579 resultados para Herbs
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The wetlands in Uganda are undergoing rapid degradation. Swamps provide a habitat for birds, fishes and other animals. They have many ecological functions and, furthermore, supply people with multiple resources, such as reeds, herbs, fish and agricultural products. Although some'uses of wetland are sustainable, others lead to rapid deterioration. The main threat to swamps are human activities. One reason for the progressive destruction of wetlands is that the people may not appreciate the existence of and the treasures represented by wetlands even if they live in arm long distance from them. Another reason is that the two most important user groups of wetlands, farmers and fishermen, although having conflicting interests concerning the wetlands, hardly interact. A study, done as part of the Ecotone Project at the Fisheries Research Institute (FIRI), tries to evaluate in monetary terms how much Uganda loses with progressive destruction of wetlands. The study looks first at which uses of the wetlands are of importance and thereafter it examines, what data is needed and available to calculate the values of those uses.
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Successful applications of expanded bed adsorption (EBA) technology have been widely reported in the literature for protein purification. Little has been reported on the recovery of natural products and active components of Chinese herbal preparations using EBA technology. In this study, the hydrodynamic behavior in an expanded bed of cation resin, 001 x 7 Styrene-DVB, was investigated. Ephedrine hydrochloride (EH) was used as a model natural product to test the dynamic binding capacity (DBC) in the expanded bed. EBA of EH directly from a feedstock containing powdered herbs has also been investigated. These particles are different from commercially available expanded bed adsorbents by virtue of their large size (20S to 1030 gm). When the adsorbent bed is expanded to approximately 1.3 to 1.5 times its settled bed height, the axial liquid-phase dispersion coefficient was found to be of the order 10(-5) m(2) s(-1), which falls into the range 1.0 x 10(-6) to 1.0 X 10(-5) m(2) s(-1) observed previously in protein purification. Because of the favorable column efficiency (low axial dispersion coefficient), the recovery yield and purification factor values of EH directly from a feedstock reached 86.5% and 18, respectively. The results suggest that EBA technology holds promise for the recovery of natural products and active components of Chinese herbal preparations.
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Invasive alien species have become one of the most serious environmental issues in the world. Data of taxon, origin, pathway, and environmental impacts of invasive alien microorganisms, invertebrates, amphibians and reptiles, fish, birds, mammals, herbs, trees, and, marine organisms in terrestrial, aquatic, and marine ecosystems of China were analyzed during 2001 and 2003, based on literature retrieval and field survey. There were 283 invasive alien species in China, and the number of species of invasive alien microorganisms, aquatic plants, terrestrial plants, aquatic invertebrates, terrestrial invertebrates, amphibians and reptiles, fish, and mammals were 19, 18, 170, 25, 33, 3, 10, and 5, respectively. The proportion of invasive alien species originated from America, Europe, Asia, Africa, and Oceania were 55.1, 21.7, 9.9, 8.1, and 0.6%, respectively. Methods for estimation of direct economic losses to agriculture, forestry, stockbreeding, fishery, road and water transportation, storage, water conservancy, environment and public facilities, and human health were established. Methods for estimation of indirect economic losses caused by invasive alien species to service functions of forest ecosystems, agricultural ecosystems, grassland ecosystems, and wetland ecosystems were also established. The total economic losses caused by invasive alien species to China were to the time of USD 14.45 billion, with direct and indirect economic losses accounting for 16.59% and 83.41% of total economic losses, respectively.
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Goal, Scope and Background. In some cases, soil, water and food are heavily polluted by heavy metals in China. To use plants to remediate heavy metal pollution would be an effective technique in pollution control. The accumulation of heavy metals in plants and the role of plants in removing pollutants should be understood in order to implement phytoremediation, which makes use of plants to extract, transfer and stabilize heavy metals from soil and water. Methods. The information has been compiled from Chinese publications stemming mostly from the last decade, to show the research results on heavy metals in plants and the role of plants in controlling heavy metal pollution, and to provide a general outlook of phytoremediation in China. Related references from scientific journals and university journals are searched and summarized in sections concerning the accumulation of heavy metals in plants, plants for heavy metal purification and phytoremediation techniques. Results and Discussion. Plants can take up heavy metals by their roots, or even via their stems and leaves, and accumulate them in their organs. Plants take up elements selectively. Accumulation and distribution of heavy metals in the plant depends on the plant species, element species, chemical and bioavailiability, redox, pH, cation exchange capacity, dissolved oxygen, temperature and secretion of roots. Plants are employed in the decontamination of heavy metals from polluted water and have demonstrated high performances in treating mineral tailing water and industrial effluents. The purification capacity of heavy metals by plants are affected by several factors, such as the concentration of the heavy metals, species of elements, plant species, exposure duration, temperature and pH. Conclusions. Phytoremediation, which makes use of vegetation to remove, detoxify, or stabilize persistent pollutants, is a green and environmentally-friendly tool for cleaning polluted soil and water. The advantage of high biomass productive and easy disposal makes plants most useful to remediate heavy metals on site. Recommendations and Outlook. Based on knowledge of the heavy metal accumulation in plants, it is possible to select those species of crops and pasturage herbs, which accumulate fewer heavy metals, for food cultivation and fodder for animals; and to select those hyperaccumulation species for extracting heavy metals from soil and water. Studies on the mechanisms and application of hyperaccumulation are necessary in China for developing phytoremediation.
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结合野外调查与室内试验对子午岭辽东栎天然林的种群生长状况,枯落层种子库,不同坡位土壤种子库物种组成、数量特征、生活型及其与地上植被的相似性进行了较为系统的研究。结果表明:(1)试验萌发鉴定出的幼苗共有24种,隶属于16科,其中多年生草本和落叶灌木物种比例最高,分别占种子库物种总数的58.33%和12.5%;(2)整个子午岭天然辽东栎林土壤种子库总密度为12 761.44粒/m2,种子主要分布在枯枝落叶层和0-2.5 cm土层中,其中,辽东栎种子密度为752.5粒/m2,占整个样地土壤种子库总密度的5.89%,表明辽东栎种子萌发能力很差,该林分群落天然更新缓慢。(3)子午岭天然辽东栎林的下坡位物种多样性指数较其它坡位高,但各个样地物种多样性指数均高于对照;(4)天然辽东栎纯林的种群生长状况良好,树龄均为成年树种;(5)方差分析表明:辽东栎的胸径、地径在不同坡位之间均具有显著性差异(P>0.05);(6)相关分析表明:枯枝落叶层厚度,重量与土壤种子库密度之间具无显著相关性(P<0.05)。
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植被生态序列是小地形对植被空间分布影响的反映。采用样线法,对安塞纸坊沟支沟拐沟中南北向短坡面深沟谷和长坡面浅沟谷断面进行植被调查,分析其植被生态序列特征、物种组成及物种多样性。结果表明:短坡面深沟谷序列主要以灌乔木等演替后期物种为主,而长坡面浅沟谷序列则主要为草本物种;同一序列中,阴坡、沟谷地具有比阳坡、沟间地复杂的演替后期群落;序列中物种主要由菊科(Compositae)、豆科(Leguminoseae)和禾本科(Gramineae)构成,生活型主要为多年生草本,生态型以旱生、中旱生为主。α多样性指数在阴坡和短坡面深沟谷序列较高,β多样性指数在地形变化活跃的沟缘线区较高。研究结果可为黄土丘陵沟壑区植被建设人工调节提供参考依据。
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采用电喷雾多极串联质谱技术,对正、负离子条件下人参中的皂苷类化合物的碎裂机理、苷元类型和糖基的种类、连接顺序及连接位点的信息进行了系统的研究。并用高效液相色谱-电喷雾质谱联用技术, 对人参中的皂苷类化合物进行了在线分析,建立了中药粗提物中皂苷类化合物快速检测的方法。 采用电喷雾质谱和高效液相色谱-电喷雾质谱联用技术对人参与不同比例酸、甘味中药:五味子、麦冬、金银花、黄芪、何首乌配伍前后溶液中人参皂苷的种类与含量的变化进行了研究。建立了一种快速、简便地鉴别药对中人参皂苷化合物的方法。试验结果表明,各单体皂苷含量的变化十分复杂。有机酸对人参皂苷的溶出和水解有较为显著的影响。 采用电喷雾质谱和高效液相色谱-电喷雾质谱联用技术对人参与不同比例苦、辛味中药:附子、黄连、赤芍、大黄、干姜配伍前后溶液中人参皂苷的种类与含量的变化进行了研究。试验结果也表明,有机酸对人参皂苷的溶出和水解有一定的影响;附子和黄连中所含的生物碱类化合物在水溶液中对人参皂苷的影响不大,而将提取液换成50%的乙醇溶液则可以促进人参皂苷的溶出。 采用高效液相色谱-电喷雾质谱联用技术对与人参相反、相恶、相畏的中药藜芦、五灵脂、莱菔子与人参的配伍进行研究,观察人参皂苷在配伍前后的变化。试验结果表明:人参与这三种中药配伍后,溶液中人参皂苷总量下降,且人参对藜芦中毒性较大的藜芦生物碱的溶出具有促进作用。 采用高效液相色谱-电喷雾质谱联用技术对不同pH值水溶液中的人参皂苷的溶出,水解变化进行研究,试验结果表明:在碱性溶液中人参皂苷的溶出量增加且不易水解;在酸性溶液中,酸性越强人参皂苷溶出量越低且更易水解,水解产物较复杂,多为失去C20位糖基的小分子量人参皂苷和其C20的手性异构体,还可发现分子量为802Da的水合分子。 采用半制备液相色谱对二醇型皂苷Rb1和三醇型皂苷Re的水解产物进行分离和鉴定。共分离出四种分子量为802Da的水解产物。通过高分辨质谱仪对这几个化合物的特征质谱行为进行了系统研究,总结了该类化合物特征的质谱裂解规律,并鉴定了它们的结构。
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药物分子与生物分子的相互作用是分子水平上研究药物构效关系及药物筛选的基础。测定形成的非共价复合物及其稳定性是研究药物与靶分子相互作用的关键。单链和双链DAN与小分子的相互作用提供了包括抗癌、抗病毒及抗菌在内的大量治疗药物的作用机理。本论文选择合成了与SARS病毒和肿瘤相关的寡聚核昔酸靶分子,利用质谱高灵敏、专一性、快速、化学计量的特点,研究靶分子与临床上确有疗效的抗病毒、抗肿瘤中药中几大类化学成分的相互作用,探讨它们相互作用的规律,通过相互作用强度的比较,考察这些中药化学成分在抗病毒、抗肿瘤方面的可能活性。在单链寡聚核营酸靶分子(RNA,DNA)与皂昔类化合物的相互作用的研究中,首先建立了区分皂普类异构体的高分辨电喷雾质谱及多级串联质谱的分析方法,通过皂普准分子离子在CID谱中产生的碎片离子,可以提供皂昔昔元、糖基类型、糖链的连接位点,为类似化合物的异构体的区分提供了一个简捷、灵敏、准确的分析方法。考察了实验条件对单链寡聚核营酸靶分子(RNA,DNA)与中药化学成分相互作用的影响;在皂营、黄酮类化合物与单链寡聚核昔酸靶分子的作用研究中,发现非共价作用强度的大小与普元、糖链的结构有关,包括昔元的类型、轻基的数目、糖链的长短,以及糖链上甲基取代的位置。单链寡聚核普酸靶分子与生物碱的相互作用研究表明,相互作用亲和力的大小与生物碱的碱性强弱有关,季胺型生物碱的作用最强,如巴马汀、药根碱、小巢碱与靶分子均生成了较强的非共价复合物。与昔类、内酩、酚类等成分的相互作用同样与其结构密切相关。双链DNA与生物碱类化合物的相互作用研究发现,它们与生物碱的作用强度与双链DNA的AF碱基对富有或GC-碱基对富有有关,且复合物离子的CID断裂途径不同。生物碱化合物的结构不同,其作用强度存在较大差异。述研究结果建立了核昔酸与中药化学成分相互作用研究的软电离质谱方法,利用该方法的研究结果,可以为中药活性成分的初步筛选提供一条可以借鉴的途径。
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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.
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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.
Resumo:
本学位论文分为四个部分,第一部分报道了用串联质谱快速分析合成药物中的微量杂质成分以及分析中药材中的化学成分。第二部分报道了通过质谱和串联质谱发现并合成新型的PdPincer 催化剂,同时对其活性进行测试。第三部分为串联质谱自动解析软件的设计及应用。第四部分概述了应用在质谱中的各种碎裂方式。 第一部分首先总结了5-溴粉防己碱及其类似物的裂解规律,并以此为根据推测出2 个微量杂质的结构。随后针对无患子(Sapindus mukurossi Gatren.)中的皂苷成分,由ESI-QTOF 得到各个皂苷成份的高分辨质量数据进而得到其分子式,然后利用ESI-IT 电喷雾串联质谱对无患子总皂苷中各皂苷成分的结构进行进一步的鉴定。进而以同样的方式,先通过ESI-QTOF 得到黄山药(Dioscoreapanthaica)总皂苷中各个组分化合物的分子式,然后对已有的薯蓣皂苷标准品做串联质谱分析,以得到该类化合物的裂解规律并给出解析该类化合物的流程图。在此利用计算化学的方法讨论了离子的丰度与裂解活化能之间的关系。然后应用APCI-MS/MS 方法探讨了四对同分异构体和几个已知的化合物,并最后用液质联用对其进行确认,同时还给出了4 个未知化合物的可能结构。 第二部分报道通过质谱和串联质谱发现并合成新型的PdPincer 催化剂,同时对其活性进行测试。钯催化的交联反应是有机合成中C-C 键形成的最有效的方法,且硫脲是一类对空气和水都稳定的化合物,因此我们设计并合成了一系列的硫脲钯催化剂并得到了很好的催化活性。我们在对其中一类环状双硫脲化合物进行质谱实验的时候,在正离子模式下发现了反常的[M.H]+,通过串联质谱进一步确定了它是一种新型的PdPincer 结构。我们将其合成出来并通过X-ray 衍射实验确定了它的结构。同时测定其催化活性并与未形成pincer 的类似物进行比较发现该类化合物具有较宽的底物适用性。 第三部分为串联质谱自动解析软件的设计及应用。通过前面两部分的启示,独立设计开发了AuMass(1.0)。其算法是:先通过查找特殊的碎片离子,中性丢失或碎片离子质量差来确定某类化合物的骨架结构,然后利用该类化合物的自动解析流程来对其周边取代基进行确认。通过它快速地对白芍中的化学成分进行解析,并对未知的化合物进行了推测。为了增加它的解析能力,我又对其它类型的化合物裂解规律进行总结,并给出了自动解析流程。实践证明该软件具有相当好的应用价值。 第四部分综述了应用在质谱上的各类母离子的碎裂技术。这里包括了碰撞诱导裂解(CID)、光诱导碎裂(LID)、电子捕获裂解/电子转移裂解(ECD/ETD)、红外多光子解离(IRMPD)、黑体辐射解离(BIRD)和PQD 裂解技术。 This dissertation consists of four chapters. The first chapter reports the rapidanalysis of trace impurities from synthetical medicine and analysis of the chemicalconstitutents from Chinese herb medicines. The second chapter elaborates the studieson the discorvery and synthesis of new type of Pd Pincer catalyst by using MS andtandem MS together with the testing of its catalyst activity. The third chapter dwellson the designation and development of automatic tandem mass spectrometry analysissoftware. The last chapter presents a review on the dissociation technique of massspectrometry. The first chapter reports the rapid analysis of trace impurities from synthesismedicine and analysis of the chemical constitutents from Chinese herb medicines. The fission mechanism of 5-bromotetrandrine was obtained by analysis of the dissociationpathways of major product, by using which the possible structure of the two traceimpurties was assumed. There are lots of saponins in Sapindus mukurossi. Except forthe good spumescence and decontamination,it possesses the bioactivity of antigenand antitch. First of all, the high resolution mass information was obtained by ESI-QTOF. Hence the possible molecular formulars were acquired too. Then weconducted the further detection of the structures of its saponins by using ESI-ITtechnology. In the same manner, first the molecular formulars of every constituentfrom Dioscorea panthaica in total saponins were obtained by ESI-QTOF, and thenacquired the fission mechanism of this type of compounds by tandem massexperiment on a series of known and available saponins. In the same time, theanalysis flowchart was concluded. Here the relationship between the ion intensity andthe corresponding dissiociation activation energy was studied by computer chemistry.Then the four pairs of isomers were differentiated by APCI-MS/MS, as well as thecharacterization of known and unknown compounds. The assumption was confirmed by HPLC-MS/MS. Among them the possible structures of four unknown saponinswas presented. The second part was discovery and synthesis of a new type of Pd pincer catalystby MS and tandem MS. The coupling reaction catalyzed by Pd is the most effectivemethod in C-C formation in organic synthesis. Apart from that, thiourea is type ofcompounds that are stable to atmosphere and moisture. Hence we designed a series ofPd thiourea catalysts. Some of them show the excellent catalyst activity. The abnormalparent ion [M.H]+ was founded in positive ESI mode when we conduct some massspectrometry experiments on the bicyclical thiourea Pd complex. The structure wasproposed by mass and tandem mass spectrometry. Because it was a new type of pincer,we want to test its catalyst activity. So the Pd pincer was synthesized and the detailstructure was obtained by x-ray experiment. It shows the more fitness in catalysis ofSuzuki reaction by comparison with the analogue. The third chapter dwells on the design and development of automatic tandemmass spectrometry analysis software. Inspired by the former two chapters, theAuMass (version 1.0) was developed. Its algorithm is: first check the diagnostic ion,diagnostic neutral loss or diagnostic ions mass intervals in database to find out whatthe analyst’s skeleton belongs to, then identify the peripheral functional group by thecorresponding analysis flowchart. The chemical constituents of Paeonia lactiflorawere identified rapidly by using AuMass. To increase the analysis ability, the othertypes of compounds from Chinese herbs was concluded. Actually, the software isproven to have the much valuable application. The last chapter presented the review on the some kinds of fission technique ofmass spectrometry. It involves the collision induced dissociation (CID), laser induceddissociation (LID), electron capture dissociation/electron transfer dissociation(ECD/ETD), infrared multiple photons dissiociation, black body irraditiondissociation and PQD fission technique from Finnigan.
Resumo:
本学位论文由4章组成。第一章是论文的主体,报道了中药射干的化学成分研究。第二章是中药射干代用品川射干的化学成分研究,并附带报道了西番莲化学成分的研究结果。第三章是射干、川射干及西番莲提取物化学成分串联质谱分析的报道。第四章为综述,概述了射干及鸢尾属植物的化学成分和药理研究进展。 在第一和二章中分别报道了射干(Belamcanda chinensis (L.) DC.)、川射干 (Iris tectorum Maxim.)及西番莲(Passiflora incarnate L.)化学成分的分离纯化与结构鉴定。采用正、反相硅胶柱层析、凝胶柱层析、薄层制备及HPLC等各种分离方法,从三种药用植物中共分离出68个不同的化合物,其中61个的结构得 得以鉴定,另外4个化合物的结构正在鉴定中,3个由于量少且有点杂质未作进一步的鉴定。 中药射干(Rhizoma Belamcandae)为射干植物的干燥根茎,从中共分离出53个化合物,通过红外、质谱及核磁共振等波谱方法鉴定了包括12个新化合物在内的48个,结构类型分别属于iridal型三萜及其新颖的二聚体、异黄酮、黄酮及黄酮醇、香豆素、甾体、芳香酸和脂肪酸及其甘油酯等。新化合物中有两个异黄酮类化合物,其结构分别鉴定为5,7,8,4′-四羟基-6-甲氧基异黄酮和5,6-二羟基-4′-甲氧基异黄酮-7-O-β-D-吡喃葡萄糖苷;八个新的iridal型三萜化合物分别鉴定为鸢尾烯(L)、16-甲氧基鸢尾烯、16-去羟基鸢尾烯、2-(E)-16-去羟基鸢尾烯、16-去羟基鸢尾烯B、3-乙酰基-16-去羟基鸢尾烯、iristectoroneL和iristectoroneM;两个结构骨架新颖的双三萜,分别命名为射干素A和射干素B,其分离纯化的困难以及结构的新颖和复杂突显出该论文的科学意义。除这些新化合物外,还有9个已知化合物为首次从中药射干中分离得到。此外,从中药射干的代用品川射干中分离得到7个已知化合物,主要是黄酮类成分及iridal型三萜化合物,其中1个三萜化合物为从射干中分离鉴定的新成分。另外还从西番莲中分离出8个化合物,鉴定了其中的6个,主要为黄酮碳苷。 第三章是关于射干、川射干及西番莲提取物化学成分的ESI-MS-MS分析,在初步探讨了从这些植物中分离鉴定出的一些异黄酮及黄酮碳苷的质谱裂解规律基础上,通过质谱和串联质谱分析,定性和半定量地检测了射干和川射干中主要的异黄酮成分以及西番莲中的黄酮碳苷成分,为这些药材品质的快速鉴定提供了一种简便方法。 第四章概述了射干及鸢尾属药用植物的化学和药理研究进展,特别是对其中异黄酮及三萜类成分的研究进展进行了深入系统的综述。 This dissertation is composed by four chapters. The first and second chapter reports the phytochemical investigation of three medicine plants, Belamcanda chinensis (L.)DC., Iris tectorum Maxim. and Passiflora incarnate L. Sixty eight different compounds were isolated and sixty one of them were identified. The third chapter described rapid ESI-MS-MS analysis of B. chinensis, I. tectorum, and P. incarnate. The forth part is a review about the progress of studies on the chemical constituents from Belamcanda chinensis and Iris species. Fifty-three compounds were isolated from Rhizoma Belamcandae, the rhizomes of B. chinensis by the methods of column chromatography (normal and reversed phase silica gel, Sephadex LH-20), preparative TLC and HPLC. On the basis of spectroscopic methods including IR, ESI-MS, 1-D and 2-D NMR, forty eight of them were identified as seventeen flavonoids, seventeen tritepenoids, one cumarin, five steroids and some benzene derivative etc. Among them, the structures of twelve new compounds were elucidated as 6-methoxy-5,7,8,4′-tetrahydryoxyisoflavoe, 4′-methoxy-5,6-dihydroxyisoflavone-7-O-β-D-glucopyranoside, iristectorene L, 16-methoxyisoiridogermanal, 16-dehydroxyisoiridogermanal, 2-(E)-16-dehydroxy isoiridogermanal, 16-dehydroxyiristectorene B, 3-acetyl-16-dehydroxyisoiridoger- manal, iristectorone L, iristectorone M, belamcandene A and belamcandene B. Last two new compounds are dimer of triterpenoids with a novel carbon skeleton. Beside the new compounds, nine known ones were isolated from this plant for the first time. Isolation of I. tectorum yielded seven compounds. On the basis of spectroscopic methods including ESI-MS, NMR and the comparison with authentic samples, three of them were determined as isoflavone, two of them were triterpenoids, and other two were β-sitosterol and apocynin. All of them are known compounds except one of iridal type triterpenoid, 16-dehydroxyiristectorene B, which also obtained from B. chinensis as a new compound. Isolation of P. incarnate yielded eight compounds. Six of them were determined on the basis of spectroscopic methods including ESI-MS, NMR and the comparison with authentic samples. Four of them are flavone-C-gluconside, and two are steroids. The third chapter describes the tandem mass spectrometry (ESI-MS-MS) analysis of the isoflavonoids from B. chinensis and I. tectorum, as well as C-glycosyl-flavonoide from P. incarnate, in order to explore the rapid methodology of validating the quality of the herbs. In addition, the fractionation rules of some iosflavonoids and C-glycosyl-flavonoids were discussed. The fourth chapter summarizes the research development on chemistry and pharmacology of medicine plants of B.chinensis and Iris species.
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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.
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日益增强的旅游活动干扰正成为九寨沟世界自然遗产的有效保护与持续管理不可回避的挑战,已成为当前区域生态保护与经济发展的焦点问题之一。阐明相关旅游的干扰活动对核心景区植物物种组成、多样性与结构的影响是九寨沟有效保护与持续管理的必要前提和基础,然而至今少有研究。选择九寨沟与旅游活动相关的九个景点、公路建设地段以及退耕地还林地,详细调查了林下植被结构、物种组成与多样性,比较了相关旅游活动干扰与基本未受干扰地段的差异。目的是阐明九寨沟核心景区旅游干扰条件下植物多样性与群落结构及其特点,揭示旅游干扰与植被结构和生物多样的相互关系,评估九寨沟旅游管理的有效性,探索减免旅游干扰影响的对策与措施。初步结论如下。 1.旅游活动引起九寨沟核心景区植物组成和群落结构特征改变显著。栈道及公路附近许多耐荫喜湿的敏感种局部消失,而早熟禾、车前草、委陵菜等耐干旱、耐践踏、繁殖能力强的植物种群扩大;外来物种频繁出现并已少量侵入干扰相对较轻的林分深处;林下群落以草本植物为优势,灌木与苔藓植物的频度、盖度、高度以及灌木密度均有所下降。可见,大量的游人活动和景区公路建设已对九寨沟丰富的乡土植物构成极大威胁,导致其生物多样性降低。而九寨沟农耕地退耕有利于九寨沟生态环境和生物多样性保护,正逐步向稳定群落演替。 2.干扰强度的差异导致九寨沟植物所受影响的程度不同。栈道附近植物受影响的程度与游人活动频率有关,活动频率高的地段干扰强度大,对植物的影响程度重,反之植物所受的影响较轻。强度干扰地段,耐荫喜湿的物种少见,伴生植物优势地位突出,生物多样性明显降低,植物群落结构特征改变也极为显著;干扰较轻的地段,伴生物种少量出现,植物群落结构变化不明显,生物多样性略为降低,部分地区结构参数值和多样性指数有所升高。公路修建是一种强度干扰,它导致附近植物种类极为单一,草本优势种异常突出,多数植物生活力低下、生长更新能力差。 3.不同植物类群受干扰影响的程度不同。草本及苔藓植物的种类组成和多样性指数受干扰影响较大,灌木和苔藓植物的结构受干扰影响较大,苔藓植物对干扰影响最为敏感。 综合分析表明,九寨沟核心景区的管理虽然比较规范,但目前核心区热点景点段的管理仍然不够,旅游活动驱动了林下植被退化明显、物种组成显著变化、生物多样性衰退、非乡土喜光耐旱种群扩大。导致九寨沟核心区旅游活动与生物多样性保护目标尖锐冲突,进一步约束旅游活动带来的干扰,强化管理,开展林下植被恢复与非乡土喜光耐旱种群调控是九寨沟自然遗产地保护一项紧迫任务。 The increasing tourism disturbance is an unavoidable challenge to effective conservation and sustained tourist management of Jiuzhaigou Nature Reserve. It has become one of the focal problems of regional ecological protect and economic development. It is important to clarify effects of tourism disturbance on plant species composition, diversity and community structure in kernel spot for effective conservation and sustained tourist management in Jiuzhaigou, China. However, there were little studies about this yet. The study investigated the vegetation structure, species composition and diversity at nine sight spot, road area and four abandoned farmlands connecting with tourism, and compared the differences between disturbed area and undisturbed area. The purpose of the this study is clarifying the plant diversity and community structure and characteristics of the disturbed area in kernel spot of Jiuzhaigou, discovering the relation between vegetation structure and biodiversity, evaluating the effect of tourist management and exploring the measure decreasing tourist disturbance. Our results are following: 1. Tourism disturbance caused a significant change in species composition and structure of plant communities in kernel Spot of Jiuzhaigou. In the vicinity of plank and road, some native shade-tolerant or hygrophilous plants had disappeared, accompanying with the population expansion of some xerophilous and disturbance-resisting species such as Poa sp. Plantago depressa, Potentiila multicaulis and some exotic and synanthropic species. Herbs were domaint species, while frequency coverage and height of shrubs and bryophytes, and shrub density decreased. In indicated that tourist activities and build of road had adversely affected on native plant species, and led to decline in biodiversity of Jiuzhaigou Nature Reserve. Abandoned farmlands maybe conduced to entironment and biodiversity conservation. 2. Nearby the plank, influency variable of tourism disturbance on plant was alosely and positively correlated with disturbance intensity. There was companion plant species and lacked shape-loving species in heavy disturbed areas, which caused decrease in biodiversity and significant change in community structure in these places. On the contrary, in the slightly disturbed areas, some companion speices displayed and biodiversity decreased slightly, but no significant change in community structure in these areas. The biuld of road is a heavy disturbance form, which led to increase of herb species and to decrease in vitality and regeneration capacity. 3. The intensity of tourism disturbance on plant depended on plant groups. Tourism interference significantly influenced species composition and diversity index of herb and bryophyte; it also significantly influenced community structure; the bryophyte was more sensitive to tourism disturbance. Our result indicated that the management in kernel spot of Jiuzhaigou is relatively reasonable, but not adequate. Tourism speed the degradation of the vegetation under woodland, the change of the species composition, the decreaing of the biodiversity and the expanding of the exotic sunloving plant populations. The contradiction between tourism and conserving biodiversity is increasing, so enforcing management, regenerating the vegetation under woodland and adjusting the exotic sunloving arid-tolerent plant populations is a pressing work to protect the Jiuzhaigou natural legacy.
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Qianyanzhou(QYZ) Ecological Station established in 1983 with an area of 204 hm~2 is affiliated to the Chinese Ecosystem Research Network.Before 1982,herbs had been dominant,sparsely dotted with shrubs.After 20-year restoration of the vegetation,the vegetation showed significant changes in both forest coverage and species diversity.Forest coverage had increased to 93.3% in 1999 from 0.4% in 1982.The vegetation could be broadly classified into two groups: artificial forest,accounting for the most percent,and natural secondary forest.These two groups could be subdivided into 12 types.Based on the 2003 field work,The authors studied plant community composition and vertical structure.The results were as follows: 1) On the study plots were there about 150 species,of which 100,49,and 47 grew in arbor layer and shrub layer and herb layer,respectively.Of 12 community types,the amount of species in shrub layer was larger than that of other two layers.As to the species richness in the different community types,Liquidambar formosana community showed the highest and Imperata cylindrical var.major community the least.The amount of species in arbor layer of artificial forest was smaller than those of natural Pinus massoniana forest,but no difference in understory.2) Loropetalum chinense,Quercus fabric and Vaccinium bracteatum were dominant shrub species with a wide distribution.Three ferns Woodwardia japonica、Dryopteris atrata and Dicrannepteris dichotoma were dominant herb species.Lianas were sparse,but Milletlia reticulata were found in all forest types.3) Up to now some natural regeneration species,such as Eurya muricata、Quercus fabri、Vaccinium bracteatum、Rhus chinensis、Adinandra bockiana,had grown in the arbor layer of artificial forests.Some herb species,such as Arundinella setosa、Miscanthus floridulus、Isachne globosa、Scirpus triqueter,which were dominant ones in the herb layer before the restoration of vegetation,disappeared now.4) The vertical structure of natural Pinus massoniana community and Liquidambar formosana community showed more complex comparing with artificial forests.For the artificial forests,the conifer and broad-leaves mixed forest had a more complex structure.In both natural Pinus(massoniana) community and Liquidambar formosana community,it was dominated by individuals with height of 3~4 m,while 10~12 m in the artificial forests.