滇金足草、凋缨菊和长喙吴萸的化学成分研究

本论文对滇金足草（Goldfussia yunnanensis）、凋缨菊（Camchaya loloana）和长喙吴萸（Evodia vestia）的化学成分进行了研究，通过色谱分离得到40个化合物。主要基于波谱数据鉴定了它们的结构，其中10个为新化合物。 1．从滇金足草地上枝叶的95%乙醇提取物中共分离鉴定了16个化合物：泽漆内酯A（1）、18-羟基泽漆内酯A（2）、18-氧代泽漆内酯A（3）、18-羟基-3-O-β-D-吡喃葡萄糖-泽漆内酯A（4）、3-O-β-D-吡喃葡萄糖-泽漆内酯A（5）、3-O-β-D-吡喃半乳糖-泽漆内酯A（6）、6-E-肉桂酰哈巴俄苷（7）、E-哈巴俄苷（8）、5，6-异亚丙二氧基哈巴俄苷（9）、β-谷甾醇（10）、β-胡萝卜苷（11）、齐墩果酸（12）、肉桂酸（13）、麦角固醇（14）、硬脂酸（15）和丁二酸（16）。其中2-7为新化合物。5，6-异亚丙二氧基哈巴俄苷（9）以人工产物形式得到。 2．从凋缨菊地上枝叶的95%乙醇提取物中分离并鉴定了13个化合物：凋缨菊内酯A~C (17-19)、1β-乙酰基凋缨菊内酯C(20)、b-谷甾醇（10）、β-胡萝卜苷（11）、羽扇豆醇（21）、桦木醇（22）、桦木酸（23）、芥子醇（24）、紫丁香苷（25）、咖啡酸（26）和熊果酸（27）。其中化合物17-20为桉叶烷内酯类新化合物。化合物17、18、20对细胞株HepG2的GI50依次为7.80、7.08、4.99 µg/mL。 3．从长喙吴萸（E. vestia）地上枝叶的95%乙醇提取物中分离并鉴定了13个化合物：佛手内酯（28）、花椒毒素（29）、异茴芹内酯（30）、七叶内酯（31）、东莨宕素（32）、瑞香素（33）、异紫花前胡内酯(34)、茵芋碱（35）、山刈碱（36）、白鲜碱（37）、黄柏酮（38）、柠檬苦素（39）和对羟基苯甲醛（40）。 4．综述了1990—2007年期间从菊科植物中发现的桉叶烷-12，6内酯的化学结构、生物活性、生物转化及化学合成方面的研究进展。 Phytochemical investigation on Goldfussia yunnanensis, Camchaya loloana, and Evodia vestia, led to the isolation of 40 compounds, 10 of which were new ones. 1. Six new compounds were isolation from 95% ethanolic extract of the aerial parts of G. yunnanensis, and identified as 18-hydroxyhelioscopinolide A (2), 18-oxohelioscopinolide A (3), 18-hydroxy-3-O-β-D-glucopyranosylhelioscopinolide A (4), 3-O-β-D-glucopyranosylhelioscopinolide A (5),3-O-β-D-Galactopyranosyl helioscopinolide A (6), 6-O-trans-cinnamoyl E-harpagoside (7). The known compounds isolated were helioscopinolide A (1), E-harpagoside A (8), 5,6-isopropylidene E-harpagoside A (9), β-sitosterol (10), β-daucosterol (11), oleanolic acid (12), cinnamic acid (13), ergosterol (14), stearic acid (15) and succinic acid (16). Compound 9 was an artifact. 2. Four new compounds, loloanolides A – C (17 - 19) and 1β-acetoxy-loloanolide C (20), were isolation from 95% ethanolic extract of the aerial parts of C. loloana. The known ones were β-sitosterol (10), β-daucosterol (11), lupeol (21), betulin (22), betulinic acid (23), sinapyl (24), syringin (25), caffeic acid (26) and ursolic acid (27). The GI50 values of compounds 17, 18 and 20 to HepG2 cell line were 7.80, 7.08 and 4.99 µg/mL, respectively. 3. Thirteen were isolated from 95% ethanolic extract of the aerial parts of E. vestia for the first time. They were determined to be bergapten (28), xanthotoxin (29), isopimpinellin (30), esculetin (31), scopoletin (32), daphnetin (33), marmesin (34), skimmianine (35), confusameline (36), dictamine (37), obacunone (38), limonin (39) and p-hydroxy phenyl aldehyde (40). 4. The structures, biological activities, biotransformation and chemical syntheses of eudesmane-12, 6-olides from the Asteraceae during 1990-2007 were reviewed.

绵参和地榆的化学成分研究

本论文由三章组成。第一章为综述，概述了植物中环烯醚萜类化合物的研究进展；第二和第三章为实验论文，分别报道了唇形科药用植物绵参和蔷薇科药用植物地榆的化学成分研究。 第一章概述了植物中环烯醚萜类化合物的研究成果，主要包括结构类型及药理活性等方面。 第二章包括两个部分。第一部分报道了藏药绵参（Eriophyton wallichii Benth）地上部分甲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7个化合物，有6个化合物为首次从该植物中分离得到，分别为β-谷甾醇（1），夏至草苦素（marrubiin，2），乌苏酸（3），cimigoside（4），5-deoxyantirrhinoside（5），8-表马钱子酸葡萄糖苷（8-epiloganic acid，6）和apigenin 7-(6''-p-coumaroyl)glucoside（7）。第二部分，采用高效液相色谱－质谱联用技术对绵参地上部分的甲醇提取物进行了分析，通过标准品对照紫、外光谱分析以及多级质谱分析与文献对照鉴定了8个成分，分别是：8-epiloganic acid（Ⅰ），quercitrin 3-glucoside-7-(6''-p-coumaroyl)glucoside（Ⅱ），ajugoside(I) （Ⅲ），chrysoeriol 7-O-E-p-coumaroyl-3-O-b-D-glucoside（Ⅳ），helichrysoside（Ⅴ），生物碱（Ⅵ），apigenin 2,3-dihydrogen-7-(6''-p-coumaroyl) glucoside（Ⅶ），apigenin 7-(6''-p-coumaroyl) glucoside（Ⅷ）。 第三章报道了中药地榆根部乙醇提取物正丁醇相的化学成分，通过正、反相硅胶柱层析等各种分离方法，从中分离得到8个化合物，分别为3,4¢- O-二甲基逆没食子酸（8），3,3¢,4¢-O-三甲基逆没食子酸（9）和3,4¢-O-二甲基逆没食子酸-4-O-b-D-木糖苷（10），19a-羟基-3-O-(a-L-阿拉伯糖)乌苏酸-28-O-b-D-葡萄糖苷（11）， 3b-[(a-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien-28-oic acid b-D- glucopyranosyl ester（13），3-O-a-L-arabinopyranosyl-urs-12,18(19)-dien-28-oic acid b-D-glucopyranosyl ester（14），儿茶素（15），还有一种可能是皂苷11的工作产物（12）。 This dissertation consisted of three chapters. The first chapter elaborated the progress of iridoids occurring in plants. The later two chapters respectively elaborated the chemical constituents of Eriophyton wallichii Benth. and Sanguisorba officinalis L. The first chapter is a review of the research progress of iridoids occurring in plants, which includes their structure and pharmacology. The second chapter consisted of two parts. The first part is about the chemical constituents of methanol extraction from the aerial parts of Eriophyton wallichii Benth. Seven compounds were isolated and identified. Among them, the compounds of marrubiin, ursolic acid, cimigoside, 5-deoxyantirrhinoside, 8-epiloganic acid，apigenin 7-(6''-p-coumaroyl)glucoside were firstly reported in this plant. A HPLC-MSn method was developed for rapid identification of major compounds of Eriophyton wallichii. A total of 8 peaks in the chromatograms were unequivocally determined (peaks 1, 8) or tentatively identified (peaks 2-7) based on the detailed UV and tandem mass spectra analysis. Seven components were identified as 8-epiloganic acid（Ⅰ），Quercitrin 3-glucoside-7-(6''-p-coumaroyl)glucoside（Ⅱ），ajugoside(I)（Ⅲ），Chrysoeriol 7-O-E-p-coumaroyl-3-O-b-D-glucoside（Ⅳ），helichrysoside（Ⅴ），apigenin 2,3-dihydrogen-7-(6''-p-coumaroyl) glucoside（Ⅵ），apigenin 7-(6''-p-coumaroyl) glucoside（Ⅶ）。 The third chapter elaborated the chemical constituents of methanol extraction from Sanguisorba officinalis L, eight compounds were isolated from this plant by repeat column chromatography over silica gel. These compounds were identified as 3,4′-O-dimethylellagic acid, 3,3′,4′-O-trimethylellagic acid, 3,4′-O-dimethylellagic acid-4-O-b-D-xyloside, 3b-O-a-L-arabinopyranosyl-19a- hydroxyl-urs-12-en-28-oic acid 28-b-D-glucopyranoside, 3b-[(a-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien- 28-oic acid b-D-glucopyranosyl ester，3-O-a-L–arabinopyranosyl-urs-12,18(19) -dien-28-oic acid b-D-glucopyranosyl ester, catechin.

尼泊尔水东哥、水麻、木姜冬青和青荚叶的化学成分研究

活性筛选中发现尼泊尔水东哥 (Saurauia napaulensis DC.) 树皮95%乙醇提取物具有α-淀粉酶抑制活性、水麻(Debregeasia orientalis) 枝叶95%乙醇提取物显示血管紧张素转化酶(ACE)抑制活性、青荚叶(Helwingia japonica (Thunb.) Dieter.) 95%乙醇提取物的中小极性部分显示蛋白酪氨酸磷酸酯酶(PTP)1B抑制活性。为全面了解它们的成分及相关活性成份，主要运用硅胶柱层析方法从这三个植物分离得到39个化合物，通过波谱分析或与已知品对照的方法对其进行了鉴定。对木姜冬青(Ilex litseaefolia Hu et Tang)的成分做了进一步的研究，取得了如下结果。 1. 从尼泊尔水东哥树皮的95%乙醇提取物分离并鉴定12个化合物： auranamide、aurantiamide benzoate、齐墩果酸、β-谷甾醇、β-胡萝卜甙、乌苏酸、2α,3α-二羟基-12-烯-28-乌苏酸、2α,3β,24-三羟基-12-烯-28-乌苏酸、(2S,3S,4R,10E)-2-[(2'R)-2' -hydroxytetracosanoylamino] -10-octadecene -1,3,4-triol、 2α,3α,24-三羟基-12-烯-28-齐墩果酸、2α,3β-二羟基-12-烯-28-乌苏酸和2α,3α,24-三羟基-12-烯-28-乌苏酸。 2. 从水麻枝叶的95%乙醇提取物分离并鉴定了18个化合物：棕榈酸、二十烷酸、二十烷酸甲酯、β-谷甾醇、Monogynol A、桦木酸、Hederagenin、β-胡萝卜甙、18αH-19(29)-烯-3-酮-乌苏烷、3，4-开环-20(30)-烯-乌苏烷-3-酸、Pomolic acid，表儿茶素、儿茶素、槲皮素、槲皮素-3-O-β-D-吡喃葡萄糖苷、紫丁香苷、紫丁香酚苷和山萘酚-3-O-芸香糖。儿茶素、槲皮素和槲皮素-3-O-β-D-吡喃葡萄糖苷为具有ACE抑制活性的成分。 3. 从木姜冬青95%乙醇提取物的乙酸乙酯部分分离并鉴定了5个化合物： 2-O-β-D-吡喃葡萄糖-6,2´-二羟基-4,4´-二香草酰氧甲基-1,1´-二苯醚（冬青苷）和四个已知化合物：七叶内酯、香草酸、3,4-二甲氧基苯乙酸和vanilloylcalleryanin。冬青苷为新化合物。 4. 从青荚叶95%乙醇提取物的中小极性部分分离并鉴定了9个化合物：β-谷甾醇、β-胡萝卜苷、羽扇豆醇、桦木醇、桦木酸、棕榈酸甘油酯、桂皮酸、6αH-4-烯-3-酮-豆甾醇和6βH-4-烯-3-酮-豆甾醇。 5. 对1985-2006年间天然二苯醚类化合物及活性研究进展进行综述. The in vitro test indicated that the 95% ethanolic extract of the barks of Saurauia napaulensis DC showed α-amylase inhibitory activity, the 95% ethanolic extract of the whole plants of Debregeasia. orientalis showed angiotensin converting enzyme (ACE) inhibitory activity and some fractions of the 95% ethanolic extract of the aerial parts of Helwingia japonica showed protein tyrosine phosphatase (PTP)1B inhibitory activity. In order to investigate components and active compounds of the three plants, they were chemically studied mainly using. Thirty-nine compounds were isolated predominantly by column chromatography identified by spectral methods or comparing them with authentic samples. Further investigation of Ilex litseaefolia Hu et Tang was carried out. Major results are as follows: 1. Twelve compounds were isolation from the 95% ethanolic extract of the barks of S. napaulensis DC. They were identified as auranamide, aurantiamide benzoate, oleanolic acid, β-sitosterol, β-daucosterol, ursolic acid, 2α,3α-dihydroxyurs-12-en-28-oic acid, 2α,3β,24-trihydroxyurs-12-en-28-oic acid, (2S,3S,4R,10E)-2-[(2'R)-2'-hydroxytetracosanoyl amino]-10-octadecene-1,3,4-triol, 2α,3α,24 -trihydroxyolean-12-en-28-oic acid, 2α,3β-dihydroxyurs-12-en-28-oic acid, and 2α,3α,24-trihydroxyurs-12-ene-28-oic acid, respectively, by spectral methods or comparing them with authentic samples. 2. Eighteen compounds were isolation from the 95% ethanolic extract of the whole plants of D. orientalis. They were identified as palmitic acid, henicosanoic acid, henicosanoic acid methyl ester, β-sitosterol, monogynol, betulinic acid, hederagenin, β-daucosterol, 18αH-urs-20(30)-en-3-one, 3,4-seco-urs-20(30)-en-3-oic acid, pomolic acid, (-)-epicatechin, (+)-catechin, quercetin, quercetin 3-O-β-D-glucopyranoside, syringin, syringiaresinol digloside and kaempferol-3-O-rutinose. (+)-Catechin, quercetin and quercetin 3-O-β-D-glucopyranoside were the ACE inhibitory active components. 3. Further phytochemical investigation of the ethyl acetate parts of 95% ethanolic extract of the whole plant of I. litseaefolia afforded 2-O-β-D-glucopyranose-4,4´-di-vanilloyloxymethyl-2,6´-dihydroxy-1,1´-diphenyl ether (ilexiside), esculetin, vanillic acid, 3,4-dimethoxybenzylacetic acid and vanilloylcalleryanin. Ilexiside was new compound. 4. Nine compounds were isolation from the 95% ethanolic extract of the whole plant of H. japonica: β-sitosterol, β-daucosterol, lupeol, betulin, betulinic acid, glycerol monopalmitate, cinnamic acid, stignast-4-en-6β-3-one and stignast-4-en-6α-3-one 5.Diphenyl ether compounds from nature between 1985-2006 were summarized.

四种药用植物的化学成分及芍药苷的微生物转化研究

本学位论文共有5章。第一章报道白芍的化学成分及芍药苷的微生物转化研究成果；第二章报道天山雪莲的化学成分研究；第三章报道两面针的化学成分研究；第四章报道通关藤的化学成分研究成果；第五章概述了花椒属植物中最近十年报道的新化合物及药理研究情况。 在第1章的第一部分报道了白芍（Paeonia lactiflora Pall.）的化学成分。我们采用正、反相硅胶柱层析等各种分离方法，从白芍的干燥根中共分离出14个化合物，其中1个为新化合物，其结构通过波谱分析证实为没食子酰白芍苷，另外还有2个为首次从该植物中分离得到。第二部分报道了芍药苷的微生物转化生产芍药苷代谢素-I的研究，从15株厌氧菌中筛选出10株有转化活性的菌株，其中短乳杆菌Lactobacillus brevis AS1.12的转化活性最好，对其转化条件进行了初步的筛选，确定了相对合理的转化工艺。 在第2章报道了天山雪莲（Saussurea involucrate Kar.et Kir.）全草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，共分离鉴定了28个化合物，结构类型分属于黄酮、倍半萜和木脂素等，其中2个新倍半萜化合物的结构分别表征为6α-羟基云木香酸6-β-D-吡喃葡萄糖苷和11βH-11,13-二氢去氢云木香内酯8α-O-(6′-乙酰)-β-D-吡喃葡萄糖苷。 第3章报道了两面针（Zanthoxylum nitidum （Roxb.）DC.）干燥根的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等波谱解析以及X-射线单晶衍射，共分离鉴定了16个生物碱，结构类型分属于苯并啡啶类、喹啉类和阿朴啡类等，其中2个新苯并啡啶类生物碱的结构分别表征为二聚双氢两面针碱和丙酮基双氢崖定椒碱。 第4章报道了通关藤（Marsdenia tenacissima (Roxb.) Wight et Arn.）水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等波谱解析以及X-射线单晶衍射，共分离鉴定了14个化合物，结构类型均属于C21多羟基甾醇，其中4个新化合物tenacigenoside A, tenacigenoside B, tenacigenoside C和tenacigenoside D的结构分别表征为3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-17β-tenacigenin B (62), 3-O-2,6- dideoxy-4-O-methyl-D-lyxo-hexopyranosly-11α-O- methylbutyryl-12β-O-acetyl-tenacigenin B (63), 3-O-6-deoxy-3-O-methyl-β-D- allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-tigloyl-tenacigenin C (64)和3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-2- methylbutyryl-tenacigenin C (65)。 第5章概述了花椒属植物的化学成分及药理活性研究进展。 This dissertation consists of 5 chapters. The first chapter elaborate the phytochemical investigation of Paeonia lactiflora Pall., and microbial transformation of paeoniforin. The second, third and four chapters elaborate the phytochemical investigation of Saussurea involucrate Kar.et Kir., Zanthoxylum nitidum (Roxb.) DC. and Marsdenia tenacissima (Roxb.) Wight et Arn., respectively. Chapter 5 is a review on chemical constituents and bioactivities of Zanthoxylum species. The part one of chapter 1 focus on the isolation and identification of chemical constituents from P. lactiflora. Fourteen compounds were isolated from the roots of P. lactiflora by repeat column chromatography over normal and reversed phase silica gel. Among them, one is a new compound and the structure was suggested as galloyl-albiflorin by spectral evidence. In addition, two compounds were firstly reported in this plant. The part 2 is about microbial transformation of paeoniforin. Chapters 2, 3 and 4 were isolations and identifications of chemical constituents from S. involucrate, Z. nitidum and M. tenacissima, respectively. From the aerial parts of S. involucrate, 28 compounds including 7 flavonoids and 13 sesquiterpenoids were isolated and identified. Among them, 2 new compounds were characterized as 6α-hydroxycostic acid 6-β-D-glucoside and 11βH-11,13-dihydrodehydro- costuslactone 8α-O-(6'-acetyl)-β-D-glucoside, respectively, by means of spectroscopic analysis. Otherwise, 11 ones were firstly reported from this plant. The third chapter is about the phytochemical investigation of Z. nitidum. Sixteen compounds were isolated and identified. Among them, 2 new benzophenanthridine alkaloids were characterized as 8-acetonyldihydrofagaridine and 1,3-bis(8-dihydronitidinyl)-acetone by spectroscopic analysis. The fourth chapter is about the phytochemical investigation of M. tenacissima. Fourteen compounds were isolated and identified. Among them, 4 new compounds, tenacigenosides A~D, were characterized as 3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-17β- tenacigenin B, 3-O-2,6-dideoxy-4-O-methyl-D-lyxo-hexopyranosly-11α-O-methyl butyryl-12β-O-acetyl-tenacigenin B, 3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl- (1→4)-β-D-oleandropyranosyl-11α-O-tigloyl-tenacigenin C, and 3-O-6-deoxy-3-O- methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-2-methylbutyryl- tenacigenin C. Chapter 5 is a review on recent progress in bioactive constituents from plants of Zanthoxylum 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.

五枫藤、小驳骨和川西茶藨的化学成分研究

八月瓜属植物五枫藤(Holboellia latifolia Wall.)和驳骨草属植物小驳骨(Gendarussa vulgaris Nees)均为药用植物, 前者化学成分研究不深入, 后者的化学成分未见报道。川西茶藨(Ribes takare D. Don)为茶藨子属植物, 没有化学成分的报道。本论文对三个植物的化学成分和活性成分进行了研究, 主要通过色谱方法分离得到了48 个化合物, 采用波谱分析或与已知标准品对照等手段鉴定了它们的结构, 其中有1 个新的原小檗碱类化合物和3 个新的联苯类化合物,发现了具有细胞毒活性和α-葡萄糖苷酶抑制活性的化合物。1、从五枫藤地上部分的95%乙醇提取物中分离得到了12 个化合物: 五加苷K (1)、hederagenin 3-O- α-L-rhamnopyranosyl-(1→2)- α-L-arabinopyranoside (2)、β-萘乙酸(3) 、3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-α-L-arabinopyranosyl oleanolic acid 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (4) 、3-O- α-L-rhamnopyranosyl-(1→2)-O- β- D-glucopyranosyl-(1→2)- α-L-arabinopyranosyl oleanolic acid (5) 、3-O-( β-D-glucopyranosiduronic acid)-oleanolic acid 28-O- β-D-glucopyranoside (6)、lup-20(29)-en-3-one (7)、lupeol (8)、β-谷甾醇(9)、齐墩果酸(10)、乌苏酸(11)、β-胡萝卜苷(12)。化合物1 对Lu-06、N-04 和Bre-04 癌细胞株的GI50 分别是0.77µg/mL、1.26 µg/mL 和1.55 µg/mL, 化合物2 对N-04 癌细胞株的GI50 为2.44 µg/mL。2、从小驳骨地上部分的95%乙醇提取物中分离得到了1 个原小檗碱类新化合物13-hydroxyl gusanlung A (25), β-谷甾醇(9)、齐敦果酸(10)、β-胡萝卜苷(12)、棕榈酸(1-)甘油酯(13)、棕榈酸(14)、阿苯哒唑(15)、阿苯哒唑砜(16)、阿苯哒唑亚砜(17)、aurantiamide acetate (18)、华良姜素(19)、芫花素(20)、(-)-丁香树酯醇(21)、gusanlung B (22) 、eupteleasaponinsⅤ acetate (23)、gusanlungA (24)、刺五加苷E (26)、岩白菜素(27)、咖啡酸(28)。化合物25 对肝癌细胞株(HepG2) 的GI50 为2.08 µg/mL。3、从川西茶藨地上部分的95%乙醇提取物中分离鉴定了22 个化合物: β-谷甾醇(9) 、β- 胡萝卜苷(12) 、O-acetyloleanolic aldehyde (29),4,7,8-trimethoxy-2,3-methylenedioxydibenzofuran (30) 、3', 5-dimethoxy-3, 4-methylenedioxybiphenyl (31) 、桦木醇(32) 、6,7-dimethoxy-1-methyl-3,4-dihydroquinolin-2-one (33)、3'-hydroxy-5-methoxy-3,4-methylenedioxybiphenyl (34) 、7-hydroxy-4,8-dimethoxy-2,3-methylenedioxydibenzofuran (35)、桦木醛(36)、没食子酸(37) 、6β- 羟基-4- 烯-3- 酮- 豆甾醇(38) 、5α, 8α-epidioxy-(22E,24R)-ergosta-6, 22-dien-3β-ol (39)、verrucofortine (40)、6-methoxycalpogoniumisoflavone A (41)、2-羟基二苯甲酮(42)、桦木酸(43), 3, 5-二甲氧基苯甲酸-4-O-β-D-吡喃葡萄糖苷(44)、洋芹素(45)、刺槐素(46)、水杨酸(47)、洋芹素-5-O- β-D-葡萄糖苷(48), 化合物30、31 和35 为新的联苯化合物。化合物30的α-葡萄糖苷酶抑制率为10.2% (1.00 mg/mL); 化合物35 的抑制率为17.2% (1.00mg/mL)。4、综述了1960 年以来原小檗碱类化合物药理活性研究进展。 Plants Holboellia latifolia Wall and Gendarussa vulgaris Nees, are used as folkmedicine. Ribes takare D. Don belongs to the genus Ribes. The three plants have notbeen chemically studied in detail. Chemical and bioactive study of three plants led tothe isolation of 48 compounds by chromatography. Their structures were elucidatedon the basis of spectroscopic evidence or comparison with authentic samples. Amongthe 48 componds isolated one protoberberine alkaloid and three biphenyls are newones. Cytotoxic and α-glucosidase inhibitory compounds had been found.1. Twelve compounds were isolated from the 95% ethanol extract of the aerial partof H. latifolia Wall. They were characterized as fellow: eleutheroside K (1),hederagenin-3-O- α-L-rhamnopyranosyl-(1→2)- α-L-arabinopyranoside (2),2-naphthyl acetic acid (3),3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-α-L-arabinopyranosyl oleanolic acid 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (4), 3-O- α-L-rhamnopyranosyl-(1→2)-O- β- D-glucopyranosyl-(1→2)- α-L-arabinopyranosyl oleanolic acid (5),3-O-( β-D-glucopyranosiduronic acid)-oleanolic acid-28-O- β-D-glucopyranoside (6),lup-20(29)-en-3-one (7), lupeol (8), β-sitosterol (9), oleanolic acid (10), ursolicacid (11), and β-daucosterol (12). Compound 1 showed moderate cytotoxicity againstLu-06 (GI50, 0.77 µg/mL), N-04 (GI50, 1.26 µg/mL) and Bre0-4 (GI50=1.55 µg/mL)and compound 2 showed moderate cytotoxicity against N-04 (GI50=2.44 µg/mL).2. A new protoberberine alkaloid, 13-hydroxyl gusanlung A (25), was isolated fromthe aerial part of Gendarussa vulgaris Nees, together with β-sitosterol (9), oleanolicacid (10), β-daucosterol (12), glycerol monopalmitate (13), palmific acid (14),albendazole (15), albendazole sulphone (16), albendazole sufloxide (17), aurantiamideacetate (18), kumatakenin (19), genkwanin (20), (-)-syringaresinol (21), gusanlung B(22), eupteleasaponinsⅤ acetate (23), gusanlung A (24), eleutheroside E (26),bergenin (27) and caffeic acid (28). Compound 25 showed cytotoxicity against HepG2 cells (GI50, 2.08 µg/mL).3. Phytochemical study of the Ribes takare D. Don led to the isolation of three newbiphenyls, 4,7,8-trimethoxy-2,3-methylenedioxydibenzofuran (30), 3', 5-dimethoxy-3,4-methylenedioxybiphenyl (31) and 7-hydroxy-4,8-dimethoxy-2,3-methylenedioxydibenzofuran (35), along with nineteenknown compounds, β-sitosterol (9), β-daucosterol (12), O-acetyloleanolic aldehyde(29), betulin (32), 6,7-dimethoxy-1-methyl-3,4-dihydroquinolin-2-one (33),3'-hydroxy-5-methoxy-3, 4-methylenedioxybiphenyl (34), betulinic aldehyde (36),gallic acid (37), stigmast-4-en-6β-ol-3-one (38), 5α, 8α-epidioxy-(22E, 24R)-ergosta-6,22-dien-3β-ol (39), verrucofortine (40), 6-methoxycalpogonium isoflavone A (41),2-hydroxybenzophenone (42), betulinic acid (43), 3,5-dimethoxygallic acid-4-O- β-D-glucopryranoside (44), apigenin (45), acacetin (46), salicylic acid (47) andapigenin-5-O- β-D-glucopryranoside (48). α-Glucosidase inhibitory rates ofcompound 30 and 35 were respectively 10.2% and 17.2% at a concentration of 1.00 mg/mL).4. Pharmacological activities of protoberberines were summarized.

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.

UV-vis spectrophotometric titrations and vibrational spectroscopic characterization of meso-(p-hydroxyphenyl)porphyrins

Sequentially spectrophotometric titrations by sodium hydroxide of meso-tetraphenylporphyrin derivatives bearing one, two, three, or four p-hydroxyl groups result in new types of spectra. The strong new bands appear in the visible region with splitting or broadening of the Soret band and its significant loss of oscillator strength. To understand the molecular origin of these phenomena, the Resonance Raman (RR) and Fourier Transform Infrared (FTIR) experiments are carried out. The results demonstrate that the charges of the deprotonated para-hydroxy substituted meso-tetraphenylporphyrins are localized on the substituents, not delocalized into the pi system of the porphyrin macrocycles and that the ground states of the macrocycles remain essentially unperturbed. Both the related behavior of diprotonated tetrakis(p-(dimethylamino)phenyl) porphyrin and protonated Schiff base porphyrins show that the new bands considered as hyperporphyrin spectra are due to pi(phenoxide anion) --> pi*(porphyrin) transitions, where pi is an orbital on the phenoxide anion substitutent and pi* is a LUMO on the porphyrin.

Structure identification of a prenylflavonol glycoside from Epimedium koreanum by electrospray ionization tandem mass spectrometry

A novel prenylflavonol glycoside, named acetylicariin, has been isolated from the aerial parts of Epimedium koreanum Nakai. The structure has been identified by electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn) and other chemical evidence, which has been elucidated as 8-prenylkaempferol-4'-methoxyl-3-O-alpha-L-rhamnopyranosyl-7-O-beta-D-(2''-O-acetyl)glucopyranoside.

A new acylated iridoid glucoside from Avicennia marina

A new acylated iridoid glucoside, namely, 2'-O-(5-phenyl-2E, 4E-pentadienoyl)mussaenosidic acid, was isolated from the aerial parts of the mangrove plant Avicennia marina. The structure of the new compound was established on the basis of various NMR spectroscopic analyses, including 2D NMR techniques (H-1-H-1 COSY, HMQC, and HMBC) and HR-FAB-MS. This compound displayed moderate antioxidant activity.

Modern changes of tidal troughs among the radial sand ridges in northern Jiangsu coastal zone

Using satellite images taken on different dates, GIS analysis of aerial photos, bathymetric maps and other field survey data, tidal troughs and major sand ridges in the northern Jiangsu coastal area were contrasted. The results show that there have been three types of movement or migration of tidal trough in this area: (1) Periodic and restricted, this type of trough usually developed along the beaches with immobile gully head as a result of the artificial dams and the swing range increased from gully head to the low reaches, so they have been obviously impacted by human activity and have longer swing periods; (2) Periodic and actively, this kind of trough, which swung with a fast rate and moved periodically on sand ridges, were mainly controlled by the swings of the host tidal troughs and hydrodynamic forces upon tidal sand ridge and influenced slightly by human constructions; (3) Steadily and slowly, they are the main tidal troughs with large scale and a steady orientation in this area and have slow lateral movement. The differences in migration mode of tidal trough shift result in different rates of migration and impact upon tidal sand ridges. Lateral accumulation on current tidal trough and deposition on abandoned tidal troughs are the two types of sedimentation of the tidal sand ridges formation. The whole radial sand ridge was generally prone to division and retreat although sand ridges fluctuated by the analysis of changes in talwegs of tidal troughs and shorelines of sand ridges.

Impact of Brunswick river mouth training walls on adjacent beaches, Brunswick heads, New South Wales, Australia

River training walls have been built at scores of locations along the NSW coast and their impacts on shoreline change are still not fully understood. In this study, the Brunswick River entrance and adjacent beaches are selected for examination of the impact of the construction of major training walls. Thirteen sets of aerial photographs taken between 1947 and 1994 are used in a CIS approach to accurately determine tire shoreline Position, beach contours and sand volumes, and their changes in both time and space, and then to assess the contribution of both tire structures and natural hydrodynamic conditions to large scale (years-decades and kilometres) beach changes. The impact of the training walls can be divided into four stages: natural conditions prior to their construction (pre 1959), major downdrift erosion and updrift accretion during and. following the construction of the walls in 1959 similar to 1962 and 1966. diminishing impact of the walls between 1966 and 1987, and finally no apparent impact between 1987 similar to 1994. The impact extends horizontally about 8 km updrift and 17 km downdrift, and temporally up to 25 years..

Net primary productivity and spatial distribution of vegetation in an alpine wetland, Qinghai-Tibetan Plateau

To initially describe vegetation structure and spatial variation in plant biomass in a typical alpine wetland of the Qinghai-Tibetan Plateau, net primary productivity and vegetation in relationship to environmental factors were investigated. In 2002, the wetland remained flooded to an average water depth of 25 cm during the growing season, from July to mid-September. We mapped the floodline and vegetation distribution using GPS (global positioning system). Coverage of vegetation in the wetland was 100%, and the vegetation was zonally distributed along a water depth gradient, with three emergent plant zones (Hippuris vulgaris-dominated zone, Scirpus distigmaticus-dominated zone, and Carex allivescers-dominated zone) and one submerged plant zone (Potamogeton pectinatus-dominated zone). Both aboveground and belowground biomass varied temporally within and among the vegetation zones. Further, net primary productivity (NPP) as estimated by peak biomass also differed among the vegetation zones; aboveground NPP was highest in the Carex-dominated zone with shallowest water and lowest in the Potamogeton zone with deepest water. The area occupied by each zone was 73.5% for P. pectinatus, 2.6% for H. vulgaris, 20.5% for S. distigmaticus, and 3.4% for C. allivescers. Morphological features in relationship to gas-transport efficiency of the aerial part differed among the emergent plants. Of the three emergent plants, H. vulgaris, which dominated in the deeper water, showed greater morphological adaptability to deep water than the other two emergent plants.

Jiangella gansuensis gen. nov., sp nov., a novel actinomycete from a desert soil in north-west China

A novel actinomycete strain, designated YIM 002(T), was isolated from a desert soil sample in Gansu Province, north-west China. This actinomycete isolate formed well-differentiated aerial and substrate mycelia. In the early stages of growth, the substrate mycelia fragmented into short or elongated rods. Chemotaxonomically, it contained LL-2,6-diaminopimelic acid in the cell wall. The cell-wall sugars contained ribose and glucose. Phospholipids present were phosphatidylinositol mannosides, phosphatidylinositol and diphosphatidylglycerol. MK-9(H-4) was the predominant menaquinone. The major fatty acids were anteiso C-15:0 (35.92%), anteiso C-17:0 (15.84%), iso C-15:0 (10.40%), iso C-16:0 (7.07%) and C(17:10)w8c (9.37%). The G+C content of the DNA was 70 mol%. Phylogenetic analysis and signature nucleotide data based on 16S rRNA gene sequences showed that strain YIM 002(T) is distinct from all recognized genera of the family Nocardioidaceae in the suborder Propionibacterineae. On the basis of the phenotypic and genotypic characteristics, it is proposed that isolate YIM 002(T) be classified as a novel species in a new genus, Jiangella gansuensis gen. nov., sp. nov. The type strain is YIM 002(T) (= DSM 44835(T) = CCTCC AA 204001(T) = KCTC 19044(T)).

Isolation, characterization and crystal structure of natural eremophilenolide from Ligularia sagitta

A new eremophilenolide 1beta, 10beta-epoxy-6beta-acetoxy-3beta-angeloyloxy-8beta-hydrox y-eremophil-7(11)-en-8, 12alpha-olide (1), together with liguhodgsonal (2), esculetin (3) and beta-sitosterol (4), was isolated from the aerial parts of Ligularia sagitta. The structure of the new constituent (1) was elucidated by spectroscopic methods and confirmed by single-crystal X-ray diffraction.