structuring and manipulating hand-drawn concept maps

Concept maps are an important tool to knowledge organization,representation, and sharing. Most current concept map tools do not provide full support for hand-drawn concept map creation and manipulation, largely due to the lack of methods to recognize hand-drawn concept maps. This paper proposes a structure recognition method. Our algorithm can extract node blocks and link blocks of a hand-drawn concept map by combining dynamic programming and graph partitioning and then build a concept-map structure by relating extracted nodes and links. We also introduce structure-based intelligent manipulation technique of hand-drawn concept maps. Evaluation shows that our method has high structure recognition accuracy in real time, and the intelligent manipulation technique is efficient and effective.

氮杂环化合物的绿色合成研究

氮杂环化合物大多数都是具有生理活性的物质，例如喹喔啉化合物与苯二氮卓类化合物，因此研究氮杂环化合物骨架的构建方法具有一定意义。绿色化学的迅速发展迫切要求化学家发展清洁、经济和环境较友好条件下的有机合成方法。其中，水相反应与绿色固体酸催化剂的使用都是实现绿色有机合成的重要途径，它们非常具有潜力，近些年受到了广泛关注。本论文的主要工作是围绕水相及固体酸催化条件下两类具有生物活性的含氮杂环小分子的合成方法而开展的，具体包括以下内容： 1. 研究和探索出了两类绿色固体酸催化剂蒙脱土（Mont. K-10）和杂多酸(H4SiW12O40), 在水相条件下成功合成出喹喔啉化合物的有效方法。两个催化体系都以无毒无公害的水作反应溶剂，实验条件温和，操作安全简便，反应速度快，底物普适性强，产率高，且产物易分离收集。两类固体酸催化剂，对设备腐蚀性小，可回收循环使用，对环境无公害; 蒙脱土催化大部分底物能得到当量产率的产物，硅钨酸催化催化剂负载量小。 2. 实现了无溶剂条件下，以杂多酸（H3PW12O40）作催化剂，高效合成1,5-苯二氮卓衍生物的合成方法。该催化体系具有以下一些优势：实验条件温和，反应速度较快，底物普适性良好，产物易分离收集，反应过程中没有加入其它有机溶剂，绿色环保。 ‘Green Chemistry’ is currently a major issue of modern chemistry. It is widely acknowledged that there is a growing need for more environmentally acceptable processes in the chemical industry. New green catalysts and green reaction media are the important and efficient strategies in green chemistry. New green catalysts include solid acid catalysts, solid base catalysts, metal catalysts not only possess higher activity and selectivity, but also are easily separated from reaction system. Green reaction media include water, supercritical fluids and ionic liquids can not only substitute traditional toxic and harmed organic solvents, but also improve reaction activity and selectivity. Meanwhile water is a promising green reaction medium for use in modern chemistry because it has a number of advantages such as the cheapest solvent available on earth, being non-hazardous and non-toxic to the environment. Solid acids had also attracted much attention for realizing green chemistry due to their unique acidity, high activity and efficiency as organic catalysts. Nitrogen-containing heterocyclic compounds of different ring sizes such as quinoxaline and benzodiazepine are the important pharmacologically active compounds. Due to the wide biological significance of these compounds, the synthesis of these types of compounds have received a great deal of attention. Despite the large availability of methods to construct nitrogen-containing heterocyclic compounds, there is still a strong need to further explore green methods to efficiently and safely synthesize these compounds. Thus, we aim at developing efficient and green methodology for the synthesis of quinoxaline and benzodiazepine carried out under water condition with solid acid catalysts. The contents of this dissertation are listed as the following: 1. We have developed two catalytic systems for the synthesis quinoxaline via the condensation of an aryl 1,2-diamine with a 1,2-diketone compound in the presence of Mont. K-10 or H4SiW12O40 as a catalyst in water solvent. Both of these two methods can be applied to wide range of substrates, tolerating aryl 1,2-diamine/1,2-diketone with the electron donating/drawing substituent. Operational simplicity, the ambient conditions, use of an economically convenient catalyst, use of water as a desirable solvent, high yields and short reaction times are the key features of these two protocols. 2. We developed a convenient and efficient protocol for the synthesis of a variety of 1,5-benzodiazepines in high yields via condensation of aryl o-phenylenediamine derivatives with a variety of ketones using H3PW12O40 as a green recyclable and heterogeneous catalyst under solvent-free condition. The simple experiment procedure combined with ease of recovery and reuse of this catalyst make this procedure quite simple, more convenient and environmentally benign.

硫手性有机小分子催化剂的设计、合成及其在不对称亚胺氢转移还原中的应用

过去十多年，世界手性药物市场需求迅速增长，手性制药工业的发展壮大，已经引起了各国政府、学术界，特别是企业界的高度重视。手性药物中含有大量的手性胺单元，因此研究高效构建手性胺结构单元的方法具有重要的意义和实用价值，而亚胺的不对称还原是合成手性胺最便捷的方法。 手性有机小分子路易斯碱催化三氯氢硅不对称还原亚胺是最近几年才发展起来的一类新的亚胺不对称还原方法。尽管在对映选择性和底物适用范围等方面已经获得了突破性的进展，但是，高性能的路易斯碱催化剂仅局限于N-甲酰氨基酸酰胺一种类型，而且其底物适用范围和催化活性仍不够理想。因此，发展新型催化剂很有必要。 手性硫氧化物作为手性诱导剂的应用已经有数十年的时间，广泛应用在不对称合成及天然产物的全合成中。理论上，硫氧结构单元也可以作为路易斯碱，对硅烷类试剂进行活化，而且硫氧键还有碳氧键难以比拟的先天优势，硫原子自带手性特征，在反应过程中，手性中心离反应位点更近，因此，从手性硫氧化合物出发，极有可能开发出新的高效手性路易斯碱催化剂。最近，Kobayashi和Khiar在亚胺的不对称烯丙基化反应中用手性亚砜活化烯丙基三氯硅烷，获得了较好的ee值，但反应中手性亚砜的用量都需要化学计量以上，因此还不能算做真正意义上的催化剂，进一步的文献调研也未见真正意义上的硫手性有机小分子催化剂。 本文首次成功将硫手性亚磺酰胺衍生物应用于催化三氯氢硅对亚胺的不对称还原，在经过对亚磺酰胺衍生物的多次结构优化，开发出了合成容易，催化活性和立体选择性都很优良，并且有着前所未有的底物普适性的新型手性路易斯碱催化剂。 我们首先尝试将商品化的20mol%叔丁基亚磺酰胺和对甲基亚磺酰胺直接用作催化剂催化三氯氢硅对亚胺的不对称还原，尽管仅获得中等的收率和很低的对映选择性，但证明我们的设计思路是可行的。在此基础上，我们以叔丁基亚磺酰胺为原料和基本骨架，设计合成了一系列的亚磺酰胺类催化剂，通过对催化剂的结构改造，发现当催化剂中存在较强酸性的酚羟基时，催化效果得到大幅提高。随着对催化剂的进一步结构优化，我们找到了一个结构简单，催化效果还不错的催化剂，经过反应条件优化以后，催化反应的收率最高能达到98%，对映选择性最高达93%，并且这个催化剂的底物适应范围比之前报道的催化剂都要广泛。针对酚羟基在催化剂中的重要作用，我们进行了仔细的机理研究后发现，在催化反应中，催化剂极有可能是通过双分子机理去活化三氯氢硅从而实现不对称催化的，而酚羟基的作用就是通过分子间氢键促进双分子催化剂与三氯氢硅的络合。受此启发，我们设计了一系列具有双齿结构的催化剂，通过对双齿催化剂的结构优化，最终筛选出了一个结构更加简单，但催化效果更好的双齿催化剂。10mol%该催化剂催化亚胺还原最高获得95%的收率和96%的ee值。这一结果也进一步验证了我们先前对催化剂机理的推测。 随后，我们还尝试将这些催化剂用于二级胺和芳香酮的直接还原胺化反应中，虽然能获得不错的收率，但对映选择性却很差，我们对反应条件进行了仔细的摸索，仍然没有获得突破。但这些实验为进一步研究二级胺和酮的不对称直接还原胺化反应奠定了良好的基础。 In the past decade, the rapid growth of the global chiral drug market and the significant development of the chiral pharmaceutical industry have attracted a great deal of attention from government, academia and enterprises. Chiral amine is an important structural motif of chiral drugs. Therefore, development of methods for the construction of this motif is of great importance. Catalytic enantioselective reduction of imines represents one of the most straightforward and efficient methods for the preparation of chiral amines. The chiral Lewis base organocatalysts promoted asymmetric reduction of imines by HSiCl3 has recently achieved significant advancements. Although big breakthroughs have been made in terms of substrate generality and enantioselectivity, the highly effective catalysts are limited to N-formyl amino acid amides, of which the efficiency and substrate scope remain unsatisfactory. Therefore, development of novel organocatalysts for this transformation is in great demand. Chiral sulfoxides have been well established as efficient and versatile stereocontrollers and have been extensively used in asymmetric synthesis and total synthesis of natural products. The S=O structural motif of sulfoxide could also behave as Lewis base activator for cholorsilane reagents, which, moreover, could be even better than caboxamide considering that the sulfur atom is chiral and thus the chirality center is closer to the reaction center. There exist great potentials that highly effective novel Lewis base organocatalysts could be developed starting from S-chiral sulfoxides. Recently, several S-chiral sulfoxides were reported by Kobayashi and Khiar to be used as Lewis base catalyst to activate allyltrichlorosilanes in asymmetric allylations and good enantioselectivities were obtained. However, these S-chiral sulfoxides were all used at a more than stoichiometric amount and were thus not authentically catalytic. A careful literature survey further revealed that there has been so far no S-chiral organocatalyst available. In this study, we, for the first time, successfully used S-chiral sulfinamides as Lewis base organocatalysts for the asymmetric reduction of ketimines by HSiCl3. After several rounds of structural optimization, we developed the first example of highly effective S-chiral organocatalysts, which promoted the asymmetric reduction of ketimines with trichlorosilane in high yield and excellent enantioselectivity with unprecedented substrate spectrum. In our initial practice, we examined 20mol% of the commercially available (R)-tert-butanesulfinamide and (S)-toluenesulfinamide as the catalyst in the hydrosilylation of ketimine. Although the product was only furnished in moderate yield and low ee, these results demonstrated that our strategy of catalyst design is on the right way. Next, starting from chiral tert-butanesulfinamide, we prepared a series of tert-butanesulfinamide derivatives via simple reductive amination and examined their catalytic efficiencies in the reduction of ketimine. We found that the catalyst bearing a phenolic hydroxyl group exhibited good reactivity and enantioselectivity. On the basis of which, we obtained a structurally simple and highly effective novel organocatalyst, affording the product in 98% yield and 93% ee under optimal reaction conditions. After careful exploration on the role of phenolic hydroxyl group in the catalyst, we speculated that two molecules of the catalyst be involved in the course of reaction, of which the assembly around the silicon center is facilitated by the intermolecular hydrogen bonding through the phenolic hydroxyl groups. Thus, we incorporated two units of sulfonamide into one molecular and prepared a new type of bissulfinamides organocatalysts and examined their catalytic efficiencies in the reduction of ketimine. After optimizing the structure of these catalysts, we finally obtained a novel organocatalyst which has even simpler molecular structure but showed better efficacies, 10mol% of which afforded up to 97% yield and 96% ee under optimal reaction conditions. These results further proved our speculation about the catalytic mechanism. We also examined the newly developed S-chiral organocatalysts in direct asymmetric reductive amination of secondary amines with aromatic ketone. The product was furnished in good yield but in low ee. No better results could be obtained despite our intense opimization efforts. Nevertheless, these experiments laid excellent foundations for eventual success.

中国青藏高原青稞抗穗发芽资源评价与α-淀粉酶基因的克隆及表达

穗发芽（PHS，preharvest sprouting）是影响禾本科作物生产的重要的灾害之一。收获时期如遇潮湿天气容易导致穗发芽发生。发生穗发芽的种子内部水解酶（主要是α-淀粉酶）活性急剧升高，胚乳贮藏物质开始降解，造成作物产量和品质严重降低。因此，选育低穗发芽风险的品种是当前作物育种工作中面临的重要任务。 青稞(Hordeum vulgare ssp. vulgare)主要分布于青藏高原，自古以来就是青藏高原人民的主要粮食。近年来，由于青稞丰富的营养成分和特有的保健品质、在燃料工业中的潜力以及在啤酒酿造工业中的利用前景，在发达国家日趋受到重视，掀起综合研究利用的热潮。我国拥有占全世界2/3 以上的青稞资源，具有发展青稞产业的得天独厚的条件。然而，由于青稞收获期间恰逢青藏高原雨季来临，常有穗发芽灾害发生，使青稞生产损失巨大。目前对青稞穗发芽研究很少，适用于育种的穗发芽抗性材料相对缺乏，不能很好的满足青稞穗发芽抗性育种的需要。本研究以青藏高原青稞为材料，对其穗发芽抗性的评价指标和体系进行构建，同时筛选青稞抗穗发芽品种并对其抗性进行评价，还利用分子生物学手段对青稞穗发芽抗性的分子机理进行了初步探讨。主要研究结果如下： 1. 本试验以来自于我国青藏高原地区的青稞为材料，对休眠性测定的温度范围进行探讨，并对各种穗发芽抗性测定方法的对青稞的适用性进行评测。通过探讨温度对13 个不同基因型的青稞籽粒发芽和休眠性表达的影响，对筛选青稞抗穗发芽资源的温度条件进行探索，并初步分析了其休眠性表达的机理。在10，15，20，25，30℃的黑暗条件下，选用新收获的13 个青稞品种为材料进行籽粒发芽实验，以发芽指数（GI）评价其休眠性。结果发现，不同品种对温度敏感性不同，其中温度不敏感品种，在各温度条件下均表现很低的休眠性；而温度敏感品种，其休眠性表达受低温抑制，受高温诱导。15℃至25℃是进行青稞休眠性鉴定的较适宜的温度范围。通过对供试材料发芽后的α-淀粉酶活性，发现温度对青稞种子的休眠性表达的影响至少在一定程度上表现在对α-淀粉酶活性的调控上。随后，对分别在马尔康和成都进行种植的34 份青稞穗发芽指数（SI），穗发芽率（SR），籽粒发芽指数（GI）和α-淀粉酶活性（AA）进行了测定和分析，发现它们均受基因型×栽培地点的极显著影响，且四个参数之间具有一定相关性。GI 参数由于其变异系数较低，在不同栽培地点稳定性好，且操作简便，是较可靠和理想的穗发芽评价参数。SI 参数可作为辅助，区别籽粒休眠性相似的材料（基因型）或全面评价材料（基因型）的穗发芽抗性特征。AA 参数稳定性较差，并且检测方法复杂，因此不建议在育种及大量材料筛选和评价时使用。此外，青稞穗发芽抗性受环境影响较大，评价时应考虑到尽可能多的抗性影响因素及其在不同栽培条件下的变异。 2. 对来自青藏高原的青稞穗发芽抗性特征及其与其它农艺性状间的关系进行研究。通过测定穗发芽指数（SI）、籽粒发芽指数（GI）和α-淀粉酶活性（AA），表明113 份青稞材料的穗发芽抗性具有显著差异。SI、GI 和AA 参数的变幅分别为1.00~8.86、0.01~0.97 和0.00~2.76，其均值分别为4.72、0.63 和1.22。根据SI 参数，六个基因型，包括‘XQ9-5’，‘XQ33-9’，‘XQ37-5’，‘XQ42-9’，‘XQ45-7’和‘JCL’被鉴定为抗性品种。综合SI、GI 和AA 参数，可以发现青稞的穗发芽抗性机制包含颖壳等穗部结构的抗性和种子自身的抗性（即种子休眠性），且供试材料中未发现较强的胚休眠品种，除‘XQ45-7’外，所有品种在发芽第四天均能检测出α-淀粉酶活性。穗部结构和种子休眠的抗性机制因基因型不同而不同，在穗发芽抗性中可单独作用或共同作用。农家品种和西藏群体分别比栽培品种和四川群体的穗发芽抗性强，而在不同籽粒颜色的青稞中未发现明显差异。相关性检验发现，青稞的穗发芽抗性，主要是种子休眠性，与百粒重、开花期、成熟期、穗长、芒长和剑叶长呈显著负相关关系，与株高相关性不显著。农艺性状可以作为穗发芽抗性材料选育中的辅助指标。本试验为青稞穗发芽抗性育种研究提供了必要的理论基础和可供使用的亲本材料。 3. α-淀粉酶是由多基因家族编码的蛋白质，在植物种子萌发时高度表达，与植物种子的萌发能力密切相关。在大麦种子发芽时，高等电点α-淀粉酶的活性远大于低等电点的α-淀粉酶。为了研究不同穗发芽抗性青稞品种中编码高等电点α-淀粉酶Amy1 基因结构与抗性间的关系，我们以筛选得到的抗性品种‘XQ32-5’（TR1）、‘XQ37-5’（TR2）、‘XQ45-7’（TR3），易感品种‘97-15’（TS1）、‘9657’（TS2）以及强休眠大麦品种‘SAMSON’（SAM）为材料，对其Amy1 基因的编码区序列进行克隆和结构分析，并对它们推导的氨基酸序列进行比较。结果显示，青稞Amy1 基因具有三个外显子、两个内含子，编码区中有13 个核苷酸变异位点，均位于2、3 号外显子，2 个变异位点位于2 号外显子。SAM 和TS1 分别在2 号外显子相应位置有5 个相同的碱基(GAACT)的插入片段。相应α-淀粉酶氨基酸序列推导发现，所有核苷酸变异中有8 个导致相应氨基酸残基的改变，其余位点为同义突变。青稞Amy1 基因编码区序列品种间相似度高达99%以上，部分序列变异可能与其穗发芽抗性有关。随后，我们又通过SYBR Green 荧光定量技术对该基因在不同发芽时间（1d~7d）的相对表达水平进行了差异性检测。结果发现，7 天内不能检测到SAM 的Amy1 基因表达，5 个青稞品种间的Amy1 基因的相对表达量均随着发芽时间延长而上升，但上升方式有所不同。弱抗品种该基因表达更早，转录本增加速率更大，且在4~5 天可达到平台期。发芽7 天中，抗性品种总转录水平明显低于易感品种。本研究结果表明，青稞Amy1 基因的转录水平是与其穗发芽抗性高度相关。 我国青藏高原青稞，尤其是农家品种的穗发芽抗性具有丰富的变异，蕴藏着穗发芽抗性育种的宝贵资源。本研究为青稞穗发芽抗性育种建立了合理抗性评价体系，筛选出可供育种使用的特殊材料，阐明了农艺性状可辅助穗发芽抗性育种，同时还对穗发芽抗性与α-淀粉酶基因的结构和表达关系进行分析，为青稞穗发芽抗性资源筛选奠定了基础。 Preharvest sprouting (PHS) is a serious problem in crop production. It often takes place when encountering damp, cold conditions at harvest time and results in the decrease of grain quality and great loss of yield by triggering the synthesis of endosperm degrading enzymes (mostly the α-amylase). Therefore, PHS is regarded as an important criterion for crop breeding. In order to minimize the risk of PHS, resistant genotypes are highly required. Hulless barley (Hordeum vulgare ssp. vulgare) is the staple food crop in Qinghai-Tibetan Plateau from of old, where is one of the origin and genetic diversity centers of hulless barley. Recently, interest in hulless barley has been sparked throughout the world due to the demonstrations of its great potential in health food industry and fuel alcohol production. Indeed, hulless barley can also be utilized to produce good quality malt if the appropriate malting conditions are used. In China, overcast and rainy conditions often occur at maturity of hulless barley and cause an adverse on its production and application. PHS resistant genotypes, therefore, are highly required for the hulless barley breeding programs. However, few investigations have been made so far on this issue. The objectives of this study were: 1) to assessment of methods used in testing preharvest sprouting resistance in hulless barley; 2) to evaluate the variability and characteristics of PHS resistance of hulless barley from Qinghai-Tibet Plateau in China; 3) to select potential parents for PHS resistance breeding; 4) to primarily study on the molecular mechanism of PHS resistance of hulless barley. Our results are as followed: 1. We investigated the temperature effects on seed germination and seed dormancy expression of hulless barley, discussed appropriate temperature range for screening of PHS resistant varieties, and analyzed the mechanism of seed dormancy expression of hulless barley. The dormancy level of 13 hulless barley were evaluated by GI (germination index) values calculating by seed germination tests at temperature of 10，15，20，25，30℃ in darkness. There were great differences in temperature sensitivity among these accessions. The insensitive accessions showed low dormancy at any temperature while the dormancy expression of sensitive accessions could be restrained by low temperature and induced by high temperature. The temperature range of 15℃ to 25℃ was workable for estimating of dormancy level of hulless barley according to our data. Analysis of α-amylase activity showed that the temperature effects on seed germination and the expression of seed dormancy be achieved probable via regulating of α-amylase activity. Furthermore, we evaluated the differences in sprouting index (SI), sprouting rate (SR), germination index (GI) and α-amylase activity (AA) between Maerkang and Chengdu among 34 accessions of hulless barley from Qinghai-Tibetan Plateau in China. These PHS sprouting parameters were significantly affected by accession×location, and they had correlation between each other. GI was the most reliable parameter because of its low CV value, good repeatability and simple operation. SI could assist in differentiating between accessions of similar dormancy or overall evaluation of the resistance. AA was bad in repeatability and had relatively complex testing method, therefore, not appropriate for breeding and evaluation and screening of PHS resistant materials. Besides, since PHS resistance of hulless barley was greatly influenced by its growth environment, possibly much influencing factors and variations between cultivated conditions should be considered. 2. In this study, large variation was found among 113 genotypes of hulless barley (Hordeum vulgare ssp.vulgare) from Qinghai-Tibetan Plateau in China, based on the sprouting index (SI), germination index (GI) and α-amylase activity (AA) which derived from sprouting test of intact spikes, germination test of threshed seeds and determination of α-amylase activity, respectively. The range of SI, GI and AA was 1.00~8.86, 0.01~0.97 and 0.00~2.76，the mean was 4.72, 0.63 and 1.22 espectively. Six resistant genotypes, including ‘XQ9-5’, ‘XQ33-9’, ‘XQ37-5’, ‘XQ42-9’, ‘XQ45-7’ and ‘JCL’, were identified based on SI. Integrating the three parameters, it was clear that both hulls and seeds involved in PHS resistance in intact spikes of hulless barley and there was no long-existent embryo dormancy found among the test genotypes. All the genotypes, except ‘XQ45-7’, had detectable α-amylase activity on the 4th day after germination. There was PHS resistance imposed by the hull and seed per se and the two factors can act together or independent of each other. Besides, landraces or Tibet hulless barley had a wider variation and relatively more PHS resistance when compared with cultivars or Sichuan hulless barley. No significant difference was found among hulless barley of different seed colors. The correlation analysis showed PHS resistance was negatively related to hundred grain weight, days to flowering, days to maturity, spike length, awn length and flag length but not related to plant height. This study provides essential information and several donor parents for breeding of resistance to PHS. 3. Alpha-amylase isozymes are encoded by a family of multigenes. They highly express in germinating seeds and is closely related to seed germination ability. In barley germinating seeds, the activity of high pI α-amylase is much higher than low pI α-amylase. The aim of this study was to determine the relationship between preharvest sprouting resistance of hulless barley and the gene structure of Amy1 gene which encodes high pI α-amylase. The coding region and cDNA of Amy1 gene of three resistant accessions, including ‘XQ32-5’ (TR1), ‘XQ37-5’ (TR2), ‘XQ45-7’ (TR3), two susceptible accessions ‘97-15’ (TS1), ‘9657’ (TS2) and one highly dormant barley accession ‘SAMSON’ (SAM) was cloned. Analysis of their DNA sequences revealed there were three exons and two introns in Amy1 gene. Thirteen variable sites were in exon2 and exon3, 2 variable sites were in intron2. SAM and TS1 had a GAACT insert segment in the same site in intron2. Only 8 variable sites caused the change of amino acid residues. There were 99% of similarity between the tested hulless barley and some of the variable sites might be related with preharvest sprouting resistance. Then, we investigated the expression level of Amy1 gene in the 7-day germination test. Results of quantitative real-time PCR indicated that the relative expression trends of Amy1 gene were the same but had significant differences in the increase fashion between hulless barleys and no detectable expression was found in SAM. Susceptible accessions had earlier expression and faster increase and reached the maximum on day 4 ~ day 5. Besides, total transcripts level was found lower in resistant accessions than susceptible accessions. This study indicated that α-amylase activity was highly related to the transcription level of Amy1 gene which not correlated to missense mutation sites. In conclusion, hulless barley, especially the landraces from Qinghai-Tibetan Plateau in China possesses high degree of variation in PHS performance, which indicates the potential of Tibetan hulless barley as a good source for breeding of resistance to PHS. This study provides several donor parents for breeding of resistance to PHS. Our results also demonstrate that agronomic traits may be used as assistants for PHS resistance selection in hulless barley. Besides, analysis of high pI α-amylase coding gene Amy1 revealed the relative high expression of was Amy1 one of the mainly reason of different PHS resistance level in hulless barley.

多通道电荷时间测量方法与电路研究

随着国家大科学工程兰州重离子加速器冷却储存环(HIRFL-CSR)建成，HIRFL-CSR实验探测系统也正在建设当中。实验探测系统由外靶系统和内靶系统构成。用于探测中子的中子墙探测器是外靶系统中的一个重要组成部分，它有252个探测单元，每一个探测器单元都要求很好的能量分辨和时间分辨，还要求有很高数据获取率。为此，我们设计研发适合于中子墙探测器这样的大型闪烁体探测器的前端电子学读出系统。论文从发展髙性能多路小型化前端电路和研究QAC、TAC的方法和电路两个方面进行研究，讨论了我们采用的新思路和新方法。 我们设计的新型的多道高精度的电荷-电压、时间转换电路.该电路主要用于在相关控制信号的配合下，将光电倍增管输出的快电流脉冲信号转化为电压信号,并在控制信号作用下,将电压信号通过数据采集系统直接送入计算机进行处理。电路采用新型的QAC方法，用于处理快速的电流信号,突出特点是转换速度快,电路结构简单,输入信号范围大,精度高,功耗低, 电路采用改进的TAC方法，用于处理快速的时间信号,利用高速DMOS开关，并优化控制逻辑时序，极大提高了测试精度。 实验室调试结果说明系统已能够适应物理实验的要求，并为最终建立一个完整的满足性能要求的前端电子学系统打下了坚实的基础

Application to polymer characterization by thermal analysis

The measured results of thermal analysis depend on experimental conditions. The international and national organizations have constituted a series of methods to characterize the physical and chemical properties for substances. The applications to physical transition, chemical reaction, and characteristic parameters of substances are given in the article as examples.

制造执行系统的边界划分方法研究

介绍了制造执行系统(MES)的含义和实现的核心功能,提出了目前信息化建设过程中存在的边界问题,针对出现的问题,给出了MES与其它系统的边界划分方法:功能边界与技术边界两种方法。并根据研究结果分析了MES与ERP、MES与PCS系统的边界划分。

微操作与微装配中微力感知方法的综述

本文介绍了微力感知的各种方法,分析了每种感知方法的基本原理、检测精度及适用范围,并对微装配与微操作中微力传感器的应用作了简要的回顾。在微操作与微装配中,实现可靠的微力感知是目前研究的重要目标之一。本文通过对各种微力感知方法的基本原理进行研究,总结出六大类方法的特点、检测精度以及适宜的使用场合。目的是为从事微力感知研究的学者提供参考,进而促进微装配和微操作的自动化加工技术水平,实现微型装备的可靠、高产量的批量制造。

基于广义正交多项式迭积微分算子的地震波场数值模拟研究

Seismic Numerical Modeling is one of bases of the Exploratory Seismology and Academic Seismology, also is a research field in great demand. Essence of seismic numerical modeling is to assume that structure and parameters of the underground media model are known, simulate the wave-field and calculate the numerical seismic record that should be observed. Seismic numerical modeling is not only a means to know the seismic wave-field in complex inhomogeneous media, but also a test to the application effect by all kinds of methods. There are many seismic numerical modeling methods, each method has its own merits and drawbacks. During the forward modeling, the computation precision and the efficiency are two pivotal questions to evaluate the validity and superiority of the method. The target of my dissertation is to find a new method to possibly improve the computation precision and efficiency, and apply the new forward method to modeling the wave-field in the complex inhomogeneous media. Convolutional Forsyte polynomial differentiator (CFPD) approach developed in this dissertation is robust and efficient, it shares some of the advantages of the high precision of generalized orthogonal polynomial and the high speed of the short operator finite-difference. By adjusting the operator length and optimizing the operator coefficient, the method can involve whole and local information of the wave-field. One of main tasks of the dissertation is to develop a creative, generalized and high precision method. The author introduce convolutional Forsyte polynomial differentiator to calculate the spatial derivative of seismic wave equation, and apply the time staggered grid finite-difference which can better meet the high precision of the convolutional differentiator to substitute the conventional finite-difference to calculate the time derivative of seismic wave equation, then creating a new forward method to modeling the wave-field in complex inhomogeneous media. Comparing with Fourier pseudo-spectral method, Chebyshev pseudo-spectral method, staggered- grid finite difference method and finite element method, convolutional Forsyte polynomial differentiator (CFPD) method has many advantages: 1. Comparing with Fourier pseudo-spectral method. Fourier pseudo-spectral method (FPS) is a local operator, its results have Gibbs effects when the media parameters change, then arose great errors. Therefore, Fourier pseudo-spectral method can not deal with special complex and random heterogeneous media. But convolutional Forsyte polynomial differentiator method can cover global and local information. So for complex inhomogeneous media, CFPD is more efficient. 2. Comparing with staggered-grid high-order finite-difference method, CFPD takes less dots than FD at single wave length, and the number does not increase with the widening of the studying area. 3. Comparing with Chebyshev pseudo-spectral method (CPS). The calculation region of Chebyshev pseudo-spectral method is fixed in , under the condition of unchangeable precision, the augmentation of calculation is unacceptable. Thus Chebyshev pseudo-spectral method is inapplicable to large area. CFPD method is more applicable to large area. 4. Comparing with finite element method (FE), CFPD can use lager grids. The other task of this dissertation is to study 2.5 dimension (2.5D) seismic wave-field. The author reviews the development and present situation of 2.5D problem, expatiates the essentiality of studying the 2.5D problem, apply CFPD method to simulate the seismic wave-field in 2.5D inhomogeneous media. The results indicate that 2.5D numerical modeling is efficient to simulate one of the sections of 3D media, 2.5D calculation is much less time-consuming than 3D calculation, and the wave dispersion of 2.5D modeling is obviously less than that of 3D modeling. Question on applying time staggered-grid convolutional differentiator based on CFPD to modeling 2.5D complex inhomogeneous media was not studied by any geophysicists before, it is a fire-new creation absolutely. The theory and practices prove that the new method can efficiently model the seismic wave-field in complex media. Proposing and developing this new method can provide more choices to study the seismic wave-field modeling, seismic wave migration, seismic inversion, and seismic wave imaging.

残留盆地分布综合地球物理研究——以大港地区为例

Macro-distribution of residual basins is a basic question in residual basin research，the main object of macro-distribution study is to build strata framework, compute thickness of residual strata and analyze characteristics of residual basins. With the guidance of the theory of integrated geology and geophysical research, the paper assembled series of methods and established the technical chart based on gravity and magnetic data, with restriction of geology, seismic and drilling data. Based on potential field data processing and analysis, forward and inverse computation, region potential field analysis and potential field separation, etc. it computed depth of gravity/magnetic basement and got strata framework. It had got effective results in the research of macro-distribution of residual basin research in the Dagang area. It did the wavelet transform of gravity/magnetic data with multi-kind of wavelet basis using a trou algorithm. From comparison of processing result and their spectral of wavelet analysis, up continuation and filter method, the wavelet approximation is better to fit the regional potential field, and it is an effective method to separate gravity/magnetic effect caused by deep geology bodies. The experiment of matching pursuit shows that te transform domain methods have great advantage in potential data analysis. From the integrated geophysical study of rock property study, gravity/magnetic basement inversion and fault system analysis of the Dagang area, it gets the strata framework and the thickness of pre-Cenozoic residual strata. Comprehensive study with gravity and magnetotelluric profile inversion and interpretation, three prospect plays of macro-distribution of residual basins are fingered out. It has great residual strata thickness in the northern part of Chengning Uplift and there is thrust fault in the deep zone and good up-Paleozoic hydrocarbon source rocks in this area. With integrated analysis, this area will be the most prospective hydrocarbon location of pre-Cenozoic residual basins.

滩海过渡带地震资料拼接处理方法研究

The technology of seismic acquirement has been more and more intact in both land area and marine area, however, since the acquirement equipment can not handle the tasks in this both two kinds of prospects at the same time, it is very hard to acquire in the prospect of seashore area, and also the quality of the raw data is poor, the related work in seashore area has been a tough task. With the development of the level of exploration, acquired equipment and technology, a certain series of processing methods has been built up, which enhanced the resolving power, the ratio of signal to noise and the quality of imaging, these methods could meet most of the requirements of exploration and the development. What is more, more and more nowadays prospects are composed by two or more 3D sub-prospect, the differences between frequencies, energy levels and the ratios of signal to noise are definitely obvious, we can not perform finely construct analysis and interpretation of reservoir without solving these problems in matching different raw data. As for the prospect that composed by both seashore and marine ones, through the analysis on the characteristics on frequency, amplitude, polarity and multiples of land prospect and marine prospect, the methods on how to eliminate those differences mentioned above were researched, and this paper gives a series of methods includes the computing of matching factor, recognizing of time difference, recognizing of phase difference, matching frequency, collapsing of abnormal energy, frequency compensating and so on, to fulfill the attenuations of energy difference, frequency difference, time difference and phase difference, and what is more, improve the innovative methods: includes the quantities method to synthetically and automatically recognize time difference and phase difference on the basis of signal match technology and according to statistic rule. And distinct the differences on phase and frequency characteristics of received raw data between velocity seismometer and piezoelectricity seismometer, and deduces that there are 90 degrees gap between data from these two seismometers, thirdly, synthetically apply zone abnormal frequency processing, surface consistent abnormal frequency compensate, residual abnormal frequency compensate, stack time equilibrium and optimize the processing seis-flow, deal with the would-be problems, such as low signal and noise rate, low resolution, poor imaging and poor state of consistent. Gain excellent effect in Da-gang oil field.

储层注聚合物后测井评价研究

Since physical properties and resistivity of mixed formation fluid change after polymer and water flood reservoir, transformational electric properties of water and polymer flooded zones challenges log interpretation. Conventional log interpretation methods to water flooded reservoirs cannot be employed to water and polymer flooded zones. According to difficulties in water and polymer flooded zones interpretation, we analyzed the variation of electric properties of mixed formation fluid, reservoir parameters and log correspondences, then got further understanding of the applicability of Archie Equations. As the results, we provided reservoir parameter evaluation model in water and polymer flooded zones in this paper. This research shows that micro pore structure, physical parameters and electric correspondence of reservoirs change after being flooded by water and polymer. The resistivity variation of mixed formation fluid depends mainly on affixation conductivity of polymer and salinity of formation water, which is the key to log interpretation and evaluation. Therefore, we summerized the laws of log correspondence in different polymer injection ways, developed electric discrimination model for water and polymer flooded zones, as well as charts to identify flooding conditions with resistivity and sonic logs. Further rock-electric tests and conductive mechanism analysis indicate that the resistivity increasing coefficient(I) and water saturation(Sw) are still in concordance with classical Archie Equations, which can be utilized in quantitative evaluation on water and polymer flooded reservoirs. This sets of methods greatly improved accuracy in water and polymer flooded zone evaluation.

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.

基于精细结构描述及数值试验的断续节理岩体力学参数智能选取

Evaluating the mechanical properties of rock masses is the base of rock engineering design and construction. It has great influence on the safety and cost of rock project. The recognition is inevitable consequence of new engineering activities in rock, including high-rise building, super bridge, complex underground installations, hydraulic project and etc. During the constructions, lots of engineering accidents happened, which bring great damage to people. According to the investigation, many failures are due to choosing improper mechanical properties. ‘Can’t give the proper properties’ becomes one of big problems for theoretic analysis and numerical simulation. Selecting the properties reasonably and effectively is very significant for the planning, design and construction of rock engineering works. A multiple method based on site investigation, theoretic analysis, model test, numerical test and back analysis by artificial neural network is conducted to determine and optimize the mechanical properties for engineering design. The following outcomes are obtained: (1) Mapping of the rock mass structure Detailed geological investigation is the soul of the fine structure description. Based on statistical window，geological sketch and digital photography，a new method for rock mass fine structure in-situ mapping is developed. It has already been taken into practice and received good comments in Baihetan Hydropower Station. (2) Theoretic analysis of rock mass containing intermittent joints The shear strength mechanisms of joint and rock bridge are analyzed respectively. And the multiple modes of failure on different stress condition are summarized and supplied. Then, through introducing deformation compatibility equation in normal direction, the direct shear strength formulation and compression shear strength formulation for coplanar intermittent joints, as well as compression shear strength formulation for ladderlike intermittent joints are deducted respectively. In order to apply the deducted formulation conveniently in the real projects, a relationship between these formulations and Mohr-Coulomb hypothesis is built up. (3) Model test of rock mass containing intermittent joints Model tests are adopted to study the mechanical mechanism of joints to rock masses. The failure modes of rock mass containing intermittent joints are summarized from the model test. Six typical failure modes are found in the test, and brittle failures are the main failure mode. The evolvement processes of shear stress, shear displacement, normal stress and normal displacement are monitored by using rigid servo test machine. And the deformation and failure character during the loading process is analyzed. According to the model test, the failure modes quite depend on the joint distribution, connectivity and stress states. According to the contrastive analysis of complete stress strain curve, different failure developing stages are found in the intact rock, across jointed rock mass and intermittent jointed rock mass. There are four typical stages in the stress strain curve of intact rock, namely shear contraction stage, linear elastic stage, failure stage and residual strength stage. There are three typical stages in the across jointed rock mass, namely linear elastic stage, transition zone and sliding failure stage. Correspondingly, five typical stages are found in the intermittent jointed rock mass, namely linear elastic stage, sliding of joint, steady growth of post-crack, joint coalescence failure, and residual strength. According to strength analysis, the failure envelopes of intact rock and across jointed rock mass are the upper bound and lower bound separately. The strength of intermittent jointed rock mass can be evaluated by reducing the bandwidth of the failure envelope with geo-mechanics analysis. (4) Numerical test of rock mass Two sets of methods, i.e. the distinct element method (DEC) based on in-situ geology mapping and the realistic failure process analysis (RFPA) based on high-definition digital imaging, are developed and introduced. The operation process and analysis results are demonstrated detailedly from the research on parameters of rock mass based on numerical test in the Jinping First Stage Hydropower Station and Baihetan Hydropower Station. By comparison，the advantages and disadvantages are discussed. Then the applicable fields are figured out respectively. (5) Intelligent evaluation based on artificial neural network (ANN) The characters of both ANN and parameter evaluation of rock mass are discussed and summarized. According to the investigations, ANN has a bright application future in the field of parameter evaluation of rock mass. Intelligent evaluation of mechanical parameters in the Jinping First Stage Hydropower Station is taken as an example to demonstrate the analysis process. The problems in five aspects, i. e. sample selection, network design, initial value selection, learning rate and expected error, are discussed detailedly.

酒泉盆地酒东坳陷下白垩统储层特征及有利勘探方向研究

Jiuquan basin, located in the middle of the Hexizoulang, is one of the major important Mesozoic、cenozoic oil-gas bearing basin in the west of China. Jiuquan basin is composed of Jiuxi depression、Huahai-jinta depression and Jiudong depression. Basement of Jiudong depression is Silurian shallow metamorphic rock. Ying-er sag , focus of this study, is the biggest sag in Jiudong depression and the targeting study object is cretacic strata. Structure evolution and geological background were carefully studied in this research. A series of methods were applied to this research: values of oxygen and carbon isotope and trace elements analysis were used to recover salinity of the palae-lake water of the sag. The evolution and distribution of sedimentary faces were carefully studied. Also, various analysis and tests were made to study the diagenesis of the reservoir sandstones、porosity evolution and porosity distribution. All the studies indicate that sedimentary faces are main macroscopic factor controlling the reservoir quality; Compaction is the main factor destroying reservoir property. Carbonate cements greatly preserved the porosity in eodiagenesis because it had prevented significant early mechanical compaction and its dissolution in the late diagenesis generated secondary pores. Carbonate cements in the late diagenesis occluded primary porosity and played a negative role in the porosity preservation. Source of the carbonate cements were also preliminarily discussed. Feldspar grains and lithic fragments were dissolved by acid fluid and formed a great amount of secondary pores and developed the reservoir quality. Also, sedimentary-diagenesis zones were identified. On basis of these studies, Reservoir forming factors were studied. Keywords: Jiudong depression, sedimentary faces，reservoirs diagenesis reservoir evaluation，secondary pores