中药射干的化学成分研究

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.

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.

钩藤和蹄叶橐吾的化学成分研究

本论文由三章组成。第一、二章分别报道钩藤、蹄叶橐吾的化学成分研究工作。从两种药用植物中共分离和鉴定了37 个化合物，其中有1 组6 个新的骨架相似的鞘糖脂类同系物及5 个新的倍半萜类化合物。第三章概述了艾里莫芬烷内酯类化合物的研究进展。 第一章报道钩藤(Uncaria rhynchophylla)带钩茎枝乙醇提取物的化学成分。采用正、反相硅胶柱层析等分离方法，运用NMR、MS 等波谱技术共分离鉴定得到22 个化合物，分属于五环三萜类化合物、鞘糖脂类化合物等，其中有1 组6个新的鞘糖脂类化合物同系物，另外有7 个化合物首次从该植物中分离得到。 第二章报道蹄叶橐吾(Ligularia fischeri)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和MS、NMR 等波谱解析，共分离鉴定得到18 个化合物，其中5 个是新化合物。它们的结构分别确定为3β-acetyl-6β, 8α, 10β-trihydroxyeremophila-7(11)-en-8, 12-olide (23), 3β-acetyl-8β,10β-dihydroxy-6β-(2-methylbutyryloxy)-eremophilenolide (24), 3β-acetyl-6β, 10β-dihydroxyeremophila-7(11), 8(9)-dien-8, 12-olide (25), 3β-acetyl-6β, 10β-dihydroxyeremophila- 7(11), 8(9)-dien-8, 12-olide (26), (3aR, 4R, 5S, 7aS)-2-acetyl-7ahydroxy-3a, 4, 5, 6, 7, 7a-hexahydro-1H-inden-5-yl acetate (27)。这5 个化合物经体外生物活性测试，结果表明化合物23 具有抑制酪氨酸磷酸酯酶的活性, 其IC50 值为1.30 μg/ml。 第三章概述了近二十年来艾里莫芬烷内酯类化合物的研究进展，包括其结构及药理活性两个方面，列举了从23 种植物中分到的114 个艾里莫芬烷内酯类化合物，同时也对其主要生物活性进行了总结。 This dissertation consists of three chapters. The first and second chapters elaborate the phytochemical investigation of Uncaria rhynchophylla and Ligularia fischeri. Thirty-seven compounds, including six new ones, were isolated and identified by spectroscopic methods and X-ray diffraction experiments. The third chapter is a review on the study progress of Eremophilanolides. The first chapter focus on the isolation and identification of chemical constituents from Uncaria rhynchophylla. Twenty-two compounds were isolated from the roots of U. rhynchophylla by repeat column chromatography over normal and reversed phase silica gel. Those compounds mainly belonged pentacyclic triterpenoids and sphingolipids. Among them, a series homologues of six sphingolipids were new compounds and seven compounds were firstly reported in this plant. The second chapter is about the phytochemical investigation of L. fischeri. Eighteen compounds were isolated and identified. Among them, four new erem-ophilanolides and a new dinoreremophilane derivative were characterized as 3β-acetyl-6β, 8α, 10β-trihydroxyeremophila-7(11)-en-8, 12-olide (23), 3β-acetyl-8β, 10β-dihydroxy-6β-(2-methylbutyryloxy)-eremophilenolide (24), 3β-acetyl-6β, 10β-dihydroxyeremophila-7(11), 8(9)-dien-8,12-olide (25), 3β-acetyl-6β, 10α-dihydroxyeremophila- 7(11), 8(9)-dien-8,12-olide (26), (3aR,4R,5S,7aS)-2-acetyl-7a-hydroxy-3a, 4, 5, 6,7, 7a-hexahydro-1H-inden-5-yl acetate (27) by spectroscopic analysis and confirmed by X-ray crystallography analysis. It was revealed that compound 23 has the ability to inhabit the PTP1B in vivo. And its IC50 is 1.30 μg/ml. The third part is a review on the study progress of Eremophilanolides.

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.

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

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

青藏高原栽培青稞遗传多样性研究

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

投加溶胞菌群对剩余污泥消化影响的初步研究

活性污泥法是目前世界上普遍应用的污水生物处理工艺，其在运行过程中产生大量的剩余污泥。由于剩余污泥处理费用巨大及污泥最终处置对环境具有潜在危害问题，污泥的处理和处置已经成为水处理领域关注的焦点。本文利用实验室筛选的溶胞菌群，在好氧消化的同时对污泥进行前处理，促进剩余污泥的破解与溶胞，再通过两相厌氧处理对污泥进行进一步消化，以研究投加溶胞菌对剩余污泥消化的影响。 本研究中溶胞菌污泥减量化技术分为两个部分，第一，污泥在溶胞菌作用下的好氧消化与污泥传统好氧消化的对比研究，利用取自成都三瓦窑污水处理厂剩余污泥，向好氧污泥消化反应器中投加溶胞菌，检测各项污泥指标，并通过同传统好氧污泥消化对比，以研究溶胞菌对污泥好氧消化的影响。第二， 经过溶胞菌处理后好氧消化的剩余污泥进行两相厌氧处理研究。通过建立好氧溶胞联合两相厌氧消化系统的来处理剩余污泥，并与相同条件运行的两相厌氧消化系统做对比，检测运行过程中系统中物质成分变化，研究了其处理能力和运行稳定性，探索了两相厌氧消化系统中的发酵类型差别，验证了好氧溶胞对剩余污泥的破解效果。 研究结果表明：污泥在溶胞菌作用下的好氧消化效果和消化效率均优于传统好氧消化。在溶胞菌群存在的情况下，剩余污泥的TSS和VSS去除率达到40%和53%，远高于传统好氧消化的12%和20%。污泥经过溶胞及好氧消化后，TCOD去除率达到54.4%。经过溶胞菌处理后的剩余污泥再进入两相厌氧处理系统，进入厌氧处理系统的剩余污泥的VSS／TSS比值约为0.62。在两相厌氧处理水力停留时间(HRT)为8d时，溶胞处理污泥厌氧消化后VSS去除率达到55.17%，对照组两相厌氧系统的VSS去除率平均值为18.53%。经过溶胞处理的两相厌氧系统的污泥减量了能力远高于对照组。两相厌氧系统的pH值和碱度说明系统运行较为稳定。产酸相的有机酸中乙酸含量高于丙酸和丁酸，说明发酵末端产物以乙酸为主。在20天的试验周期内，污泥溶胞处理后、两相厌氧系统产甲烷相产气量累积产气量为1.2L，对照组只有375ml。气体中甲烷含量都在55%左右。该研究结果表明，好氧溶胞对污泥有破解能力，溶胞处理对两相厌氧中产酸相水解污泥细胞有明显的促进作用，提高了产酸相的水解酸化能力和效率。该研究对于利用生物溶胞途径提高污泥消化效率具有重要意义。 The actived sludge process has been used more and more extensively, but the procedure will lead to a large quantity of excess sludge. The treatment of Excess activated sludge has becomes a focuses not only for it is a seriously negative effect on environment but also for the costly disposal comes subsequently. The cell lysing bacterium was keeped in our lab to joined in the digestion of the excess activated sludge which was carrying at the same time with pre-processing of sludge to investigated the influence of cell lysing bacterium on excess sludge. There are two part in the method of cell lysing bacterium digesting sludge technology, the first, comparison of excess sludge digestion between anaerobic Cell-lysing Pretreatment and Conventional Aerobic Process. The sludge which was collected from San Wanyao disposal plant in Chengdu was thrown into the aerobic process system with cell-lysing bacterium, then, the indexes were detected to compare the difference between the cell-lysing bacterium in aerobic process and the traditional method to determine the influence of cell-lysing bacterium on aerobic process ; The second, the research on the sludge which was pro-treated with cell-lysing and aerobic digestion in the diphase of anaerobic digestion system. The system of cell-lysing combined with diphase of anaerobic digesting was created to compare to the diphase of anaerobic digested system, the changes of mass constituent was detected to study the ability and steady of disposal. Moreover, the research explored the difference among the types of fermentation. The efficacious of aerobic process was been proved. The result shows that the digesting rate of aerobic process with cell-lysing bacterium was higher than the traditional process. The ratio of sludge is reach to 40%~53%, which was far more effectively than the traditional process rate of 12%~20%. The TCOD of sludge which was treated with cell lysing bacterium and Aerobic Process is reach to 54.4%. Then, the sludge was thrown into the diphase of anaerobic digesting system. VSS／TSS of sludge is 0.62, HRT is 6d, the reduction of VSS is reach to 40.8%. The pH and alkalinity indicate the steady running of the diphase anaerobic digest system. In the acerbity phasing, the content of acetic acid was more than butanoic acid and propanoic acid in organic acid, it is demonstrated that the main composition of final production of fermentation was Acetic Acid. During the 20d of experiment, methylhydride phasing of diphase anaerobic digest system produced 1.2L methylhydride, however, there is only 375ml in CK, the content of methylhydride in all gas phase was around the rate of 55%. The average ratio of VSS was 18.53% in CK diphase anaerobic digest system which was far more unavailable than the mass sludge rate of 55.17%. Results demonstrated that aerobic cell-lysing digested the sludge, the treat of cell-lysing could obviously promoted the hydrolyzeing of sludge cell in the acerbity phasing, which improved the ability and rate of hydrolization and acidification. This study is significant in inhenceing the rate of sludge digestion in the method of cell-lysing bacterium.

eta-production on the proton via electromagnetic and hadronic probes

The reactions pi(-)p -> eta n and gamma p -> eta p are investigated within a dynamical coupled-channels model of meson production reactions in the nucleon resonance region The meson-baryon channels included are pi N, pi Delta, sigma N, and rho N The direct eta-photoproduction process is studied within a formalism based on a chiral constituent quark model approach, complemented with a one-gluon-exchange mechanism, to take into account the breakdown of the SU(6)circle times O(3) symmetry In the models search, the following known nucleon resonances are embodied S-11(1535), S-11(1650), P-11(1440), P-11(1710), P-13(1720), D-13(1520), D-13(1700), D-15(1675), and F-15(1680). Data for the pi(-)p -> eta n reaction from threshold up to a total center-of-mass energy of W approximate to 2 GeV are satisfactorily reproduced For the photoproduction channel: two additional higher mass known resonances, P-13(1900) and F-15(2000), are also considered However, reproducing the data for gamma p -> eta p requires, within our approach, two new nucleon resonances, for which we extract, mass and width

Three-Particle Coincidence of the Long Range Pseudorapidity Correlation in High Energy Nucleus-Nucleus Collisions

We report the first three-particle coincidence measurement in pseudorapidity (Delta eta) between a high transverse momentum (p(perpendicular to)) trigger particle and two lower p(perpendicular to) associated particles within azimuth |Delta phi| < 0.7 in root s(NN) = 200 GeV d + Au and Au + Au collisions. Charge ordering properties are exploited to separate the jetlike component and the ridge (long range Delta eta correlation). The results indicate that the correlation of ridge particles are uniform not only with respect to the trigger particle but also between themselves event by event in our measured Delta eta. In addition, the production of the ridge appears to be uncorrelated to the presence of the narrow jetlike component.

eta production off the proton in a Regge-plus-chiral quark approach

A chiral constituent quark model approach, embodying s- and u-channel exchanges, complemented with a Reggeized treatment for the t channel is presented. A model is obtained allowing data for pi(-)p ->eta n and gamma p ->eta p to be described satisfactorily. For the latter reaction, recently released data by the CLAS and CBELSA/TAPS Collaborations in the system total energy range 1.6 less than or similar to W less than or similar to 2.8 GeV are well reproduced by the inclusion of Reggeized trajectories instead of simple. and. poles. The contribution from "missing" resonances, with masses below 2 GeV, is found to be negligible in the considered processes.

Role of five-quark components in radiative and strong decays of the Lambda(1405) resonance

Within an extended chiral constituent quark model, the three- and five-quark structure of the S-01 resonance Lambda(1405) is investigated. Helicity amplitudes for electromagnetic decays [Lambda(1405)->Lambda(1116)gamma, Sigma(1194)gamma] and transition amplitudes for strong decays [Lambda(1405)->Sigma(1194)pi, K- p] are derived, as well as the relevant decay widths. The experimental value for the strong decay width, Gamma(Lambda(1405)->(Sigma pi)degrees) = 50 +/- 2MeV, is well reproduced with about 50% of a five-quark admixture in the Lambda(1405). Important effects owing to the configuration mixing among Lambda P-2(1)A, Lambda P-2(8)M, and Lambda P-4(8)M are found. In addition, transitions between the three- and the five-quark components in the baryons turn out to be significant in both radiative and strong decays of the Lambda(1405) resonance.

Charged and strange hadron elliptic flow in Cu plus Cu collisions at root s(NN)=62.4 and 200 GeV

We present the results of an elliptic flow, v(2), analysis of Cu + Cu collisions recorded with the solenoidal tracker detector (STAR) at the BNL Relativistic Heavy Ion Collider at root s(NN) = 62.4 and 200 GeV. Elliptic flow as a function of transverse momentum, v(2)(p(T)), is reported for different collision centralities for charged hadrons h(+/-) and strangeness-ontaining hadrons K-S(0), Lambda, Xi, and phi in the midrapidity region vertical bar eta vertical bar < 1.0. Significant reduction in systematic uncertainty of the measurement due to nonflow effects has been achieved by correlating particles at midrapidity, vertical bar eta vertical bar < 1.0, with those at forward rapidity, 2.5 < vertical bar eta vertical bar < 4.0. We also present azimuthal correlations in p + p collisions at root s = 200 GeV to help in estimating nonflow effects. To study the system-size dependence of elliptic flow, we present a detailed comparison with previously published results from Au + Au collisions at root s(NN) = 200 GeV. We observe that v(2)(p(T)) of strange hadrons has similar scaling properties as were first observed in Au + Au collisions, that is, (i) at low transverse momenta, p(T) < 2 GeV/c, v(2) scales with transverse kinetic energy, m(T) - m, and (ii) at intermediate p(T), 2 < p(T) < 4 GeV/c, it scales with the number of constituent quarks, n(q.) We have found that ideal hydrodynamic calculations fail to reproduce the centrality dependence of v(2)(p(T)) for K-S(0) and Lambda. Eccentricity scaled v(2) values, v(2)/epsilon, are larger in more central collisions, suggesting stronger collective flow develops in more central collisions. The comparison with Au + Au collisions, which go further in density, shows that v(2)/epsilon depends on the system size, that is, the number of participants N-part. This indicates that the ideal hydrodynamic limit is not reached in Cu + Cu collisions, presumably because the assumption of thermalization is not attained.

Contributions of qqqq(q)over-bar Components to Axial Charges of Proton and N(1440)

The axial charges of the proton and N(1440) are studied in the framework of an extended constituent quark model (CQM) including qqqq (q) over bar components. The cancellation between the contributions of qqq components and qqqq (q) over bar components gives a natural explanation to the experimental value of the proton axial charge, which can not be well reproduced in the traditional CQM even after the SU (6) circle times O(3) symmetry breaking is taken into account. The experimental value of axial charge pins down the proportion of the qqqq (q) over bar component in the proton to about 20%, which is consistent with the ones given by the strong decay widths and helicity amplitudes. Besides, an axial charge for N(1440) about 1 is predicted with 30% qqqq (q) over bar component, which is obtained by the strong and electromagnetic decays.

Melatonin in Chinese medicinal herbs

Melatonin is a highly conserved molecule that not only exists in animals, but also is present in bacteria, unicellular organisms and in plants. Since melatonin is an antioxidant, in plants melatonin was speculated to protect them from intrinsic and environmental oxidative stress. More importantly, melatonin in edible plants inevitably enters animals and human through feed and food. In this study, more than 100 Chinese medicinal herbs were analyzed using the methods of solid phase extraction and HPLC-FD on-line with MS to determine whether melatonin is present in these commonly used herbs. Melatonin was detected in majority of these plants. Sixty-four of them contain melatonin in excess of 10 ng per gram dry mass. Melatonin levels in several herbs are in excess of 1000 ng/g. It is well known that normal average physiological plasma levels of melatonin are only 10-60 pg/mL. These high level-melatonin containing plants are traditionally used to treat diseases which presumably involve free radical damage. The current study provides new information concerning one potentially effective constituent present in a large number of medicinal herbs. The results suggest that these herbs should be reevaluated in reference to their nutritional and medicinal value. (C) 2003 Elsevier Science Inc. All rights reserved.