唐古特瑞香和大果大戟的化学成分研究

本学位论文由两部分共3章组成。第一部分分别报道2种藏药唐古特瑞香和大果大戟化学成分的研究成果，从2种药用植物共分离鉴定了60个不同的化合物，其中12个为新结构，特别有意义的是发现了2个具有同一新骨架的二萜化合物。第二部分概述了大戟科植物多环二萜的研究进展。 第一部分包括第1和2章。在这2章中分别报道了唐古特瑞香（Daphne tangutica Maxim）和大果大戟（Euphorbia wallichii Hook. f. Fl）化学成分的分离纯化与结构鉴定。实验采用正、反相硅胶柱层析、薄层制备及HPLC等分离方法，从唐古特瑞香的根皮中共分离出32个化合物，通过红外、质谱及核磁共振等波谱方法鉴定了其中的31个，结构类型分别属于瑞香二萜类、木脂素类、香豆素类、苯丙素类及甾体类，其中有三个新的瑞香二萜型化合物，经波谱分析将它们的结构分别鉴定为1,2a-二氢-20-棕榈酰瑞香毒素、1,2a-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯及1,2b-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯，另外还有13个已知化合物为首次从该植物中分离得到。从大果大戟的根部共分离出33个化合物，鉴定了其中的30个，其主要成分为种类丰富的二萜，包括巨大戟烷型、续随子烷型、对映－阿替生烷型、对映－贝壳杉烷型、对映－松香烷型、ent-trachylobane型、对映－异海松烷型及一新骨架五环二萜ent-wallichane型，另外还有香豆素、甾体、三萜和一些简单的小分子化合物。其中新化合物有9个，经波谱分析将它们的结构分别鉴定为5-O-(2E,4E,6E)-癸三烯酰基-3,20-O-二乙酰基巨大戟醇、5-O-(2E,4Z)-癸二烯酰基-3-O-乙酰基-20-去氧巨大戟醇、3-O-(2E,4Z)-癸二烯酰基-5b,6b-氧-交京大戟醇、7-苯甲酰氧基-3,5,15-三乙酰基-续随子醇、ent-trachylobane-3-one-17-oic-acid、3α-羟基-对映-阿替斯-16-烯-14-酮、3α,6-二羟基-对映-异海松-7-烯-2,15-二酮、wallichanol A 和 wallichanol B，其中，wallichanol A 和 wallichanol B属于一新骨架类型的五环二萜。除此以外，另有13个已知化合物为首次从该植物中分离得到。 第2部分即第3章，首次概述了大戟属植物中多环二萜的化学和药理研究进展。 This dissertation is composed by two parts. The first part reports the phytochemical investigation of two Tibetan medicine plants, Daphne tangutica Maxim and Euphorbia wallichii Hook. f. Fl. Sixty different compounds including ten new compounds and two novel diterpenoids possessing a new carbon skeleton were isolated and identified. The second part is a review about the progress of studies on the polycyclic diterpeniods of the plant family of Euphorbia. The first part consists two chapters, which expatiate on the isolation and identification of chemical constituents from D. tangutica and E. wallichii. Thirty-one compounds were isolated from the root barks of D. tangutica by methods of column chromatography (silica gel, including reversed phase), preparative TLC and HPLC, and their structure were identified as nine daphnane diterpenes, six lignans, nine cumarin derivatives, five phenylpropanoid derivatives, a steroids and a benzoate on the basis of spectroscopic methods including IR, MS and NMR. Among them, three are new diterpenes with skeleton of daphnane and the structure were determined as 1,a-dihydro-20-palimoyl-daphnetoxin, 1,2a-dihydro-5b- hydroxy-6a,7a-epoxy-resiniferonol-14-benzoate and 1,2b-dihydro-5b-hydroxy- 6a,7a-epoxy-resiniferonol-14-benzoate. In addition, thirteen known ones were isolated from this plant for the first time. Isolation of the roots of E. wallichii yielded thirty compounds, twenty-four of them were elucidated as diterpenoids, which belong to different skeleton types of ingenol, lathyrane, ent-atisane, ent-kaurane, ent-abietane, ent-trachylobane, ent-isopimarane and a new pentacyclic skeleton ent-wallichane respectively. The remains including a cumarine, a triterpenoid, a steroid and three compounds with small molecule. Nine new compounds were characterized as 5-O-deca-2E,4E,6E- trienoyl-3,20-O-diacetylingenol, 5-O-deca-2E,4Z-dienoyl-3-O-acetyl-20- deoxyingenol, 3-O-deca-2E,4Z-dienoyl-jolkinol-5b,6b-oxide, 7-benzoyl-3,5,15- triacetyl-7-hydroxylathyrol, ent-trachylobane-3-one-17-oic-acid, 3α-hydroxy-ent- atis-16-en-14-one, 3α,6-dihydroxy-ent-isopimarane-7-en-2,15-dione, wallichanol A and wallichanol B, respectively, by means of comprehensive spectroscopic analysis. Among them, wallichanol A and wallichanol B were two notable novel pentacyclic diterpenoids processing a new rearranged carbon skeleton. And more, thirteen ones were firstly reported from this plant. The third chapter summarizes the research development on chemistry and pharmacology of polycyclic diterpenes from the plant family of Euphorbia for the first time.

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.

Gas-phase isothermal chromatography with short-lived technetium isotopes

In order to study the gas-phase chemical behavior of transactinides, an on-line isothermal chromatography apparatus has been developed and applied to separate short-lived technetium isotopes in the form of TcO3 from fission products. The fission products from a Cf-252 source were continuously and rapidly transported through the capillary to the isothermal chromatography apparatus using the N-2/KBr gas-jet techniques. Volatile oxide molecules were formed at the reaction zone kept at 900 degrees C since a trace amount of oxygen existed in the N-2 carrier gas. With the new developed isothermal chromatography apparatus, a selective separation of Tc from fission products was achieved. After isothermal chromatographic separation, Tc-101,Tc-103,Tc-104,Tc-105,Tc-106,Tc-107,Tc-108 were dominantly observed together with their Ru daughters in the gamma-spectrum, The chemical yields of Tc-101, and Tc-104 and Tc-105 isotopes with longer half-lives are about 55-57%, and those of Tc-103, Tc-106 and Tc-108 isotopes with shorter half-lives dropped down to 25-28%. The adsorption enthalpy of the investigated compounds on quartz surfaces was determined to be -150 +/- 5 kJ/mol by fitting the measured retention curves with a Monte Carlo model. The observed species of technetium oxide is attributed to TcO3, which is in good agreement with previous experimental results. That means our system worked properly and it can be used to investigate the gas-phase chemical behavior of transactinides.

Characterization of complex hydrocarbons in cigarette smoke condensate by gas chromatography-mass spectrometry and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry

Gas chromatography-mass spectrometry with electron ionization and positive-ion chemical ionization and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-TOF-MS) were applied for the characterization of the chemical composition of complex hydrocarbons in the non-polar neutral fraction of cigarette smoke condensates. Automated data processing by TOF-MS software combined with structured chromatograms and manual review of library hits were used to assign the components from GC x GC-TOF-MS analysis. The distributions of aliphatic hydrocarbons and aromatics were also investigated. Over 100 isoprenoid hydrocarbons were detected, including carotene degradation products, phytadiene isomers and carbocyclic diterpenoids. A total of 1800 hydrocarbons were tentatively identified, including aliphatic hydrocarbons, aromatics, and isoprenoid hydrocarbons. The identified hydrocarbons by GC x GC-TOF-MS were far more than those by GC-MS. (C) 2004 Elsevier B.V. All rights reserved.

Prediction of soil organic carbon partition coefficients by soil column liquid chromatography

To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (K-OC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (K-OW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for K-OC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (k(soil)) and K-OC measured by batch equilibrium method were studied. Good correlations were achieved between k(soil) and K-OC for three types of soils with different properties. All the square of the correlation coefficients (R-2) of the linear regression between log k(soi) and log K-OC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of K-OC from K-OW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (k(CN)) was comparatively evaluated for the three types of soils. The results show that the prediction of K-OC from k(CN) and K-OW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the K-OC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict K-OC largely depends on the properties of soil concerned. (C) 2004 Elsevier B.V. All rights reserved.

Direct characterization of bitter acids in a crude hop extract by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

The applicability of on-line coupling of reversed-phase high-performance liquid chromatography to atmospheric pressure ionization tandem mass spectrometry for the separation and characterization of hop acids mixture from the crude extract of Humulus lupulus was investigated. The solvent system consisting of acetonitrile-aqueous formic acid was used to give proper separation of the six main hop bitter acids within 30 min. Further structural information about the components was acquired by collision-induced dissociation (CID). On the basis of analyses of the fragmentation patterns of the major alpha- and beta-bitter acids respectively, identification of the minor ones was performed using selected reaction monitoring (SRM) with a group of qualitatively relevant selected precursor-product ion transitions for each bitter acid in a single high performance liquid chromatography (HPLC) run. Using this technique, six minor hop acids, including "adprelupulone" observed for the first time in natural resources, were detected along with the six major acids. This hyphenated techniques provides potency for rapid qualitative determination of analogs and homologs in mixtures. (C) 2004 American Society for Mass Spectrometry.

Determination and identification of isoflavonoids in Radix astragali by matrix solid-phase dispersion extraction and high-performance liquid chromatography with photodiode array and mass spectrometric detection

The isoflavonoids in Radix astragali were determined and identified by HPLC-photodiode array detection-MS after extraction employing matrix solid-phase dispersion (MSPD). As a new sample preparation method for R. astragali, the MSPD procedure was optimized, validated and compared with conventional methods including ultrasonic and Soxhlet extraction. The amounts of two major components in this herb, formononetin (6) and ononin (2), were determined based on their authentic standards. Four major isoflavonoids, formononetin (6), ononin (2), calycosin (5) and its glycoside (1), and three minor isoflavonoids, (6aR,11aR)-3-hydroxy-9, 10-dimethoxypterocarpan (7), its glycoside (3), and (3R)-7,2'-dihydroxy-3',4'-dimethoxyisoflavone-7-O-beta-D-glycoside (4), were identified based on their characteristic two-band UV spectra and [M + H](+), [aglycone + H](+) and [A1 + H](+) ions, etc. The combined MSPD and HPLC-DAD-MS method was suitable for quantitative and qualitative determination of the isoflavonoids in R. astragali. (C) 2003 Elsevier B.V. All rights reserved.