质谱在高分子热分解及油脂分析中的应用

本论文主要包括三个部分。第一部分简单介绍了四极杆质谱仪的工作原理和所用实验技术；第二部分首先综述了质谱技术在高分子链结构和热分解机理研究中的应用，然后以直接裂解质谱（DPMS）为主要手段研究了聚对苯硫醚（PPS）、聚噻吩（PT）、聚苯胺（PAn）、聚邻甲基苯胺（POT）和聚β-羟基丁酸酯（PHB）及其共聚物的热分解行为和某些结构性质。主要讨论了电子能量、裂解温度、电离方式等对高分子裂解产物的影响，表明DPMS是研究高分子热分解机理的有效方法。几种导电聚合物的热分解均以自由基方式降解，PPS裂解形成环状和线状齐聚物，PT、PAn及POT只能形成线状齐聚物；聚β-羟基烷酸酯的热分解通过β-CH转移反应形成由羟基和烯烃结尾的齐聚物，形成的齐聚物准分子离子可进一步脱去一个分子水。第三部分用GC、GC/MS分离鉴定了山核桃油中的脂肪酸，并用FABMS测定了山核油中混合甘油三酸酯的组成。FABMS能反映不同甘油三酸酯的组成和含量，而GC、GC/MS能对各种脂肪酸进行定性和定量分析，两种方法相互补充，较全面地获得了山核桃油的组成信息。

某些大分子物质的质谱研究

本论文运用多种质谱手段，对两类有代表意义的大分子物质－－金属富勒烯与西洋参多糖进行了详细的研究：改进方法高效率地合成、提取了稀土金属富勒烯；并利用解吸电子轰击、激光解吸／电离方式，获得了其分子量信息；通过质谱结果对比大致估计了稀土金属富勒烯的电离能、电子亲和势等常数，提出了双镥金属富勒烯的非笼内包裹结构；还利用气相离子／分子反应说明了笼内金属勒烯较强的给电子性质，并推断这是由其特殊的“超级原子”型的电子结构造成的。采用水提醇沉、柱层析分离的方法，得到了具有良好药理活性的西洋参多糖；利用基质辅助激光解吸／电离质谱测定了其分子量，并深入研究了糖类化合物基质辅助激光解吸／电离过程；利用三甲基硅醚化和还原乙酰化方法，对多糖完全水解产物进行了化学修饰，由GC－MS分析了多糖中单糖的组成；还利用Hakomori改良法，确定了PPQI各组分的中性多糖中单糖的连接方式，并尝试用实验式描述了其中性多糖部分的结构；最后利用电喷雾多级串联质谱方，对多糖PPQI－4部分水解产物进行了分析，获得了其序列信息，进一步验证了甲基化分析结果。

稠油废水处理中优势微生物种群组成及变化规律

针对辽河油田锦采污水处理厂稠油废水，利用传统培养方法和PCR-DGGE诊断技术，对稠油废水处理过程中优势微生物种群组成和多样性进行全面系统的研究。结果表明，微生物对稠油废水生物处理的作用为细菌>真菌>放线菌。细菌数量、基因多样性指数与废水中TPH、CODCr均正相关，可以作为稠油废水水质评价的生物指标。 对影响稠油废水生物降解的主要因子进行优化表明，当30℃，pH值7.5，HRT为216h，添加N、P营养盐使N:P比为5.63:1时，CODCr去除率最高，去除后CODCr值满足污水综合排放一级标准（GB8978-1996）。利用GC-MS技术分析降解前后稠油废水中主要有机成分表明，微生物对饱和烃类化合物降解率最高，其次是低分子量芳香烃，而高分子量芳香烃、胶质和沥青质最低。 以稠油为唯一碳源，对筛选出的菌株进行摇瓶实验表明，各菌株对稠油均具有一定的降解能力，其中F0504除油能力最强，56d去除率可达63.3%；动力学方程拟合表明稠油生物降解过程符合一级动力学方程。降解后残油组分分析表明，B0505和F0501对烷烃、B0510、F0505和F0507对芳香烃、B0501和F0504对胶质、沥青质的去除率均较高，去除率都在30c%之间。 经鉴定，优势菌株B0501和B0505分别为液化金杆菌（Aureobaterium liquefaciens）和弗氏丙酸杆菌（Propionibacterium freuclenreichii），主要真菌有青霉（Penicillium）、曲霉（Aspergillus）、木霉（Trichoderma）和交链孢霉（Alternaria）。

化感物质鉴定及其在土壤中的活性—以三裂叶豚草、水稻为例

化感物质鉴定及其活性研究是化感作用研究的核心问题。本研究以三裂叶豚草和化感水稻为例，在鉴定化感物质结构的基础上，深入探讨化感物质的生物活性，尤其是重点研究了化感物质与土壤生物因子的化学作用。 研究结果表明： (1) 三裂叶豚草能通过产生和释放挥发性化感物质到环境中抑制小麦等作物的萌发生长，而对稗草则显示出促进效应，并证实其挥发物可经土壤载体对其他植物及微生物显示化感效应。其挥发油对受试病原菌表现出不同程度的抑菌活性。顶空采样分析显示，三种单萜类物质berneol、alcanfor和 berneol acetate是三裂叶豚草周围空气中的主要化感物质。采用GC-MS结合滞留指数对三裂叶豚草挥发油进行了定性分析，在鉴定出的35个组分中，单萜类及其衍生物占总量的84.2%。 (2) 从三裂叶豚草发生地毒性土壤中分离鉴定出两种胡萝卜烷型倍半萜1α-angeloyloxycarotol和1α-(2-methylbutyroyloxy)-carotol，并检测出两种物质在毒性土壤中的浓度范围已超过其对小麦的抑制临界浓度(11.5µg/g和16.5µg/g)，进而推测两个萜类物质是三裂叶豚草干扰小麦生长的主要化感物质。 (3) 发现化感水稻组织含有尿囊素后，又从3个水稻化感品种和8个非化感品种的组织和培养基质中均检出尿囊素，证实尿囊素与水稻化感特性无相关性；水稻根分泌的尿囊素对稗草和稻田可培养微生物具有促生效应，而灭菌土壤中尿囊素半衰期(20.2 h, r2=0.95)超过非灭菌土壤(7.3 h, r2=0.92)3倍，表明土壤尿囊素中降解和转化速率较快，上述结果暗示尿囊素是参与水稻和其它生物间化学相互作用的一种促生物质。 (4) DGGE分析表明尿囊素能显著提高土壤细菌的丰富度和多样性指数；通过比较PLFA指纹图谱，一方面，尿囊素不但能显著增加PLFA总量，而且还能显著改变微生物的群落结构；主成分分析显示，在淹育和非淹育条件下，第一和第二主成分分别揭示了总方差的67.8%和55.3%。另一方面，添加黄酮甙和根分泌物均能显著改变土壤微生物的群落结构，第一和第二主成分累积方差变异之和占总变异的59.1%，并且化感品种根分泌物与黄酮甙处理的土壤样品呈正相关关系；而化感水稻根分泌物中化感物质含量与非化感水稻差异显著，暗示化感物质在影响微生物群落结构上的重要性。

多氯联苯污染土壤的钯/铁双金属还原和生物降解联合修复研究

本文以土壤为介质，以2,4,4′-三氯联苯、2,2′,5,5′-四氯联苯、2,2′4,5,5′-五氯联苯、2,2′,3,4,4′,5-六氯联苯和2,2′,3,4,4′,5,5′-七氯联苯为目标污染物，对钯/铁双金属、微生物及其联合修复多氯联苯污染土壤进行了研究。 对钯/铁双金属还原脱氯多氯联苯的影响因素和动力学进行了研究，研究结果表明：较高的钯化率、反应温度，弱酸性pH条件对脱氯反应有促进作用；在实验所考察的初始浓度范围内，脱氯效果与多氯联苯的初始浓度关系较小；而钯/铁双金属投加量则存在一个适宜值，不宜太高或太低。多氯联苯催化脱氯符合准一级反应动力学。反应速率与多氯联苯初始浓度关系很小；反应速率随钯化率、钯/铁投加量和反应温度升高而增大；初始pH为5.5时反应速率最快。且联苯环上氯取代数越少，越难以脱氯。 从受多氯联苯长期污染的土样中筛选出一株高效降解多氯联苯的细菌（H1），菌株初步鉴定为芽胞杆菌属。在本实验条件下，微生物对土壤中多氯联苯的降解较为适宜的条件为：微生物接种量10%、反应温度在30℃左右、pH在7左右。在此条件下，微生物对PCBs的降解，随初始浓度的增加，降解速率逐渐降；且随氯取代数目的增加，降解率逐渐降低。 采用化学和微生物方法联合修复多氯联苯污染土壤是可行的。经过钯/铁双金属和好氧微生物连续处理后，2,4,4′-三氯联苯和2,2′,5,5′-四氯联苯几乎被完全降解，而2,2′4,5,5′-五氯联苯、2,2′,3,4,4′,5-六氯联苯和2,2′,3,4,4′,5,5′-七氯联苯还原脱氯后生成的低氯代同系物（2,2′,5-三氯联苯）也很容易被微生物所降解。 利用GC-MS对多氯联苯的中间产物及最终产物的分析，推测多氯联苯降解的反应机理为：在钯/铁双金属——水体系中，铁作为还原剂给出电子，水为质子供体。在催化剂钯作用下，H+与铁给出的电子在双金属表面结合，形成具有高反应活性的中间产物——新生态H*。H *攻击多氯联苯取代联苯环上的氯形成脱氯产物和氯离子。反应体系中的溶解氧与溶解铁结合在钯/铁表面形成氧化层，阻碍反应进行。过多的H2气泡也会覆盖活性反应位，对脱氯反应不利。

土壤氨基酸和氨基糖聚合物的矿化过程研究

土壤中氨基酸和氨基糖是土壤有机氮的重要组成部分，对土壤氮素供给和土壤碳、氮循环过程有重要贡献。研究氨基酸和氨基糖聚合物的矿化，对于减少氮素损失，提高氮肥利用率能够提供一定的理论依据。 当向土壤中(本试验为黑土)同时添加葡萄糖和(15NH4)2SO4时，在土壤微生物的作用下，(15NH4)2SO4会被用以合成土壤15N-氨基酸和氨基糖聚合物。新合成的这部分氨基酸和氨基糖聚合物与土壤中原有氨基酸和氨基糖聚合物的性质是否不同并且是否受到外源底物的调控。为了解决上述问题，本试验将采用Stanford and Smith的间歇好气矿化淋洗培养法，结合高效液相色谱/质谱、气相色谱/质谱联机技术(HPLC/MS，GC/MS)跟踪测定土壤中15N-氨基酸和氨基糖的同位素富集比例及其含量的变化，探讨土壤中新合成15N-氨基聚合物的矿化特征，通过研究添加葡萄糖、玉米秸秆和无机氮肥对土壤中新合成15N-氨基聚合物矿化过程的影响以及对有机氮聚合物解聚的动力－酶活性的影响，从而阐明土壤氨基聚合物矿化的碳源营养调控机制和氮源反馈调节机制及其解聚机理。研究结果表明： 1. 土壤中新合成的氨基酸和氨基糖聚合物与土壤原有氨基酸和氨基糖聚合物相比具有较高的循环速率，并且不同种氨基酸和氨基糖也分别表现出不同的矿化特征。较高循环速率的存在，将为调控其矿化过程奠定基础，因为只有快速循环的氮素才能够被调控，而且调控新合成有机氮的矿化过程，可以不断地满足作物生长对氮素养分的需求。 2. 土壤中新合成氨基聚合物的矿化受到不同外源底物调控。其中碳源(葡萄糖和玉米秸秆)能够抑制氨基聚合物矿化，但是活性碳源葡萄糖的抑制程度高于活性较低的碳源玉米秸秆，表明氨基聚合物矿化受到不同碳源活性调控。不同浓度以及不同形式氮源也能够调控土壤氨基聚合物的矿化，并且适量氮肥的加入能够抑制土壤中新合成氨基聚合物的矿化，存在氮肥的反馈抑制机制。 3. 土壤中蛋白酶、芳基酰胺酶和几丁质酶活性受到不同碳源和氮源的影响。其中碳源表现为促进作用，而氮源则表现为抑制作用。氮源对土壤酶活性的反馈抑制作用是控制土壤氮素转化的关键，而碳源只是起到维持土壤酶活性的作用。三种酶活性对外源底物的敏感性，将对于调控土壤氮素循环奠定一定的理论依据。 4. 不同处理酶活性与有机氮矿化之间表现出不同的相关性，说明酶与氮矿化之间的关系受到多方面因素影响。总体来看，蛋白酶、芳基酰胺酶和几丁质酶在水解土壤氨基酸和氨基糖聚合物的过程中起到重要作用，是有机氮聚合物重要的解聚酶。

石油污染土壤堆腐清洁技术研究

本项研究利用自行设计的国内首创的生物堆腐池对污染土壤中的石油降解条件进行研究，并优化其运行工艺参数。本研究采用三株真菌进行堆腐败石油污染土壤的实验。堆腐池为：长 * 宽 * 高 = 118.5 * 65.5 * 12.5 = 0.097M~3，通气、养分、水分等调控在好氧条件下进行。本实验设计了5个处理组，进行了室内小试实验和室外中试实验，探讨了污染土壤中石油的净化效果，为此技术推广应用奠定了基础。研究结果如下：1 室内模拟实验表明，P菌能有效地降解污染土壤的石油。在50天的时间，达到66.1%的降解率，比次位的土著F菌61.8%，高出近5个的百分点。说明，其可以高效降解污染土壤的石油，可以用于石油污染土壤的生物修复处理。2 通气的调控是本实验中微生物生长好坏的一个非常重要的指标。利用生物泥浆反应器进行室内堆腐实验的模拟。设计了6个处理的比较实验，反应容积为4710cm~3，在50天的实验过程中得出，通气为每立方米土，22.37m~3/min(通气10分），是最佳通气条件。3 在微生物降解污染土壤中，设计正交实验，确立了土壤生物修复的调控因子，表明，温度对实验过程的影响最大，养分次之，pH和温度作为调控因子，对实验过程的影响较小。最后确立条件：温度25 ℃,湿度20%（W/W），pH6-8，C:N:P为100:10:1。4 处理的污染土样组分，进行了GC/MS的谱图分析。表明，污染土壤中含有14，15，16，17，18烷，菲，萘等，还有烯烃和环烷烃，而且本底很高，说明本污染土壤是一个复杂的混合物。5 通过设计不同浓度，不同温度，进行了土壤中组分的挥发性实验。得出，在浓度一定时，温度高的挥发率大于温度低的；在温度一定时，低浓度挥发率高于高浓度的。而原始污染土壤中的挥发率则很低，可以忽略。6 通过室外堆腐实验中的呼吸强度，耗氧变化，油降解能力之间的实验观察，发现三者之间成正相关，调控前二者之间的变化，就可以促进油的降解，为该工艺的应用提供了技术参数。7 在二年度室外实验过程中，得出，白腐真菌P菌为一株良好的石油降解菌，在200天时间内，初始浓度为5.8%的石油污染土壤，石油降解率能达到79.1%，在其后，降解曲线上升平缓，其原因还需今后进一步研究。8 通过对温主观气体CH_4和N_2O二种温室气体的实验观测，研究了污染土壤在生物修复过程中的温室气体的排队放通量。结果表明，N_2O, CH_4通量较小，本实验堆腐过程中不是温室气体的一个源。

石油污染物微生物降解与石油废水生物处理工艺研究

根据石油废水的代表性目标污染物，从石油废水和污泥中分离、筛选到一大批有价值的微生物降解菌株，对降解菌株的降解特性、降解机理进行了研究。利用合成石油废水和洛阳石化石油废水分别进行了复合SBR工艺和脉冲SBR工艺实验室小试研究。同时对不同来源的石油废水分别进行了不同工艺的批式试验。通过试验研究得到以下结论：1．分离到一株以环已烷为唯一碳和能源的降解菌株LHGl、LHCl菌株能够利用环烷烃、环烷酮、链烃、芳烃和酚类。环已酮对LHGl菌株羟化酶具有特异诱导能力。GC／MS分析表明，LHGl菌株降解环已烷和环戊酮的代谢产物与已知途径代诱导产物不同。经质粒检测，在LHGl菌株中没有发现质粒。2．复合SBR工艺与脉冲SBR工艺对石油废水污染物的去除均具有很好的效果，两工艺均可获得较高的总氮去除效率。3．GC／MS分析表明，复合SBR工艺处理石油废水后，绝大部分污染物得到完全降解，出水中仅检出微生物部分代谢产物和微量难降解污染物。4．投加优势菌种后，能够提高SBR工艺对石油废水污染物的去除效率，能够正常处理含盐量达2.0%的石油废水。5．投加碳源能够显著提高SBR工艺对低浓度石油废水的污染物去除效率，增强微生物的活性，改善微生物的絮凝性能。

西藏产雪莲花的化学成分研究

本学位论文报道了作为传统藏药材广泛使用的西藏产雪莲花化学成分的研究。论文由五章组成，第一章是三种西藏产雪莲花的化学成分的系统分离纯化和结构鉴定；第二章为西藏产雪莲花化学成分的液-质及串联质谱联用分析；第三章提出了以HPLC和TLC为检测方法的雪莲花药材质量标准草案；第四章给出了对西藏产雪莲花挥发油化学成分的气-质联用分析结果；第五章概述了雪莲花的化学成分及药理研究进展。 第一章包括三个部分。第一部分报道了绵头雪莲花(Saussurea laniceps Hand.-Mazz.)全草乙醇提取物化学成分的分离鉴定。采用正相硅胶柱层析及凝胶柱层析等分离方法，从西藏产绵头雪莲花的乙醇提取物中共分离鉴定出15个化合物。其中11个化合物为首次从该植物中分离得到，当中2个化合物系在凤毛菊属植物中首次发现。第二部分报道了水母雪莲花(Saussurea medusa Maxim.)全草乙醇提取物的化学成分。采用正、反相硅胶柱层析及凝胶柱层析等分离方法，共分离鉴定出15个化合物，其中1个为新化合物，另有4个化合物为首次从该植物中分离得到。新化合物结构通过质谱和一维及二维核磁共振等波谱解析方法及碱水解反应确定为巴豆酰基-高车前苷(M-7)。第三部分报道了三指雪莲花 (Saussurea tridactyla Sch.-Bip. ex Hook. f.)全草乙醇提取物的化学成分。采用正相硅胶柱层析及凝胶柱层析等分离方法，共分离鉴定出7个化合物，其中1个化合物为首次从该植物中分离得到。 第二章也包括三个部分。首先是采用液-质联用(HPLC-DAD-ESI-MSn)分析方法，对7个西藏不同产地的三指雪莲花化学成分进行了分析，通过与标准品的 UV和MS数据比较，共鉴定出14个峰，并对其中8个共有成分进行了定量测定。其次是关于八种西藏产雪莲花化学成分的液-质联用(HPLC-DAD-ESI-MSn)分析，通过与标准品的UV和MS数据比较，共鉴定出15个峰，并对其中8个共有成分进行了定量检测。最后通过对八种西藏产雪莲花主要化学成分的多级串联质谱(ESI-MSn)分析，快速、灵敏地鉴定出10个黄酮和3个香豆素化学成分。 第三章同样包括三个部分。首先是以绵头雪莲花中主要香豆素成分东莨菪素和伞形花内酯为对照品，通过TLC定性检测和HPLC含量测定，草拟出较严谨的药材质量标准。其次是将绵头雪莲花、三指雪莲花和雪兔子作为一个药材看待，草拟了以东莨菪素和伞形花内酯的TLC检测为指标的药材质量标准。最后是针对水母雪莲花，以主要黄酮成分芹菜素-7-O-b-D-葡萄糖苷为对照品作TLC检测，并草拟出该药材的质量标准草案。 第四章报道了西藏产雪莲花挥发油的化学成分分析。采用传统水蒸气蒸馏法分别从八种雪莲花全草中提取挥发油，利用气相色谱-质谱联用技术分别从水母雪莲花、绵头雪莲花、槲叶雪莲花、云状雪兔子、拉萨雪兔子、小果雪兔子、雪兔子和三指雪莲花中分别鉴定出83、83、56、34、21、20、24和20个化学成分，分别占其挥发油总量的70.7%、76.0%、82.2%、55.4%、49.7%、70.4 %、76.2%和 76.7%。 第五章为综述，总结和概括了雪莲花的化学和药理研究进展。 The dissertation reports the investigation of the chemical constituents of the genus Saussurea. Quite a lot of species in this genus are traditional Tibetan medicinal plants, and hence have been widely used in traditional Tibetan medicine. This dissertation consisted of five chapters. The first chapter is on the chemical constituents of three Saussurea plants. The second section is about the analysis of chemical constituents of Saussurea plants using HPLC-MS and ESI-MS/MS. In the third chapter, we proposed quality-control standards for the Genus Saussurea based on TLC (thin layer chromatography) and HPLC. The fourth chapter is about chemical compositions of the essential oil from the whole plant of Saussurea plants. The last chapter reviews the research progress of the Genus Saussurea. The first chapter consists of three parts. The first part is about chemical constituents of ethanol extracts from whole plant of Saussurea laniceps Hand.-Mazz. Fifteen compounds were isolated by column chromatography on normal phase silica gel and Sephadex LH-20. Among them, eleven compounds were isolated from this plant for the first time, and two compounds were isolated from Genus Saussurea for the first time. The second part is about chemical constituents of ethanol extracts from whole plant of Saussurea medusa Maxim. Fifteen compounds were isolated by column chromatography on normal phase, reversed phase silica gel and Sephadex LH-20. Five of them were isolated from this plant for the first time, and there is one new flavonoid glucoside which was identified as 6″-O-crotonoyl-homoplantaginin (M-7) based on the evidence of one- and two-dimensional nuclear magnetic resonance, mass spectrometry analysis, and alkaline hydrolysis reaction. The last part is about chemical constituents of ethanol extracts from whole plant of Saussurea tridactyla Sch.-Bip. ex Hook. f.. Seven compounds were isolated by column chromatography on normal phase silica gel and Sephadex LH-20. There is one compound which was isolated from this plant for the first time. The second chapter consists of three parts. In the first part, we analyzed the chemical constituents of S. tridactyla collected from seven different places in Tibet using HPLC-DAD-ESI-MSn. Fourteen peaks in the HPLC were identified by comparison of UV and MS spectra with those of authentic compounds, among which eight common peaks were quantified. In the second part, we analyzed the chemical constituents of eight Saussurea species using HPLC-DAD-ESI-MSn method. Fifteen peaks in the HPLC were identified by comparison of UV and MS spectra with those of authentic compounds and eight main peaks of them were quantified. In the last part, we analyzed the chemical compounds of the above eight Saussurea plants directly by ESI-MS/MS. Thirteen major compounds, including 10 flavonoids and 3 coumarins were easily rapidly identified. The third chapter consists of three parts. In the first part, we proposed a comparative high quality-control standard for S. laniceps, based on quality detection by TLC and quantity analysis by HPLC using two major compounds (umbelliferone and scopoletin) as standard compounds. In the second part, in viewing S. laniceps, S. tridactyla and S. gossypiphora as the members of one family of medicinal herbs, we suggested a quality-control standard based on the TLC detection of the two major compounds (umbelliferone and scopoletin). In the last part, we proposed a quality-control standard for S. medusa based on the TLC detection of its major component (apigenin 7-O-glucoside). The four chapter analyzed the chemical constituents of essential oil of eight Saussurea species. The essential oils were extracted from the whole plants of these samples with water stream distillation. By GC-MS analysis, we identified eighty-three compounds from S. medusa, eighty-three from S. laniceps, fifty-six from S. quercifolia, thirty-four from S. aster, twenty-one from S. kingii, twenty from S. simpsoniana, twenty-four from S. gossypiphora, and twenty from S. tridactyla respetively, which accounted for 70.7%, 76.0%, 82.2%, 55.4%, 49.7%, 70.4 %, 76.2% and 76.7% of the total essential oil, respectively. The last chapter reviews the research progress of the Genus Saussurea.

几种植物药材的色谱－质谱联用分析

本论文由四章组成，第一、二、三章为实验论文，分别报道了中药羌活、菊花、全缘叶绿绒蒿的化学成分的高效液相色谱(HPLC)和液相色谱-质谱(LC-MS)联用分析以及挥发油的气相色谱-质谱(GC-MS)联用分析。第四章概述了重要藏药材化学成分的研究进展。 第一章首先对28批不同产地的羌活药材进行了HPLC分析，建立了羌活的指纹图谱。结果表明，不同产地羌活的化学成分基本相似，但是各组分在含量上存在较大差异。其次，对羌活的主要化学组分包括紫花前胡苷、紫花前胡素、6'-O-反式阿魏酸紫花前胡苷、茴香酸对羟基苯乙酯、羌活醇和异欧前胡素进行了定量分析。此外，针对同一产地不同采集时间的羌活挥发油进行系统分析，结果表明它们的化学成分基本相似，主要含有a－蒎烯、b－蒎烯、柠檬烯和龙脑乙酸酯等，只是各组分含量有所变化，这说明采集药材时要注意采集时间。 第二章分别报道了不同产地不同品种菊花非挥发性成分的液相色谱－二极管阵列检测－串联质谱(LC-PDA-MSn)分析和挥发性成分的气相色谱－质谱(GC-MS)联用分析比较。首先通过液相色谱－质谱－串联质谱对各色谱峰进行定性分析，通过与标准品对照，以及UV和MSn提供的结构信息，结合文献报道共鉴定了11个化学成分，包括绿原酸和10个黄酮化合物，并比较了不同品种菊花的化学成分相同之处和不同之处。另外，对七种不同品种不同产地的菊花挥发性成分通过GC-MS分析表明其主要挥发性成分为单萜类、倍半萜类化合物，共有成分樟脑、龙脑和龙脑乙酸酯等，各成分在不同挥发油中的含量变化明显。 第三章为藏药全缘叶绿绒蒿不同部位挥发油成分的气相色谱－质谱(GC-MS)联用分析，比较其挥发油化学成分及其含量变化的异同点。研究结果表明，全缘叶绿绒蒿花精油的化学成分明显多于全草部位，且两者主要成分有较大的差别。 第四章综述了青藏高原重要藏药材化学成分的研究进展。分别对藏药的资源特色和110多种常用重要藏药材的化学成分的研究情况以及藏药未来发展思路进行了阐述，以期对相关的研究提供一些信息。 This dissertation consists of four parts. The first part reports studies on the fingerprint of Notopterygium incisum and N. forbesii by HPLC-PDA-MSn, and on the constitutents of essential oil by GC-MS. The second part elaborates the chemical constitutents of Chrysanthemum L. by LC-MS and GC-MS analysis. The third part reports the chemical compositions of the essential oil from the different parts of Meconopsis integrifolia. The fourth part reviews on the progress of the studies on the chemical constitutents in Tibetan medicines. The first chapter is about HPLC analysis of a traditional Chinese herbal medicine Qiang-huo (Notopterygium incisum and N. forbesii ). Firstly, based on analyzing and contrasting the relative retention time and relative paek area in chromatographic fingerprint, the HPLC chromatographic fingerprint of Notopterygium incisum was established, which can used as a scientific basement for the quality evalution of this herb. Secondly, quantitative analysis were performed on the main chemical constitutents of Notopterygium incisum and N. forbesii including nodakenin, nodakenetin, 6’-O-trans-feruloylnodakenin, p-hydroxypenethylanisate, notopterol and isoimperatorin. The results indicated that the contents were variable related to different growth regions. Lastly, the essential oil of Notopterygium incisum collected in different harvest times is analyzed by GC-MS. The second chapter is about HPLC-MS and GC-MS analysis of several species of Chrysanthemum L. Firstly, eleven compounds including chlorogenic acid and ten flavone compounds were identified in the methanol extract of Chrysanthemum morifolium Ramat. from different regions by HPLC-MS analysis. Secondly, the essential oil of seven different species of Chrysanthemum L.were extracted by steam distillation, and its compositions were isolated and identified by GC-MS. The main active constitutents such as camphor, borneol and bornyl acetate were detected, but the relative content varied notably. The third chapter is about GC-MS analysis of the essential oil from different parts of Meconopsis integrifolia. It indicated great difference of the chemical compositions of their oil in the flowers and residual overground part. The last chapter is a review of the research progress of the Tibetan medicines, which includes their features and their main chemical constitutents.

丁香和升麻的化学成分研究

本论文由三部分共四章组成。第一部分介绍丁香化学成分的研究成果，第二部分为升麻的化学成分研究，第三部分综述了环菠萝蜜烷三萜结构和活性关系的研究现状。 第一部分包括第一和第二章。第一章介绍了丁香（Eugenia caryophyllataThunb.）花蕾的化学成分和结构鉴定。采用正、反相硅胶柱层析等各种分离方法，从其乙醇提取物的乙酸乙酯萃取物和正丁醇萃取物中共分离出34 个化合物，它们的结构类型分属黄酮、三萜、鞣质等。其中1 个为新的酚苷类化合物，其结构经波谱分析鉴定为2-O-(6'-O-没食子酰基)-b-D-葡萄糖基苯甲酸甲酯（24），另外还有12 个化合物为首次从该植物中分离得到。第二章介绍了丁香挥发油的气相色谱- 质谱联用（ GC-MS ）和正丁醇萃取物的高效液相色谱- 质谱联用（HPLC-MS/MS）分析，尝试简单快速地检测丁香挥发油及极性部分的主要化学成分的方法。 第二部分为第三章。本章介绍了传统中药升麻（Cimicifuga foetida L.）根部乙醇提取物化学成分的分离纯化和结构鉴定。通过正、反相硅胶柱层析等分离纯化方法和MS、NMR 等波谱解析技术，共分离鉴定了20 个化合物，主要为环菠萝蜜烷三萜，其中5 个新三萜化合物分别鉴定为cimicidol-3-one（38）、3'-O-乙酰基升麻苷H-1（41）、2'-O-乙酰基升麻苷H-1（42）、(3b,12b,16b)-12-乙酰氧-16,23-环氧-9,19-环羊毛甾烷-22-烯-24-酮3-O-b-D-吡喃木糖苷（44）和升麻碱（54）。新化合物54 为结构新颖的环菠萝蜜烷三萜皂苷生物碱，这是首个发现的具有环菠萝蜜烷三萜骨架的生物碱，也是从升麻属植物中发现的第一个三萜生物碱，它的结构通过多种波谱解析，特别是2D-NMR 的充分应用，并结合化学降解和反应得到证实。此外，还介绍了分离得到的一种具有明显抑制破骨细胞活性的化合物(QS29)的体外活性研究。 第三部分即第四章，综述了升麻属植物中环菠萝蜜烷三萜与其生物活性的构效关系研究现状。 This dissertation consists of three parts. In the first and the second parts, thechemical constituents from the flower buds of Eugenia caryophyllata and therhizomes of Cimicifuga foetida were reported. The third part is a review on astructure-activity relationship of the cycloartane triterpenoid from Cimicifuga species. The first part is composed of two chapters. The chapter 1 is about the isolationand identification of the chemical constituents from the flower buds of E.caryophyllata. A new phenolic glucoside gallate, methyl 2-O-(6’-O-galloyl)-b-D-glucopyranosylbenzoate (24), together with thirty-three known compounds has beenisolated from the ethanol extract of the flower buds of E. caryophyllata throughrepeated column chromatography on normal and reversed phase silica gel. Thestructure of the new compound was elucidated on the basis of spectral and chemicalevidence. Those kno wn compounds were belonged to flavone, triterpenoid, tannin andsome simple compounds. Among them, 12 compounds were isolated from the titleplant for the first time. The second chapter describes the capillary GC-MS analysis ofthe volatile components and the HPLC-MS/MS analysis of the polar constituents fromthe flower buds of E. caryophyllata, in order to detect the main constituents in thecrude extract rapidly and precisely. The third chapter is about the chemical constituents of the rhizomes C. foetida, atraditional Chinese medicine which was used as anti-inflammatory, analgesic andantipyretic agents. Our investigation of the bioactivities constituents of the rhizomesof C. foetida led to the isolation of five new cycloartane triterpenoids, which werecharacterized as cimicidol-3-one (38), 3'-O-acetyl cimicifugoside H-1 (41),2'-O-acetyl cimicifugoside H-1 (42), (3b,12b,16b)-12-acetoxy-16,23-epoxy-9,19-cyclolanost-22-ene-24-one 3-O-b-D-xylopyranoside (44) and cimicifugadine (54),along with fifteen known compounds through repeated column chromatography onnormal and reversed phase silica gel. Among them, 54 is a novel cycloartanealkaloid and first discovered as a new type alkaoid from nature. The structures ofthese compounds were elucidated on the basis of spectral and chemical evidence, andcimicidol-3-one was confirmed by X-ray crystallography analysis. Moreover, onecompound exhibited strong anti-osteoporosis activity in vitro experiment. The fourth part is a review on a structure-activity relationship analysis of thecycloartane triterpenoid from Cimicifuga species.

双花千里光、川芎及宽叶羌活的化学成分研究

本论文由四章组成。第一、二和三章分别报道了双花千里光、川芎和宽叶羌活的化学成分研究。从三种药用植物中共分离和鉴定了40 个化学成分，其中8个为新化合物。第四章概述了藳本属植物及日本川芎的化学成分研究进展。 第一章包括三个部分。第一部分报道双花千里光（Senecio dianthus Franch.）地上部分乙醇提取物的化学成分。采用正、反相硅胶柱层析等各种分离方法，从中共分离出8 个艾里莫酚型倍半萜内酯，其中5 个是新化合物，并且有1 个为首次发现的连接了含氮原子取代基的艾里莫酚型倍半萜内酯。它们的结构经MS、IR、NMR及X-单晶衍射等解析方法确定为2b-angeloyloxy-10b-hydroxyeremophil-7(11)-en-8a,12-olide (1)、6b-angeloyloxy-10b-hydroxyeremophil-7(11)-en-8a,12-olide (2)、2b-angeloyloxy-8b,10b- dihydroxyeremophil-7(11)-en-8a,12-olide (3)、2b-angeloyloxy-8a-hydroxyeremophil-7(11),9(10)-dien-8b,12-olide (4)和8b-amino-10b- hydroxyleremophil-7(11)-en-8a,12-olide (5)。这8 个倍半萜内酯经体外生物活性测试表明均具有通过抑制巨噬细胞增殖抵制破骨细胞增生的活性。第二部分对艾里莫酚型倍半萜内酯的质谱裂解规律进行了初步探讨。第三部分报道双花千里光茎、和叶花的挥发油成分分析。采用传统水蒸气蒸馏法分别提取了双花千里光茎、叶和花的挥发油，用气相色谱－质谱联用（GC-MS）技术分别分离鉴定了其化学成分，从茎、叶和花挥发油中各分离和鉴定出70、80 和73 种化学成分，分别占挥发油总量的91.2％、85.7％及93.4％。 第二章包括两个部分。第一部分报道川芎（Ligusticum chuanxiong Hort.）根茎乙醇提取物的化学成分。通过正、反相硅胶柱层析等分离纯化和MS、NMR及X-单晶衍射等解析方法，共分离鉴定了21 个化合物，结构类型分属于苯酞、二聚苯酞、香豆素和脂肪酸类。其中2 个为结构比较新颖的二聚苯酞类化合物：chuanxiongnolide A (19)和chuanxiongnolide B (20)，化合物19 的结构经X-单晶衍射得到确证。第二部分报道川芎挥发油的化学成分。采用不同的提取方法（溶剂萃取法、水蒸气蒸馏法、CO2 超临界流体萃取法）提取川芎挥发油，同时采集不同产地（四川彭县、四川郫县、云南鹤庆）及不同品质（川芎、奶芎、苓子）的川芎产品，利用GC-MS 技术分离鉴定其挥发油的化学成分，计算各成分的相对含量，并对比分析其中的异同。 第三章报道宽叶羌活（Notopterygium forbesii Boiss.）根茎化学成分的分离纯化和结构鉴定。通过正、反相硅胶柱层析等分离纯化和MS、NMR 等解析方法，共分离鉴定了13 个化合物，结构类型分属于香豆素、二氢异香豆素、甾体和羧酸类。其中1 个新二氢异香豆素类成分鉴定为6-methoxy-hydrangenol (37)。 第四章概述了藳本属植物及日本川芎化学成分的研究进展。 This dissertation consisted of four chapters. The former three chaptersrespectively elaborated the phytochemical investigation of three herbal medicines:Senecio dianthus Franch., Ligusticum chuanxiong Hort. and Notopterygium forbesiiBoiss.. Forty compounds, including eight new ones, were isolated and identified byspectral and chemical evidence. The fourth chapter elaborated the study progress ofchemical constituents of Ligusticum genus and Cnidium offcinale. The first chapter consisted of three parts. The first part is about the chemicalconstituents of ethanol extraction and essential oils from the aerial parts of S. dianthu.Eight eremophilenolides were isolated and identified. Among them, five ones are newcompounds and one of them is a novel eremophilenolide attched with an amino group.The structures of the new compounds were identified as 2b-angeloyloxy-10b-hydroxyeremophil-7(11)-en-8a,12-olide (1)，6b-angeloyloxy-10b-hydroxyeremophil-7(11)-en-8a,12-olide (2)，2b-angeloyloxy-8b,10b-dihydroxyeremophil-7(11)-en-8a,12-olide (3)，2b-angeloyloxy-8a-hydroxyeremophil-7(11),9(10)-dien-8b,12-olide (4) and8b-amino-10b-hydroxyeremophil-7(11)-en-8a,12-olide (5) by spectral evidence andX-ray crystallography analysis. All the compounds were evaluated for theiranti-osteoclstogenesis activity using a proliferation inhibit assay with microphagecells. The second part elementarily discussed the characteristic fragmentation oferemophilenolides isolated from S. dianthus in ESI-MS.The latter part is about thechemical constituents of essential oil extracted from stems, leaves and flowers of S.dianthus with steam distillation. By the GC-MS analysis, 70, 80 and 73 compoundswere respectively isolated and identified which accounted for more than 91.2％, 85.7％ and 93.4％ of total essential oil. The second chapter, including two parts, is about the the chemical constituents ofethanol extraction and essential oils from rhizomes of L. chuanxion. In the first part, twenty-one compounds were isolated and iedntified. Two ones are novel dimericphthalides and the structures were suggested as chuanxiongnolide A (19) andchuanxiongnolide B (20) by spectral evidence and confirmed by X-raycrystallography analysis. In the second part, the samples were collected from differentextract techniques (solvent extraction, steam distillation and supercriticalfluid extraction), different habitats (Peng and Pi counties, Sichuan province; Heqing,Yunnan province) and different qualities (Chuanxiong, Naixiong and Lingzi). Thechemical constituents of essential oil from L. chuanxiong were analyzed by GC-MS and were compared each other. The third chapter is about the chemical constituents of rhizomas of N. forbesii,which belongs to a endemic genus of China. Thirteen compounds were isolated andidentified. One of them is a new dihydroisocoumarin and the structure was identifiedas 6-methoxy-hydrangenol (37) by spectral evidence. The fourth chapter is a review on study progress of chemical constituents ofLigusticum species and Cnidium offcinale.

千金子和暖地大叶藓的化学成分研究

本论文由三部分共4 章组成。第一部分阐述了大戟科大戟属传统中药千金子（Euphorbia lathyris L.）化学成分、生物学活性以及千金子化学成分的HPLC、UPLC-MS、GC-MS 分析成果。第二部分介绍了民族药材暖地大叶藓（Rhodobryum giganteum (Schwaegr.) Par.）的化学成分研究和结构鉴定。第三部分概述了大戟属 植物中大环二萜酯的研究进展。 第一章包括1－3 节。在第1, 2 节中报道了千金子（Euphorbia lathyris L.）95% 乙醇提取物的化学成分分离鉴定。我们采用正、反相硅胶柱层析、重结晶等各种分离方法，凭借MS、IR、NMR、X-ray 等现代仪器手段,从中共分离鉴定22 个化合物。其中8 个是高活性化合物前体-续随子烷型大环二萜及3 个巨大戟烷型二萜，还有香豆素、生物碱、甾体等类型，其中完成对5 个大环二萜酯构型的确认，对2 个二萜酯构型进行了修正。第3 节中介绍对千金子化学成分的细胞毒性、α-葡萄糖苷酶抑制活性、P-gp 表达抑制活性的模型筛选结果。 第二章包括3 节，第1 节报道不同产地千金子高效液相色谱定量分析结果。第2 节介绍了各大环二萜酯的HPLC-MS/MS 的分析结果，并且对其质谱裂解规律、UPLC-MS 快速鉴定方法做了进一步讨论。第3 节介绍了千金子挥发油成分分析。采用传统水蒸气蒸馏方法提取千金子中的挥发油，并经气相色谱－质谱联用（GC-MS）技术共分离鉴定出 49 个化合物，占挥发油总量的90.48％。 第三章包括1, 2 两节，第1 节报道了暖地大叶藓化学成分。采用正、反相硅胶，凝胶柱层析等各种分离方法和MS、IR、NMR 等解析手段，共分离鉴定10个化合物，其中一个环肽化合物为新化合物。第2 节介绍了暖地大叶藓挥发油成分分析，共分离鉴定出 52 个化合物，占其挥发油总量的85.67％。 第四章概述了大戟科大戟属植物中大环二萜酯的研究进展。 This dissertation consists of three parts. In the first part, it is elaborated that the phytochemical investigation from the traditional Chinese medicine: seeds of Euphorbia lathyris L.. Biological activity and constituents analysis by HPLC、UPLC-MS、GC-MS were reported. In the second part, it is discussed that the chemical constituents were isolated and identificated from minority nationalitical herb－Rhodobryum giganteum (Schwaegr.) Par.. The third part is a review about the progress of studies on macrocyclic diterpenes from Euphorbia. The first part is composed of 1－3 sections. The section 1and 2 is focused on the isolation and identification of chemical constituents from seeds of E. lathyris. 22 compounds were isolated from the seeds of E. lathyris. by isolation methods of column chromatography (silica gel, including reversed phase) and recrystallisation on the basis of spectroscopic methods including IR, MS, NMR and X-ray. In 8 macrocyclic and 3 ingenane diterpenes, the relative configuration of 5 macrocyclic diterpenes were confirmed, in which 2 were amended. In the third section, cell cytotoxic activity, restraining activity of α-Glucosidase and multidrug resistance (MDR) reversing activity about P-gp were tested. 5 potential revsering reagents were found. The second part is composed of 1－3 sections. In first section it is described that the quality of the chemical constituents of E. lathyris from 5 sources , which were analyzed by high-performance liquid chromatography. In addition, the fractionation rules of some macrocyclic diterpenes were discussed and Ultra Performance Liquid Chromatography/ electrospray ionization mass spectrometry (UPLC-MS) was applied for quick determination of compounds in the second section. In the third section, chemical analysis of the essential oil from seeds of E. lathyris by GC-MS were reported. The essential oil from the seeds of E. lathyris L. in Sichuan was extracted by steam distillation and 49 compounds were isolated and identified from the essential oil by gas chromatography-mass spectrometer (GC-MS). These compounds are accounted for 90.46% of the total essential oil. The second part, including section 4 and 5, is about the phytochemical investigation of R. giganteum. In the former section, ten compounds were isolated and identified. Among them, a new peptide was characterized by spectroscopic analysis including IR, MS and NMR. In the other section, 52 compounds were isolated and identified from the essential oil by gas chromatography-mass spectrometer (GC-MS). These compounds are accounted for 85.67% of the total essential oil. The third part is a review about the progress of studies on macrocyclic diterpenes from Euphorbia.

低极性化合物的电喷雾质谱检测方法及几种中藏药材的活性成分研究

本学位论文首先报道了为解决低极性化合物的电喷雾质谱（ESI-MS）分析难题而建立的一种衍生化分析方法；然后从色谱-质谱联用分析、分离纯化和结构鉴定等方面分别报道了几种中藏药材的活性成分研究。论文由下述六章组成： 第一章报道了盐酸羟胺衍生化方法在电喷雾质谱 (ESI-MS) 分析中的应用。该方法利用盐酸羟胺和羰基成肟的快速反应，建立了针对三萜酮等含酮或醛羰基低极性化合物的ESI-MS 信号增强技术。此方法不仅可应用于增强羰基化合物的ESI-MS 质谱信号，还可检测化合物中羰基的个数以及辨别涉及羰基官能团的同分异构体。此外，通过简单的氧化反应，还可将该方法拓展到三萜醇、甾醇等含羟基的低极性化合物，增强它们的ESI-MS 信号。对比已报道的相关ESI-MS 增强质谱信号的衍生化方法，此方法有经济、实用、快速和简便的显著特点。 第二章是关于野生羌活及其栽培品种化学成分的色谱-质谱联用分析。对不同产地野生羌活生长过程中活性成分的动态变化、野生羌活不同形态部位和人工栽培羌活中的活性成分含量进行了HPLC 定量分析。结果表明主要活性成分羌活醇和异欧前胡素都随生长期存在规律性变化，羌活不同形态部位中的活性成分含量也有明显不同。这些实验结果有些较好地印证了传统中医的用药理论，有些也对羌活的传统使用方法提出了新的建议。 第三章介绍了几种传统中藏药材的色谱-质谱联用及串联质谱分析。通过GC-MS 方法，从藏药材长花党参挥发油中共分离鉴定出45 个化合物；利用HPLC方法测定了该藏药材中的主要化学成分——木犀草素的含量（0.7%）；利用串联质谱技术，对西番莲和射干中的主要成分进行了快速鉴定，从西番莲中鉴定了4个黄酮碳苷；从不同产地的射干和川射干中鉴定了8 个主要异黄酮成分，其中包括一个未见报道的化合物。 第四章的内容为藏药材石莲叶点地梅的活性成分研究。从植物石莲叶点地梅(Androsace integra (Maxim.) Hand.-Mazz.) 乙醇提取物的正丁醇萃取部分共分离和鉴定了6 个化合物，利用MS 和NMR 等现代波谱学技术阐明了它们的结构：其中包括4 个三萜类化合物：分别是androsacin (1)、 ardisiacrispin A (2) 、saxifragifolin A (3) 和20(29)-lupen-3-one (4)；一个神经酰胺：4-羟基-Δ8,9(Z)-鞘氨醇-2'-羟基正二十四碳酸酰胺(5)；一个甾体类化合物：胡萝卜苷(6)。化合物1为新的13,28-epoxy-oleanane 型三萜皂苷，在其结构表征的过程中，采用LC-MS 进行糖分析，获得了值得推广的好结果。通过活性筛选发现化合物1~3 对HepG2肝癌细胞表现出不同程度的抑制活性，其中化合物2 活性最好，其IG50 为1.65μg/mL。 第五章是关于一些传统中藏药材的农药活性筛选。利用Syngenta 公司的活性筛选平台对68 种传统中藏药材醇提物进行了抗菌和除草的生物源农药活性筛选。结果表明所筛选的68 种植物提取物中，共有14 种样品表现出明显的除草/杀虫活性，其中水母雪莲花、松萝和茯神木等植物提取物还具有多种生物活性。活性成分还有待进一步追踪分离、纯化和结构鉴定。 第六章为文献综述，概述了羌活药材的研究进展。对羌活属及药用羌活植物从分类学、本草学、品质评价、人工栽培、化学成分及药理作用等方面进行了文献归纳和总结。 In this dissertation, an electrospray ionization mass spectrometry (ESI-MS) signal enhancement method, as well as the work of bioactive components study, HPLC-MS/MS application, bioassay screening, chromatograph separation and structure identification of the metabolites in several medicinal herbs have been reported. First chapter expounded a rapid, simple ESI-MS sensitivity enhancement method for detecting carbonyl groups in natural products has been developed by using hydroxylamine hydrochloride (NH2OH·HCl) as a derivatization reagent. We use the oxime formed during the derivatization reactions and its Beckmann rearrangement intermediates as a means of detecting the carbonyl groups originally present in these triterpenoids. In comparison with other derivatization methods in the literature, this method is simple, specific and can be used to detect carbonyl groups in triterpenoids which have low polarity and are poorly or non-ionizable. Moreover, it can also be used to detect hydroxyl groups by using the Dess-Martin periodinane (DMP) to convert primary and secondary hydroxyls into carbonyl groups. Chapter 2 reported an HPLC-MS method for analyzing the main bioactive compounds in both wild and cultured Notopterygium incisum. The results indicated that the main bioactive compounds varied through different seasons regularly, and in different commercial parts of this herb the content of these compounds also differed from each other. The quantitative analysis results showed that in the traditional commercial parts, the content of main chemical constitutes in Silkworm Notopterygium, Bamboo Notopterygium and Irregular-nodal Notopterygium are higher than that in Striped Notopterygium. This result is tally with the traditionally concept that the quality of Notopterygium, Bamboo Notopterygium and Irregular-nodal Notopterygium are better than that of Striped Notopterygium, which means that the quality of rhizomes is better than main roots. The chemical constituents of cultured N. incisum is reported for the first time in this dissertation and the analysis results showed some growth curves of chemical constituents in this plant, but still left some questions unanswered. Chapter 3 discussed the GC/LC-MS analysis of the traditional Chinese medicines Codonopsis thalictrifolis, Passiflora incarnate, Belamcanda chinensis and Passiflora incarnate. The main constituent, luteolin was isolated and identified from the traditional Tibet medicine of C. thalictrifolis. The quantitative analysis by HPLC has revealed that the content of luteolin in this herb is 0.7%. GC-MS was employed to analyzed chemical constituents of the essential oil from the flower of C. thalictrifolis. More than 60 peaks were detected and 45 of them were identified by comparing their spectra with that of the standards in the database and literatures. ESI-MS/MS was used to analyze the n-butanol extract of Passiflora incarnate. Based on the information of pseudo molecular ions and fragment ions of the glycosides, four major flavone-C-glycosides have been detected and identified as 7-methoxyluteolin-6-C-β-D-glucopyranoside, vitexin, swertisin and orientin. The isoflavone compounds in theextracts of three samples of B. chinensis collected in Gansu, Sichuan and Hunan, and the extract of Iris tectorum collected in Sichuan were analyzed by using TOF-HRMS and IT-MS. From the extracts of these herbs, a new isoflavone, identified as 5’,5,6,7-tetrahydroxy-3’4’-dimethoxyl isoflavon, and 7 known ones have been identified by analyzing the fragmentation patterns and their molecular formulas given by HRMS and the tandem mass spectrometry acquired by IT-MS. Chapter 4 elucidated the isolation and identification of a new triterpene saponin, androsacin (1), along with five known compounds (2-6) were isolated from the whole plants of Androsace integra (Maxim.) Hand.-Mazz., an herb used in traditional Chinese and Tibetan medicine. The chemical structure of the new compound was established as 3β-O-{β-D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-[O-β-D-glucopyranosyl-(1→2)]-α-L-arabinopyranosyl}-16α-hydroxy-13β,28-epoxy-olean-30-al by analyzing its MS, 1D- and 2D-NMR spectra. Compound 2 was cytotoxic toward HepG2 cancer cell with the GI50 value of 1.65 μg/mL. Chapter 5 described the biogenic pesticide activity screening of 68 traditional Chinese and Tibetan medicine extractions. The intention of this study is to explore bioactive natural compounds from these traditional medicinal herbs for biogenic insecticides use. Based on Syngenta’s bioassay, 14 extractions of these traditional medicines showed pesticide activities, and some of them had multi-activities on antibacterial and insecticidal. Chapter 6 is a review on the chemical and bioactivity research progress of Notopterygium incisum and N. forbesii.

三种藏药材的化学成分研究

本学位论文报道了西藏产三种藏族传统植物药材的化学成分研究。论文由四章组成，前三章是实验部分，分别报道了尼泊尔黄堇(Corydalis hendersonii Hemsl.)、藏波罗花(Incarvillea younghusbandii Sprague)和全缘叶绿绒蒿(Meconopsis interifolia Franch.)的化学成分研究结果。从这三种青藏高原药用植物中共分离鉴定出33 个化合物，其中1 个是新化合物。第四章概述了罂粟科紫堇属植物的化学和药理研究进展。 第一章为尼泊尔黄堇的化学成分研究。通过正、反相硅胶柱色谱等分离方法从药用植物尼泊尔黄堇的地上部分共分离纯化得到12 个化合物。运用MS、1H-NMR、13C-NMR、DEPT、HMBC、NOESY 等现代波谱学方法将它们的结构鉴定为：刺罂粟碱(1) ， 普托品(2) ， 新那亭(3) ， 斯可任(4) ， tetrahydrothalifendine (5) ，9-methyl-decumbenine C (6)，tetrahydroberberrubine (7)，隐品碱(8)，α-别隐品碱(9)，6,7-methylenedioxy-1(2H)-oxoisoquinolinone (10)，6-丙酮基-5,6 -二氢血根碱(11)和β-谷甾醇(12)。其中化合物6 为新化合物，为首次发现的分子骨架上C-9 位连有甲基的苯肽异喹啉类型生物碱。另外，除化合物1 和2 外，其它9 个生物碱（3～11）均为首次从该种植物中分离得到。同时，我们还对对尼泊尔黄堇中的总生物碱进行了串联质谱分析。 第二章为藏波罗花的化学成分研究。从该药用植物的地上部分共分离得到16个化合物，通过理化常数和波谱数据鉴定为：异佛手柑内酯(1)，6-甲氧基当归素(2)，欧前胡素(3)，花椒毒内酯(4)，珊瑚菜素(5)，水合氧化前胡素(6)，rivulobirin A (7)，齐墩果酸甲酯(8)，咖啡酸甲酯(9)，银桦酸(10)，(D)-boschniakinic acid (11)，对羟基苯甲酸(12) ， tert-O-β-D-glucopyranosyl-(R)-heraclenol (13) ， 5-methoxy-8-O-β-D-glucopyranosyloxypsoralen (14)，前胡苷V(15)和苯乙醇-O-β-D-吡喃葡萄糖-(1→2)-O-β-D-吡喃葡萄糖苷(16)。所有以上化合物均为首次从该种植物中分离得到。另外我们还首次对藏波罗花挥发油的化学成分进行了气相色谱-质谱(GC-MS)联用分析，共鉴定出39 个挥发性成分。 第三章为全缘叶绿绒蒿化学成分的分离鉴定。从传统藏药材全缘叶绿绒蒿地上部分共分离纯化出8 个化合物。通过理化常数和波谱数据将他们的结构分别鉴定为：去甲血根碱(1)，β-谷甾醇(2)，3-羟基-齐墩果烷-12(13)-烯-30-酸(3)，6-丙酮基-5,6-二氢血根碱(4)，木犀草素(5)，胡萝卜苷(6)，quercetin 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (7)和普托品(8)。其中化合物1，4 和7 为首次从该种药用植物中分离得到。 第四章为综述，总结和归纳了近年来罂粟科紫堇属植物的化学和药理研究进展。 This dissertation consists of four parts. The first, second and third parts report the studies on the chemical constituents from the medicinal plants of Corydalis hendersonii, Incarvillea younghusbandii and Meconopsis interifolia. The forth part reviews the progress of the studies on Corydalis species. The first chapter is about the isolations and identifications of alkalids from the aerial parts of C. hendersonii which is a traditional Tibetan medicine to treat febrifuge, high blood pressure and hepatitis. A new isoquinoline alkaloid, 9-methyl-decumbenine C (6), together with ten known alkaloids, stylopine (1), protopine (2), canadine (3), scoulerine (4), tetrahydrothalifendine (5), tetrahydroberberrubine (7), cryptopine (8), α-allocryptopine (9), 6,7-methylenedioxy-1(2H)-isoquinolinone (10) and 6-acetonyl-5,6-dihydrosanguinarine (11), and β-sitosterol (12) were isolated. Their structures were elucidated by spectroscopic methods. Furthermore, the total alkaloids were analyzed by ESI-MSn. The second chapter is about the isolations and identifications of chemical constituents from the aerial parts of I. younghusbandii. Sixteen compounds were isolated and purified by normal and reversed phase silica gel column chromatography. By spectral analysis, there structures were identified as isobergapten (1), sphondin (2), imperatorin (3), xanthotoxin (4), phellopterin (5), heraclenol (6), rivulobirin A (7), methyl oleanolate (8), methyl caffeate (9), grevillic acid (10), (D)-boschniakinic acid (11), 4-hydroxybenzoic acid (12), tert-O-β-D-glucopyranosyl-(R)-heraclenol (13), 5-methoxy-8-O-β-D-glucopyranosyloxypsoralen (14), decuroside Ⅴ(15), and phenylethyl-O-β-Dglucopyranosyl-(1→2)-β-D-glucopyranoside (16). All of these compounds were isolated from this plant for the first time．By the way, the chemical components of the essential oil from I. younghusbandii were analyzed by GC-MS for the first time. The third chapter is about the the isolations and identifications of the chemical constituents of M. interifolia. Eight compounds were isolated and identified as norsanguinarine (1), β-sitosterol (2), 3-hydroxyolean-12(13)-en-30-oic acid (3), 6-acetonyl-5,6-dihydrosanguinarine (4), luteolin (5), daucosterol (6), quercetin 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (7) and protopine (8). The compounds 1, 4 and 7 were isolated from this herb for the first time. The last chapter is a review of the research progress of the studies on Corydalis species, which includes the chemical constituents in this genus and their pharmacology.