C-sulfinylations with the comined use of sodium benzene sulphinate, DAMc and MeSiCl3, efficiently furnishing the β-amino vinylsulfoxide products in high yield, affording a practical and highly efficient methods for synthesis of functional vinylsulfoxides.

青藏高原栽培青稞遗传多样性研究

青稞，是我国藏区居民对裸大麦的称谓，它不仅是藏民的主要食粮、燃料和牲畜饲料，而且也是啤酒、医药和保健品生产的原料；青稞不仅为藏区人民的健康和经济发展做出了很大的贡献，而且对人类健康和社会经济的可持续发展都有重要的意义。青藏高原是我国及世界上青稞分布和种植面积最大的地区，资源极其丰富。虽然从经典遗传直到分子标记对我国大麦遗传多样性都有研究，但研究手段、数量仍然不够深入，对我国大麦资源遗传多样性研究的信息非常有限，不能很好地满足大麦遗传研究和育种应用的需要，尤其是对西藏栽培大麦的遗传多样性的研究还只是刚刚开始，关于栽培青稞多态性的研究报道很少。本研究采用SSR标记和蛋白质电泳两类技术，从SSR标记位点、单体醇溶蛋白、B组醇溶蛋白和淀粉粒结合蛋白（SGP）等四个方面对我国青藏高原栽培青稞的遗传多样性进行了综合评价。 SSR标记具有基因组分布广泛、数量丰富、多态性高、容易检测、共显性、结果稳定可靠、实验重现性好、操作简单、经济、易于高通量分析等许多优点，被认为是用于遗传多样性、品种鉴定、物种的系统发育、亲缘关系及起源等研究的非常有效的分子标记。本研究采用SSR标记分析了64份青藏高原栽培青稞的遗传多样性，同时评估SSR标记在我国大麦育种和品种鉴定中的应用潜力。选择了30个已知作图位点SSR标记，其中25个标记与重要性状的控制位点连锁紧密。选择的30个SSR标记，5个未得到很好的扩增产物，3个无多态性。22个多态性SSR标记位点中，每位点检测出等位基因2~15个，共检测出等位基因132个，平均每位点6.0 个。各多态位点检测出基因型为2~11种，位点HVM33的基因型最多。各多态位点的多态信息指数为0.16~0.91, 平均为0.65。根据PIC值选择了13个SSR标记用于我国青藏高原栽培青稞基因型鉴定，这些标记的PIC值为0.6以上。结合PIC值和基因型差异，选择了8个多态信息含量高的SSR标记，构建了高效指纹图谱，此图谱能把64份材料完全区分。 贮藏蛋白电泳分析是研究相关编码蛋白基因多态性的非常有效的方法。大麦单体蛋白与小麦醇溶蛋白相对应，具有丰富的多态性，可用于大麦遗传多样性、品种鉴定和群体进化等研究。本研究通过A-PAGE电泳技术研究了84份青藏高原栽培青稞的单体醇溶蛋白多态性。大麦单体醇溶蛋白图谱与小麦醇溶蛋白电泳图谱类似，所分离的蛋白清晰地分为ω－，γ－，β－和α－四个部分。青藏高原栽培青稞单体醇溶蛋白具有丰富的多态性，84份青稞材料中存在43条不同的蛋白带，75种组合带谱；其中67种为单一材料所独有，另8种则分别包含了2-3份材料。每份材料中拥有醇溶蛋白带为6－16条，含有6-10条单体醇溶蛋白带材料较多。西藏和四川材料群体单体醇溶蛋白多态性不同，具有区域特异性。西藏材料中发现了40条不同蛋白带，3条特异带，46 种蛋白组合；四川材料中出现了40种不同蛋白带，26种条带组合, 3条特异带。基于单体蛋白多态性的聚类与材料的来源有一定的相关性。A-PAGE单体蛋白具有丰富的多态性，可作为遗传研究和品种鉴定的标记。 大麦醇溶蛋白（hordein）是大麦籽粒的主要贮藏蛋白，与大麦的营养品质和加工品质密切相关，而且具有丰富的多态性，广泛用于品种鉴定、种质筛选、遗传多样性和亲缘关系研究。B组醇溶蛋白是主要的醇溶蛋白组份，约占总醇溶蛋白的80%，而且具有丰富的多态性。本研究采用SDS-PAGE分析了72份青藏高原栽培青稞B组醇溶蛋白的遗传多样性。青藏高原栽培青稞B组醇溶蛋白具有丰富的多态性，72份青稞材料中存在15种蛋白带，30种组合带谱，其中15种为单一材料所独有，另15种则分别包含了2-10份材料。每份材料中B组醇溶蛋白条带数为4-8条，含5、6条的材料较常见。不同来源的群体材料间B组醇溶蛋白组成存在差异，西藏青稞含有26种蛋白组合带谱，其中有19种特异带谱；四川群体中共发现11种蛋白组合带型，其中有4种特有带谱。两群体中都存在稀有条带。聚类分析将材料分成三组，材料聚类与材料来源地没有明显的相关性。 淀粉粒蛋白（Starch granule proteins, SGPs）是一类与淀粉粒结合的微量蛋白，一些淀粉粒蛋白具有淀粉生化合成中主要的酶蛋白功能，其变异会影响淀粉含量和特性，从而影响淀粉的应用。关于我国大麦淀粉粒组成研究还未见报道。本实验首次开创了我国大麦淀粉粒结合蛋白的研究工作。采用SDS-PAGE电泳技术研究了青藏高原栽培青稞的SGP组成，并分析了不同SGP组合间淀粉含量的差异，初步探索了所分离的SGP蛋白与淀粉合成的关系。66份青稞材料中分离了10种主要的SGP，其表观分子量为40-100KD，低于60KD的SGP带有7条，共有16种组合带谱；各SGP蛋白和组合带谱出现的频率存在差异，青藏高原青稞的SGP组成存在多态性。西藏青稞和四川青稞的SGP组成有很大差异，SGP组成具有地域差异性，西藏青稞含有12种蛋白组合带谱，其中有9种特异带谱；四川群体中共发现7种蛋白组合带型，其中有4种特有带谱；两群体中仅有3种共同的蛋白组合带谱。SGP蛋白特性将66份青稞分为三组, 即Ⅰ、Ⅱ、Ⅲ，材料聚类与材料来源具有一定的相关性。不同组合带谱材料间淀粉含量差异显著性检验结果显示，不同带谱间材料的总淀粉含量、直链淀粉含量和支链淀粉含量有差异，带谱2（SGP1+3+7+9+10）和8（SGP1+2+4+6+8）的总淀粉含量及支链淀粉含量显著大于组合带谱3（SGP1+3+7+10）的总淀粉含量。组合带谱7（SGP1+2+6+8）的直链淀粉含量显著低于带谱11（SGP1+5+8）的直链淀粉。带谱SGP2、3、4、5、6、7、8、9、10可能参与淀粉合成，SGP9可能与高支链淀粉的合成相关。 SSR标记位点、单体醇溶蛋白、B组醇溶蛋白、淀粉结合蛋白等四个方面的研究结果表明青藏高原SSR标记多态性、单体醇溶蛋白多态性、B组醇溶蛋白多态性和SGP多态性都非常丰富，与青藏高原是栽培青稞的多样性分布中心的观点一致。 青藏高原栽培青稞的SSR标记、单体醇溶蛋白、B组醇溶蛋白和SGP多态性表现出很大差异。SSR标记覆盖了整个基因组，多态性非常高。单体蛋白、B组醇溶蛋白、SGP蛋白是育种中非常关注的性状，他们只是代表基因组中的某一区域或位点，多态性相对较低。但单体蛋白多态性很高，84份材料中检测出43条不同蛋白带，75种不同的组合带谱。SSR标记技术和单体蛋白技术都是遗传多样性研究的有力工具，但单体蛋白技术不仅多态性高，而且经济、操作简便，是种质鉴定的理想方法。 对不同标记的多态性材料数据进行聚类，聚类图能为我们提供各材料间的遗传相似信息，为材料选择提供参考。但材料聚类与材料来源的地理区域的相关性表现不一致。SSR聚类和B组醇溶蛋白聚类与材料的来源地无相关性，而单体醇溶蛋白和SGP聚类与材料来源地有一定相关性，即西藏群体和四川群体分别有集中类群，这可能是人为选择的附加效应。 不同来源的群体材料的遗传多样性不同，具有区域特异稀有基因，加强不同地区间资源的交换和配合使用，有利于增加群体遗传多样性和新品种培育。 青藏高原栽培青稞的麦芽浸提性状、淀粉性状、病虫及裸粒等重要农艺性状控制位点存在丰富的变异，遗传基础宽广，可能蕴藏着多种不同的等位基因，是研究重要性状遗传特性、基因资源挖掘和遗传育种的宝贵资源库。 Hulless barley, due to its favorable attributes such as high feed value, good human nutrition，rich dietary fiber and ease processing, attracts people,s attention . Hulless barley plays a very important role in Tibetan life, used as essential food crop, main animal feed and important fuel. In addition to tsampa (roasted barley flour), a main food for Tibetan, hulless barley is also made into cake, soup, porridge, recent naked barley liquor and cornmeal. Qinghai-Tibet Plateau is one of a few areas which plant naked barley widely in the world and also has a long growing history. Genetic diversity of the cultivated hulless barley in this region , however, has not been documented. The study of genetic diversity existing within this population is of particular interest in germplasm identification, preservation, and new cultivar development. This study analyzed the genetic diversity of the cultivated naked barley from Qinghai-Tibet plateau through the study of SSR marker loci and monomeric prolamins, B-horden and starch granule proteins. SSRs are present abundantly in genomes of higher organisms and have become a popular marker system in plant studies. SSRs offer a number of advantages, such as the high level of polymorphisms, locus specificity, co-dominance, reproducibility, ease of use through PCRand random distribution throughout the genome. In barley, several hundred SSRs have been developed and genetically mapped and can therefore be selected from specific genomic regions. The genetic diversity of 64 cultivated naked barley from Tibet and Sichuan was studied with 30 SSRs of known map location.Among the selected SSR markers, PCR products of 5 SSR markers were not obtained and 3 SSR marker loci were monomeric. A total of 132 alleles were identified at 22 polyomeric SSR loci. The number of alleles per locus ranged from 2 to 15, with an average of 6.0. The polymorphism information content values for the SSRs ranged from 0.08 to 0.94, with an average of 0.65. 13 SSR markers with the PIC value >0.6 have been selected for discrimination of Qinghai-Tibet naked barley genotypews. A finger Print map was developed through 7 SSR markers with the high PIC value. It could be used as an efficient tool for gene discovery and identification of gernplasm. Hordeins, the main storage proteins of the barley seed, are composed of momomeric and polymeric prolamins and divided into -A, B, C and D groups in order of decreasing electrophoretic mobility. Hordeins show high inter-genotypic variation and have been extensively used as markers for cultivar identification and analyzing the genetic diversity. This study analyzed the genetic diversity of B-hordein in 72 naked barley from Qinqhai-Tibet Plateau. Extensive diversity was observed. A total of 15 different bands and 30 distinct patterns were found. Jaccard's coefficient of similarity was calculated, and the accessions were divided into three　main groups by cluster analysis using UPGMA. Differentiation among the populations from different collecting regions based on the polymorphism of B-hordein was investigated. Monomeric prolamins show high inter-genotypic variation and have been used as molecular markers for cultivar identification, analyzing the genetic diversity in collections and investigating the evolution processes and structure of populations However, the cultivated hulless accessions from Qinghai-Tibet Pateau in China have never been examined with respect to monomeric prolamins. This study analyzed the genetic diversity of monomeric prolamins (protein fraction corresponding to wheat gliadins) using the Acid -PAGE technique in eighty-four cultivated hulless barley from Qinqhai-Tibet Plateau in China. Extensive diversity was observed. A total of 43 different bands were found, of which 21 different bands were in the region of ω group, 8 in the region of γ, 8 in the region of β, and 6 in the region of α group. Among the 86 accessions, 75 distinct patterns were identified. The number of bands ranged from 6 to 16, depending on the variety. Jaccard’s coefficient of similarity was calculated, and the lines were grouped by cluster analysis using UPGMA. A dendrogram was obtained from the analysis of the groups and five main clusters were identified. No relationship between the distribution in the dendrogram and growth habits and origins of the cultivars could be detected. Starch is the major constituent of the cereal endosperm, comprising approximately 65% of the dry weight of the mature wheat grain. The starch formed in all organs of plants is packaged into starch granules, which vary widely between species and cultivars in size and shape. Wheat endosperm starch granules contain about corresponding to the main biosynthase of starch. This report firstly dealed with intraspecific variation of the major SGPs in cultivated naked barley from Qinghai-Tibet plateau. A total of 10 major SGPs were observed in the range of 40KD-100KD and 16 types of patterns were found. Based on the variation of SGPs, accessions studied were classified into 3 groups. A geographical cline of electrophoregram was observed. In addition, significance test of the difference of starch content among groups and types of patterns were done, and the results indicated those SGPs could be related to the content of starch. Diagram obtained through cluster analysis exhibited a structuration of diversity and genetic relationship among cultivated hulless accessions. In breeding program, parents with genetically distant relationship for hybridization will increase genetic diversity of progenies. In conclusion, cultivated naked barley from Qinghai-Tibet Plateau in China presents a high variability with respect to monomeric prolamins，SSR markers , B- hordeins and SGPs. The result of this study supports Qinghai-Tibet Plateau is the center of cultivated hulless barley and the cultivated naked barley is considered to be a gene pool with large diversity and could be applied to breeding for cereal.

基于语义的Web服务匹配及其框架模型研究

随着Internet上异构应用系统的大量增加和SOA技术的空前发展，Web服务技术变得越来越重要，已经成为了学术界和工业界关注的热点。在Web服务技术中，服务发现为Web服务消费者调用Web服务提供者提供的服务提供了桥梁，起到非常重要的承接作用，成为了Web服务技术中的重点。目前的Web服务发现机制主要有两种，第一种是传统的Web服务发现方式，主要基于UDDI（Universal Description， Discovery and Integration）的纯粹关键字查找；第二种是基于Web服务的语义信息，进行Web服务间的语义匹配。 第一种方法的基础UDDI是国际标准，而且应用也最为广泛，但UDDI中对于Web服务的描述是基于语法的，而且缺乏Web服务所特有的I/O属性和服务质量属性等信息。第二种方法基于Web服务的语义信息，包括Web服务所特有的I/O属性，但因为缺乏灵活有效的Web服务匹配方法和与之对应的Web服务匹配框架，限制了其应用。 基于此，本文在对当前语义Web服务匹配技术分析和研究的基础上，对当前的语义Web服务匹配方法进行了改进，同时提出了基于过滤器（filter）的语义Web服务匹配框架模型。本文的主要工作有： 1）对目前的语义Web服务匹配技术进行了较为全面深入的探讨和综述。 2）对当前的语义Web服务匹配的各个阶段进行了详细的分析，对其中的匹配方法进行了改进。提出了基于向量空间模型(VSM)和TF-IDF(Term Frequency–Inverse Document Frequency)思想的本体权重的计算方法，本体层次关系图中边的权重的计算方法和本体之间相似度的计算方法。 3）提出了基于web服务黑盒属性的语义。 4）语义Web服务匹配框架方面，本文提出了基于filter的语义Web服务匹配框架，并将其延伸到非语义Web服务系统中。

Tuning the Energy Level of Organic Sensitizers for High-Performance Dye-Sensitized Solar Cells

Cost-effective organic sensitizers will play a pivotal role in the future large-scale production and application of dye-sensitized solar cells. Here we report two new organic D-pi-A dyes featuring electron-rich 3,4-ethylenedioxythiophene- and 2,2'-bis(3,4-ethylenedioxythiophene)-conjugated linkers, showing a remarkable red-shifting of photocurrent action spectra compared with their thiophene and bithiophene counterparts. On the basis of the 3-f{5'-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-2,2'-bis(3,4-ethylenedioxythiophene)-5-yl}2-cyanoacrylic acid dye, we have set a new efficiency record of 7.6% for solvent-free dye-sensitized solar cells based on metal-free organic sensitizers. Importantly, the cell exhibits an excellent stability, keeping over 92% of its initial efficiency after 1000 h accelerated tests under full sunlight soaking at 60 degrees C. This achievement will considerably encourage further design and exploration of metal-free organic dyes for higher performance dye-sensitized solar cells.

Development of expressed sequence tags from the bay scallop, Argopecten irradians irradians

The bay scallop, Argopecten irradians irradians, introduced from North America, has become one of the most important aquaculture species in China. Inan effort to identify scallop genes involved in host defense, a high-quality cDNA library was constructed from whole body tissues of the bay scallop. A total of 5828 successful sequencing reactions yielded 4995 expressed sequence tags (ESTs) longer than 100 bp. Cluster and assembly analyses of the ESTs identified 637 contigs (consisting of 2853 sequences) and 2142 singletons, totaling 2779 unique sequences. Basic Local Alignment Search Tool (BLAST) analysis showed that the majority (73%) of the unique sequences had no significant homology (E-value >= 0.005) to sequences in GenBank. Among the 748 sequences with significant GenBank matches, 160 (21.4%) were for genes related to metabolism, 131 (17.5%) for cell/organism defense, 124 (16.6%) for gene/protein expression, 83 (11.1%) for cell structure/motility, 70 (9.4%) for cell signaling/communication, 17 (2.3%) for cell division, and 163 (21.8%) matched to genes of unknown functions. The list of host-defense genes included many genes with known and important roles in innate defense such as lectins, defensins, proteases, protease inhibitors, heat shock proteins, antioxidants, and Toll-like receptors. The study provides a significant number of ESTs for gene discovery and candidate genes for studying host defense in scallops and other molluscs.

Winter counter-wind currents off the southeastern China coast: A review

This review covers the discovery and studies of the year-round northeastward currents off the southeastern China coast, paying special attention to its upwind characteristic in winter, mainly focusing on work by Chinese oceanographers. This current system is a prominent and unique phenomenon in the shelf circulation of the world ocean. The general features of the current system are summarized. The evidence for the existence and the variation of the three parts of the currents-the South China Sea Warm Current, the Taiwan Strait Warm Current and the Taiwan Warm Current-are separately elucidated. The formation mechanisms of the current as a whole are explained using dynamic analysis and numerical simulation results. Some suggestions for further studies are also made.

转炉钢渣对海洋生态环境影响及碳的生物利用探索研究

利用“铁肥”方法增加海洋初级生产力、吸收大气中的CO2、降低温室效应是目前国际上的一个研究热点。为此，本文利用炼钢企业产生的废料转炉钢渣，系统研究了其对海洋微藻生长的影响， 同时研究了转炉钢渣对海水水质及海洋生物的影响，探讨了其作为“铁肥”材料的可行性。 本文首先研究了转炉钢渣对海水水质的影响，包括金属、营养盐、pH、COD及浊度等理化参数。研究发现，在天然海水中加入转炉钢渣后营养盐均有不同程度的溶出；实验条件下，在天然海水和人工海水中加入钢渣，金属大部份被吸附，个别金属溶出，但基本都达到了一、二类海水标准，而pH明显增高，大多超过了海水水质三、四级（6.88.8）的范围，COD低于一类海水水质标准。实验结果显示，钢渣粒度越小、浓度越大，水质浊度越大，但钢渣的比重一般较大，在水体中可以较快的沉降，所以在实际应用过程中不会对水体的透明度造成不良影响。 研究了转炉钢渣对典型海洋底栖生物（紫贻贝）、海洋游泳生物（日本对虾和中国对虾幼虾）的影响。在实验浓度范围内，钢渣对紫贻贝的急性毒性作用基本可以忽略，但紫贻贝的生长率和摄食率随钢渣浓度的增加有所下降，血细胞个数有所下降，但形态没有显著变化，对紫贻贝的免疫功能没有太大影响。钢渣对日本对虾幼虾的半致死浓度为1.62g/L，对中国对虾幼虾的半致死浓度要高于日本对虾，说明在实验条件下中国对虾幼虾的适应能力高于日本对虾幼虾。 另外，重点考察了转炉钢渣对海洋浮游植物－赤潮异弯藻和中肋骨条藻生长的影响，发现加入钢渣以后，相对于对照组微藻生物量显著增加。当钢渣浓度为124248mg/L时赤潮异弯藻的生物量达到最大，当钢渣浓度达到61124mg/L时，中肋骨条藻的生物量最大；钢渣对两种微藻生长的影响规律是相同的，但是影响程度因不同藻种而有所不同，其中对中肋骨条藻的促进作用更加显著，可能与钢渣中能溶出较大量的硅酸盐有关。在室内实验的基础上，初步估算了通过钢渣对微藻生长的促进作用，近海每平方公里海域对二氧化碳吸收的增加量。

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.

地球介质非线性与各向异性的地震波响应及其成像效应

The practice of geophysical prospecting shows us the complex interior earth. The studies of the complexity play an important role and practical guide for the subsurface structure. At present, the complexity of the earth mainly means lateral and vertical homogeneity, anisotropy and non-linear quality. And the anisotropy and non-linear media studies become the frontier in seismology and exploration seismology. This paper summarizes the development of complexities and presents the forward and inverse in the non-linear and anisotropic media. Firstly, the paper introduces the theory of seismic wave propagation in the non-linear and anisotropic media, the theoretical basis for simulation and inversion research. Secondly, high quality numerical simulation method with little dispersion has been developed to investigate the influence of complexity including anisotropy and non-linear multi-component seismograms. Because most real data in seismology have a single component, we developed two aspects work on anisotropic multi-component imaging. One is prestack reflection migration. The result show that distorted images are obtained if data from anisotropic media are migrated using isotropic extrapolation. Moreover, image quality will be improved greatly after considering anisotropy in subsurface layers. The other one is the we take advantage of multi-component data to inversion of the anisotropic parameters jointly seimic reflection travel time and polarization information. Based on these research works, we get the following results: 1.Combing numerical simulation, systematical studies indicate that anisotropy and non-linear seismograms characters are significant to detect cracked belts in the earth and to understand deformation field and mechanism. 2.Based on anisotropic media models, we developed an efficient prestack migration method for subsurface structure and different observation methods seismic data, which improving the imaging quality with VSP, seismograms and real data. 3.Jointly seismic inversion combining seismic anisotropic reflection traveltimes and polarizations data show that the complete wrong inversion and the following explanation will be resulted by ignoring anisotropy.

东北亚构造-盆地演化及油气资源控制作用

The oil and gas potential of Northeast Asia is enormous, but the degree of exploration is very low in Northeast Asia (the degree is below 3%-10%).The reasons are as follows: First, it is relatively difficult to study the oil and gas bearing basins(OGB), which are of multiple types, in different tectonic settings, with complex geologic frameworks and with long-term geologic evolution. Secondly, because of the non-equilibrium in development of economy and regional market, application of theories and techniques and the research levels in different countries, the conclusions are not conformable, and even contradictory. Thirdly, most of the former researches were limited to one territory or one basin, and lack of systematical and in-depth study on geotectonic evolution, classification of basins, and the evaluation of hydrocarbon resources. In this thesis, integrated study of the regional tectonic feature and basin features of Northeast Asia was done, to understand the basin evolution history and the controlling action on oil and gas. Then, new conclusions are and exploration proposals are as following: 1. Geotectonic evolution in Northeast Asia: The main structural motion system in Paleozoic Era was longitudinal, and in Meso-cenozoic was latitudinal with the Pacific Ocean. The whole evolution history was just the one of pulling-apart, cutting-out, underthrusting and collision of the Central Asia- Mongolia Ocean and the Pacific Ocean. 2. The evolution characteristics of basins in Northeast Asia: mainly developed from longitudinal paste-up, collision and relaxation rifting motion in Paleozoic-Early Mesozoic Era and from underthrust, accretion, and receding of subducted zone of the Pacific Ocean in Late Mesozoic Era-Cenozoic Era. 3. The research in basin classification of Northeast Asia: According to geotectonic system, the basins can be classified into three types: intracratonic, pericratonic and active zone basin. And they can be further classified into 18 different types according to genetic mechanism and dynamic features. 4. The master control factors of oil and gas accumulation in Northeast Asia: high quality cap-rock for craton and pericrationic basin, the effective source rock and high quality cap-rock for Mesozoic rifted basins, intra-arc, fore-arc and back-arc basins. Graded exploration potential of oil and gas for basin in Northeast Asia according to 7 factor, hereby, divided the oil and gas potential of basins into 5 levels. 5. Evaluation of hydrocarbon resources: The difference of resource potential among these basins is huge in Northeast Asia. The evaluation of Mesozoic rifted basin and Pacific Ocean basin showed that the large scale rifted basin and retroarc basin(including backarc marginal sea basin) have great resource potential. 6. The writer believes that the next step should pay more attention to the evaluation of petroleum resource in Far East part of Russia and trace them. On the other hand, according to integrated analysis of oil/gas resource potential and the operation difficulty in this area, suggests that East-Siberia basin, East-Gobi-Tamchag basin, Sakhalin basin, North-Okhotck basin, West-Kamchatka basin could be as cooperation priority basins in future.

松辽盆地长岭断陷火山岩储层识别与勘探目标评价

Changling fault depression is the biggest fault subsidence in south of Songliao Basin. In its Lower Cretaceous Yingcheng and Shahezi formations developed thick source rocks of deep lake facies and developed poly-phase volcanic rock reservoirs as well. In recent years, significant breakthroughs have been obtained in hydrocarbon exploration of volcanic rock reservoir in the different fault depressions in Songliao basin. Lately, I have been involved in hydrocarbon exploration in the Changling rift depression, especially volcanic rock reservoirs and exploration targets research, participating in the deployment of well Yaoshen 1 which gained over 40 × 104m3 natural gas flow. As quick changes of lithology and facies in Changling area in the south of Songliao basin, and the volcanic rock interludes distribution in continental clastic rock and shale in 3D space, so the identification of volcanic rock types and distribution become a difficult problem. Thus, based on the integrated research of the wild outcrop observation, gravity, magnetic and seismic data, geophysical logging, drilling and coring, laboratory test, this paper carried out the reservoir identification, description and prediction of volcanic rocks in Changling fault depression. In this area, this paper analyzed the volcanic rocks litho-facies, the eruption period, and characteristics of cycles. At the same time, tried to know how to use logging, seismic data to separate volcanic rocks from sandstone and shale, distinguish between volcanic reservoir and non-reservoir, distinguish between intermediate-basic and acidic volcanic rocks, and how to identify traps of volcanic rocks and its gas-bearing properties, etc. Also it is summarized forming conditions and distribution of traps, and possible gas-bearing traps were optimized queuing management. Conclusions as follows: There are two faulted basements in Changling fault depression, granite basement in the southeast and upper paleozoic epimetamorphic basement in the northwest. The main volcanic reservoirs developed in Yingcheng period, which was the intermediate-basic and acidic volcanic eruptions, from the south to north by the intermediate-basic to acid conversion. The volcanic vents are gradually young from south to north. According to information of the re-processing 3D seismic data and gravity-magnetic data, the large volcanic vent or conduit was mainly beaded-distributed along the main fault. The volcanic rocks thickness in Yingcheng formation was changed by the deep faults and basement boundary line. Compared with the clastic rocks, volcanic rocks in Changling area are with high resistance and velocity (4900-5800), abnormal Gamma. All kinds of volcanic rocks are with abnormal strong amplitude reflection on the seismic stacked section except tuff. By analyzing the seismic facies characteristics of volcanic rocks, optimizing seismic attributes constrained by logging, using seismic amplitude and waveforms and other attributes divided volcanic rocks of Yingcheng formation into four seismic zones in map. Currently, most volcanic gas reservoirs are fault-anticline and fault-nose structure. But the volcanic dome lithologic gas reservoirs with large quantity and size are the main gas reservoir types to be found.

油气勘探中的弱磁异常提取与区域场分析

Petroleum and natural gas is an important strategic resources. The short of the reserves will block the development of economy and threaten the safety of nation, along with the main oil fields of our country coming to the height of power and splendor of the exploitation and exploration. Therefore, it makes a great sense to inaugurate new explorative field and increase the reserves of petroleum and natural gas. Magnetic exploration is a main method of geophysics exploration. the developing observation apparatus and the perfect processing method provide wide space for magnetic exploration in these years. The method of magnetic bright spot is an application of magnetic exploration. The vertical migration of the hydrocarbon changes physical and chemical environment above the hydrocarbon reservoir, the new environment make tervalent iron translate into bivalent iron, that produce small scale magnetic anomaly, that is magnetic bright spot. The method of magnetic bright spot explores oil and gas field by the relation between the hydrocarbon and magnetic anomaly. This paper systemically research to pick-up and identify magnetic bright spot combining an oil field item, then point out advantaged area. In order to test the result, the author use the seismic information to superpose the magnetic bright spot, that prove the magnetic bright spot is reliable. then, the author complete a software to pick and identify the magnetic bright spot. The magnetic basement is very important to research forming and evolvement of the basin, especially, it is a crucial parameter of exploring residual basin in the research on pre-Cenozoic residual. This paper put forward a new method to inverse the interface of the magnetic layer on the basis of previous work, that is the method of separation of magnetic field step by step. The theory of this method is to translate the result of magnetic layer fluctuation to the result of magnetization density change, and the magnetic layer is flat, the paper choose thickness of magnetic layer as unit thickness, and define magnetic layer as a unit-thickness layer in order to convenient calculation, at the same time, define the variational magnetization density as equivalent magnetic density. Then we translate the relation between magnetic field and layer fluctuation to the relation between magnetic field and equivalent magnetic density, then, we can obtain the layer fluctuation through calculating equivalent magnetic density. Contrast to conventional parker method, model experimentation and example checkout prove this method is effective. The merit of this method is to avoid flat result in a strongly fluctuant area because of using a uniform average depth, the result of this method is closer to the fact, and this method is to inverse equivalent magnetic density, then translate equivalent magnetic density to layer fluctuation, this lays a foundation to inverse variational magnetic density in the landscape orientation and portrait.

济阳坳陷深层地质构造与演化

Based on geophysical and geological data in Jiyang depression, the paper has identified main unconformity surfaces (main movement surfaces) and tectonic sequences and established tectonic and strata framework for correlation between different sags. Based on different sorts of structural styles and characteristics of typical structures, the paper summarized characteristics and distribution of deep structures, discussed evolution sequence of structure, analyzed the relation between tectonic evolution and generation of petroleum. The major developments are as following: Six tectonic sequences could be divided from bottom to top in the deep zone of Jiyang depression. These tectonic sequences are Cambrian to Ordovician, Carboniferous to Permian, lower to middle Jurassic, upper Jurassic to lower Cretaceous, upper Cretaceous and Kongdian formation to the fourth member of Shahejie formation. The center of sedimentation and subsidence of tectonic sequences distinguished from each other in seismic profiles is controlled by tectonic movements. Six tectonic evolution stages could be summarized in the deep zone in Jiyang depression. Among these stages, Paleozoic stage is croton sedimentation basin; Indosinian stage, open folds of EW direction are controlled by compression of nearly SN direction in early Indosinian (early to middle Triassic) while fold thrust fault of EW – NWW direction and arch protruding to NNE direction are controlled by strong compression in late Indosinian (latter Triassic); early Yanshanian stage (early to middle Jurassic), in relatively weak movement after Indosinian compressional orogeny, fluviolacustrine is deposited in intermontane basins in the beginning of early Yanshanian and then extensively denudated in the main orogenic phase; middle Yanshanian (late Jurassic to early Cretaceous), strike-slipping basins are wide distribution with extension (negative reversion) of NW – SE direction; latter Yanshanian (late Cretaceous), fold and thrust of NE – NNE direction and positive reversion structure of late Jurassic to early Cretaceous strike-slipping basin are formed by strong compression of NW–SE direction; sedimentation stage of Kongdian formation to the fourth member of Shahejie formation of Cenozoic, half graben basins are formed by extension of SN direction early while uplift is resulted from compression of nearly EW direction latterly. Compression system, extension system and strike-slip system are formed in deep zone of Jiyang depression. According to identifying flower structure of seismic profiles and analysis of leveling layer slice of 3D seismic data and tectonic map of deep tectonic interface, strike-slip structures of deep zone in Jiyang depression are distinguished. In the middle of the Jiyang depression, strike-slip structures extend as SN direction, NNW direction in Huimin sag, but NNE in Zhandong area. Based on map of relict strata thickness, main faults activity and regional tectonic setting, dynamic mechanisms of deep structure are preliminary determination. The main reason is the difference of direction and character of the plate’s movement. Development and rework of multi-stage tectonic effects are benefit for favorable reservoir and structural trap. Based on tectonic development, accumulation conditions of deep sub-sags and exploration achievements in recent years, potential zones of oil-gas reservoir are put forward, such as Dongying sag and Bonan sag.

准噶尔盆地滴南凸起中生界层序地层及有利勘探目标优选

Based on the theories of sequence stratigraphy and sedimentology, as well as comprehensive studies of seismic data, drilling data, core interpretation and setting of this area, the thesis presents an analysis for Mesozoic formation in Dinan uplift. By means of recognizing the boundary of the sequence, dividing and correlating the systems tract, Mesozoic of Dinan uplift is divided into ten sequences and twenty-five systems tracts during the establishment of the sequence framework. In the framework, some sequences are featured by mature systems of lowstand, water-transgression and highstand, while some undeveloped systems of lowstand or highstand. The main sedimentary facies in Mesozoic of Dinan uplift are braided river, meandering river, delta and lake. The braided river was divided into sandy river and rudaceous river by the lithology of the river channel and was divided into dry climate and wet climate condition by the color of the flood plain. Additionally, The concept of “wetland” is put forward for the first time and regarded as the consequence of wet climate. The analysis includes the classification of six types of traps: (1) stratigraphic overlap trap, (2) lithologic trap with updip pinchout, (3) stratigraphic unconformity trap, (4) fault-lithology trap, (5) fault trap, (6) anticlinal trap, and combining with the research of the characteristics and distribution rules for the known reservoir, it draws out that “fault control” is the petroleum accumulation pattern in this area, in which fault is the key element of the transporting system. Finally the thesis concludes the distribution characteristics and optimized some targets for the potential exploration zone.

油气勘探风险评价与决策技术研究

PetroChina and other national petroleum incorporations need rigorous procedures and practical methods in risk evaluation and exploration decision at home and abroad to safeguard their international exploration practice in exploration licence bidding, finding appropriate ratio of risk sharing with partners, as well as avoiding high risk projects and other key exploration activities. However, due to historical reasons, we are only at the beginning of a full study and methodology development in exploration risk evaluation and decision. No rigorous procedure and practical methods are available in our exercises of international exploration. Completely adopting foreign procedure, methods and tools by our national incorporations are not practical because of the differences of the current economic and management systems in China. The objective of this study is to establish a risk evaluation and decision system with independent intellectual property right in oil and gas exploration so that a smooth transition from our current practice into international norm can take place. The system developed in this dissertation includes the following four components: 1. A set of quantitative criteria for risk evaluation is derived on the basis of an anatomy of the parameters from thirty calibration regions national wide as well as the characteristics and the geological factors controlling oil and gas occurrence in the major petroleum-bearing basins in China, which provides the technical support for the risk quantification in oil and gas exploration. 2. Through analysis of existing methodology, procedure and methods of exploration risk evaluation considering spatial information are proposed. The method, utilizing Mahalanobis Distance (MD) and fuzzy logic for data and information integration, provides probabilistic models on the basis of MD and fuzzy logic classification criteria, thus quantifying the exploration risk using Bayesian theory. A projection of the geological risk into spatial domain provides a probability map of oil and gas occurrence in the area under study. The application of this method to the Nanpu Sag shows that this method not only correctly predicted the oil and gas occurrence in the areas where Beibu and Laoyemiao oil fields are found in the northwest of the onshore area, but also predicted Laopu south, Nanpu south and Hatuo potential areas in the offshore part where exploration maturity was very low. The prediction of the potential areas are subsequently confirmed by 17 exploration wells in the offshore area with 81% success, indicating this method is very effective for exploration risk visualization and reduction. 3. On the basis of “Methods and parameters of economic evaluation for petroleum exploration and development projects in China”, a ”pyramid” method for sensitivity analysis was developed, which meets not only the need for exploration target evaluation and exploration decision at home, but also allows a transition from our current practice to international norm in exploration decision. This provides the foundation for the development of a software product “Exploration economic evaluation and decision system of PetroChina” (EDSys). 4. To solve problem in methodology of exploration decision, effort was made on the method of project portfolio management. A drilling decision method was developed employing the concept of geologically risked net present value. This method overcame the dilemma of handling simultaneously both geological risk and portfolio uncertainty, thus casting light into the application of modern portfolio theory to the evaluation of high risk petroleum exploration projects.