丁香和升麻的化学成分研究

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

几种中药材的化学成分及其定性定量检测方法研究

本论文由四部分组成。第一部分报道了佛手参提取物的化学成分研究，建立了活性成分含量测定的高效液相测定和指纹图谱研究，采用液质联用技术鉴定了主要色谱峰；第二部分报道了丹参及其复方制剂的特征图谱研究；第三部分探讨了两面针生物碱的电喷雾质谱裂解规律，并采用液质联用技术分离鉴定了提取物中的多种生物碱。第四部分概述了液质联用在药物代谢研究中的运用。 第一部分包括第一、第二和第三章。第一章针对佛手参（Gymnadeniaconopsea）块茎的甲醇提取物，采用大孔树脂和反相硅胶柱层析等各种分离方法，共分离鉴定出4 个化合物，通过波谱分析将它们的结构确定为dactylorhin B (1)、loroglossin (2)、dactylorhin A (3)和militarine (4)。这4 个化合物均是首次从佛手参中分离得到的琥珀酸葡萄糖苷类成分。第二章采用高效液相色谱法对西藏、四川、河北、青海和尼泊尔等不同地区产的十个佛手参样品进行腺嘌呤核苷和对羟基苯甲醇的定量分析，结果表明这2 个成份可视为佛手参的特征成分，但也注意到产地不同该2 个特征成分的含量也有所不同。第三章采用标准中药指纹图谱相似度计算软件，以10 个佛手参样品HPLC 图谱的平均值为相似性评价对照模板，对10 个样品进行了相似度评价，并经液质联用分析指认了7 个共有峰，分别为腺嘌呤核苷(1)、对羟基苯甲醇(2)、对羟基苯甲醛(3) 、dactylorhin B(4) 、loroglossin(5)、dactylorhin A(6)和militarine(7)。 第二部分包括第四、第五、第六和第七章。第四章运用电喷雾质谱检测了对照药材和五个不同产地的丹参药材中脂溶性和水溶性成分，系统地探讨了多种成分的电喷雾质谱规律，并以对照药材为标准建立了特征指纹图谱。五个产地的药II材通过与对照药材相对比，采用聚类分析的方法，得到了定性的鉴别与判断。并采用液质联用技术对丹参药材提取液中的化学成份进行分析，推测了九个特征峰，并对六样品的液相色谱图进行了聚类分析。第五章探讨了三七皂苷的电喷雾质谱电离和裂解规律，并采用电喷雾质谱法对三七标准药材，血通片中的皂苷成分进行了分析。第六章运用电喷雾质谱研究复方丹参片提取液的特征图谱，并和单味药材丹参和三七的特征图谱进行了对比研究。并运用HPLC-ESI MSn 分析鉴定了复方丹参片提取液中的化学成分，推测了12 个色谱峰。第七章总结了电喷雾质谱和液质联用技术在丹参药材，三七药材及复方丹参制剂中的运用的优势和局限性。 第三部分（第八章）研究了两面针生物碱中二氢白屈菜红碱(1)、二氢两面针碱(2)、8-酮基二氢白屈菜红碱(3)、8-丙酮基二氢两面针碱(4)、两面针碱(5)、和1,3-二(8-二氢两面针碱)丙酮(6)等六个苯并菲啶型生物碱的电喷雾质谱裂解规律，其中二氢两面针碱和二氢白屈菜红碱，8-丙酮基二氢两面针碱和8-酮基二氢白屈菜红碱是两对二个甲氧基分别在C-9 和C-10，C-10 和C-11 的同分异构体。实验结果表明，在相同的碰撞能下，这类位置异构体的ESI MS2 质谱二级碎片离子的相对峰度存在很大差异，这可以用于区分该类同分异构体，采用液-质联用可以对两面针的总生物碱提取物中的这些同分异构体加于区分。同时在本实验采用的液相色谱条件下，多种生物碱得到较好的分离，通过和对照品的保留时间，紫外吸收光谱及电喷雾质谱图对照，鉴定了11 个主要色谱峰。 第四部分（第九章）对液质联用技术在药物代谢中的运用进行了综述。 This dissertation consisted of four sections. The first two sections elaborated thephytochemical investigation of the rhizomes Gymnadenia conopsea R. Br., methoddevelopment for rapid identifying and qutifying the chemical condtituent of thistibetant medicine, and the chemical fingerprint analysis of rhizomes of G. conopsea,Salviae miltiorrhiza and P. notoginseng. The third section studied the fragmentationmechanism of six alkaloids from Zanthoxylum nitidium and method development forrapid identifying varieties of alkaloids from the extract of this herbal medicine. Thefourth section reviewed HPLC- MS method in drug metabolism studies. The first section consisted of chapters 1, 2, 3. Chapter 1 elaborated the phytochemicalinvestigation of Gymnadenia conopsea R. Br. Four succinate derivative esters wereisolated from the methanol extract of the rhizomes of G. conopsea through repeatedcolumn chromatography on normal and reversed phase silica gel, their structures weredetermined by ESI-MS, 1D and 2D NMR evidence. They were firstly discoveredfrom this species. In chapter 2, a high-performance liquid chromatography.diodearray detection (HPLC-DAD) method has been firstly developed for quantitation oftwo characteristic constituents, adenosine and 4-hydroxybenzyl alcohol, from theextract of rhizomes of G. conopsea. All 10 samples of G. conopsea contained differentamount of adenosine and 4-hydroxybenzyl alcohol. Adenosine and the4-hydroxybenzyl alcohol can be applied in identification and quality control for theroots of G. conopsea. In chapter 3, a high-performance liquid chromatography.diodearray detection.tandem mass spectrometry (HPLC-DAD-MSn) method has been firstly developed for chemical fingerprint analysis of rhizomes of G. conopsea andrapid identification of major compounds in the fingerprints. Comparing the UV andMS spectra with those of authentic compounds, seven main peaks in the fingerprintswere identified as adenosine, 4-hydroxybenzyl alcohol, 4-hydroxybenzyl aldehyde,dactylorhin B, loroglossin, dactylorhin A and militarine. The Computer AidedSimilarity Evaluation System for Chromatographic Fingerprint of TraditionalChinese Medicine (CASES) was employed to evaluate the similarities of 10 samplesof the rhizomes of G. conopsea collected from Sichuan, Qinghai and Hebei provincesand Tibet autonomous region of China, and Nepal. These samples from differentsources had similar chemical fingerprints to each other. The second section consisted of chapters 4, 5, 6 and 7. In chapter 4，both thecharacteristic spectra of liposoluble tanshinones and aqueous-soluble salvianolic acidswere established by the electrospray ionization mass spectrometry (ESI MS)technique and the differences between standard and crude rhizomes of Salviaemiltiorrhiza Bge. from 5 sources were analyzed. The law of electrospray ion trap mass(ESI ITMS) of typical tanshinones and salvianolic acids is studied.The analysis of the chemical constituent of rhizomes of Salviae miltiorrhiza Bge. byliquid chromatography coupled with mass spectrum (LC/MS) technique wasestablished，and the distances among standard herb and crude herb from 5 sourceswere calculated by clustering analysis. According the DAD spectra and MS2 data，9tanshinones could be speculated. In chapter 5, the character spectra of total saponinsin P. notoginseng extracts were established by ESI ITMS and selective ion monitoring(SIM) technology. The law of notoginsenosides by ESI MS2 was studied. In chapter 6,the characteristic spectra of Compound Danshen Tablet established and compared byESI-MS and HPLC/DAD/MS, 6 known tanshinones and 3 saponins were speculated.In chapter 7, the advantage and disadvantage of the strategy, using the ESI ITMS andLC/MS techniques for study of characteristic spetra of danshen and Compound Danshen Tablet, were summerized. The third section (chapter 8) studied the fragmentation mechanism of six alkaloids,dihydronitidine, dihydrochelerythrine, 8-acetonyl dihydronitidine,8-acetonyldrochelerythrine, nitidine and 1,3-bis (8-dihydronitidinyl)-acetone, by ESIMSn. Tandem mass spectrometry experiments indicated that different substitutionsites of the methoxyl groups at C-9 and C-10 or at C-10 and C-11 determined thedifferent abundances of the MS2 fragmentation ions using the same collision energy.According to the different abundances of MS2 product ions, positional isomericbenzo[c] phenanthridine alkaloids can be differentiated. Moreover, ten constituents inthe crude alkaloids extract from the roots of Zanthoxylum nitidium were rapidlyidentified by high-performance liquid chromatography coupled with tandem massspectrometry (HPLC-MSn), through comparing the retention times and ESI MSn spectra with the authentic standards. The fourth section (chapter 9) is a review on HPLC-MS method development in drug metabolism studies.

余甘子、细叶草乌及土荆皮化学成分研究

本论文由三部分共6 章组成。第一部分报道了余甘子、细叶草乌和土荆皮等三种药用植物的化学成分研究成果；第二部分报道了细叶草乌和土荆皮中分离得到的化合物的活性测试，以及这两种植物的质谱分析；第三部分概述了土荆皮的研究现状。第一部分包括1－3 章。在第1 章、第2 章和第3 章中分别报道了余甘子(Phyllanthus emblica L.) 、细叶草乌(Aconitum richardsonianum var.pseudosessiliflorum) 和土荆皮( pseudolarix kaempferi) 的化学成分。采用正、反相硅胶柱层析等各种分离方法，从余甘子中共分离出10 个化合物，其中1 个为新化合物，另外还有2 个为首次从该植物中分离得到。细叶草乌的化学成分研究尚未见报道，我们从该植物中共分离出15 个化合物，其中6 个为二萜生物碱，9个为非生物碱成分。从土荆皮中分离得到16 个化合物，其中8 个二萜、1 个三萜和7 个其它类型化合物，其中有4 个化合物为首次在该植物中分离得到；从土荆皮挥发油中分离鉴定出了22 个化合物，占挥发油总量的90%。第二部分包括4－5 章。第4 章报道了从细叶草乌和土荆皮中分离得到的13个化合物的药理活性研究，结果显示，展花乌头宁和土荆乙酸葡萄糖苷等表现出较高的组织蛋白酶K 抑制活性；土荆乙酸葡萄糖苷表现出较高的组织蛋白酶B抑制活性；8-去乙酰滇乌碱表现出较高的蛋白质酪氨酸磷酸酶抑制活性。第5 章报道了细叶草乌和土荆皮总浸膏的质谱( ESI-MS ) 分析，研究结果表明，ESI-MS 法可以简单快速地检测这两种植物的主要成分；通过ESI-MS2 分析初步探讨了一些化合物的裂解规律，尝试质谱在其结构测定中的具体应用。第三部分为第6 章。从化学成分、药理、构效关系、主要成分的定量分析、及其合成研究等方面概述了土荆皮的研究进展。 This dissertation consists of three parts. The first part elaborate thephytochemical investigation of three medicinal plants, Phyllanthus emblica L.,Aconitum richardsonianum var. pseudosessiliflorum and pseudolarix kaempferi. Thesecond part reported the bioassay of 13 constituents from Aconitum richardsonianumvar. pseudosessiliflorum and pseudolarix kaempferi, and ESI-MS analysis of these twoplant . The third part is a review on the research progress of pseudolarix kaempferi.The first part is composed of three chapters. Chapters 1-3 focus on the isolationand identification of chemical constituents from Phyllanthus emblica L., Aconitumrichardsonianum var. pseudosessiliflorum and pseudolarix kaempferi. 10 compoundsincluding a new tannin were isolated from the fruits of Phyllanthus emblica by repeatcolumn chromatography over normal and reversed phase silica gel, 2 of them werefirstly reported in this plant. The chemical constituents of Aconitum richardsonianumvar. pseudosessiliflorum never reported before, 15 compounds including 6 diterpenealkaloids were isolated and identified from the roots of this plant. 16 compoundsincluding 8 diterpenes , 1 triterpene and 7 other compounds were isolated from the bark of pseudolarix kaempferi, among them, 4 compounds were firstly reported fromthe EtOH extracts of this plant, and 22 compounds were identified from its essentialoil, representing 90% of the total essential oil.The second part includes chapters 4 and 5. Chapter 4 reported thepharmacological activities of 13 compounds isolated from Aconitum richardsonianumvar. pseudosessiliflorum and pseudolarix kaempferi. Results demonstrated that chasmanine and pseudolaric acid B-β-D-glucoside exhibit relatively high anti-Cathepsin K activities; pseudolaric acid B-β-D-glucoside exhibits relatively highanti-Cathepsin B activity; 8-deacetyl-yunaconitine exhibits relatively high anti-PTP1Bactivity. Chapter 5 reported the ESI-MS analysis of extractions from Aconitumrichardsonianum var. pseudosessiliflorum and pseudolarix kaempferi, it was showedthat ESI-MS can be used as an useful tool in analyzing the major constituents of thesetwo plant much quick and easy, in addition, the fragmentation rules of somecompounds were discussed, in order to find some applications of ESI-MS2 method in their structure determination.The third part is a review on the research progress of pseudolarix kaempferi,including the chemical constituents, pharmacology, structure-activity relationship(SAP), quantitative analysis and synthesis of the major constituents.

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.

中药蜘蛛香的化学成分研究及以羧甲基魔芋葡苷聚糖-壳聚糖为细胞膜的天冬酰胺酶人工细胞研究

本论文由三章组成。第一章介绍了中药蜘蛛香的化学成分的研究成果，第二章为羧甲基魔芋葡苷聚糖-壳聚糖为细胞膜的天冬酰胺酶人工细胞的研究，第三章综述了人工细胞在生物医学领域的应用。 第一章报道了中药蜘蛛香（Valeriana wallichii）根部乙醇提取物的化学成分，采用正、反相硅胶层析等分离方法和MS、NMR等多种波谱手段，从中共分离鉴定出17个化合物，分别为缬草素(valtrate，1)，valechlorine（2），homobadrinal（3），baldrinal（4），乙酰缬草素(acevaltrate 5)，valeriotetrate C（6），valeriotetrate B（7），对羟基苯乙酮(4'-hydroxy-acetophenone 8)，7-hydroxy valtrate（9），8-methylvalepotriate（10），1,5-dihydroxy-3,8-epoxyvalechlorine A（11），二氢缬草素(didrovaltrate 12)，胡萝卜苷（13），橙皮苷 (hesperidin 14)，prinsepiol-4-O-β-D-glucopyranoside（15），longiflorone（16），乙基糖苷（17）。其中化合物6、7、10、和11为新化合物，化合物9、15、16为首次从该植物中得到。新化合物11为含有氯原子的刚性骨架环烯醚萜，并且确定了其绝对构型。 第二章报道了以羧甲基魔芋葡苷聚糖（CKGM）和壳聚糖（CS）为膜的固定化L-天冬酰胺酶人工细胞研究成果。利用羧甲基魔芋葡苷聚糖和壳聚糖两种生物相容性很好的天然多糖之间的静电吸引力，在非常温和的条件下制备成具有半透过性膜的人工细胞，将治疗儿童急性成淋巴细胞性白血病(ALL)的药物L-天冬酰胺酶包裹在内。通过考察温度和pH对人工细胞的影响,结果表明以CKGM- CS为膜的L-天冬酰胺酶人工细胞对温度和pH的稳定性和耐受性均高于自由酶，说明CKGM-CS对酶具有保护作用，而且小分子底物和产物可以自由进出膜内外，而包裹在膜内的生物大分子则不能泄露出来。 第三章综述了微囊化人工细胞的研究进展。 This dissertation consists of three parts. In the first part, the chemical constituents from the root of Valeriana wallichii were reported. In the second part, preparation and characteristics of L-Asparaginase Artificial cell were reported. The third part is a review on progress of microcapsule artificial cell. The first chapter is about the isolation and identification of the chemical constituents from the root of V. wallichii. Seventeen compounds were isolated from the ethanol extract of roots of V. wallichii through repeated column chromatography on normal and reversed phase silica gel. By the spectroscopic and chemical evidence, their structures were elucidated as valtrate (1), valechlorine (2), homobadrinal (3), baldrinal (4), acevaltrate (5), valeriotetrate C (6), valeriotetrate B (7), 4'-hydroxy-acetophenone (8), 7-hydroxy valtrate (9), 8-methylvalepotriate (10), 1,5-dihydroxy-3,8-epoxyvalechlorine A (11), didrovaltrate (12), daucosterol (13), hesperidin (14), prinsepiol-4-O-β-D-glucopyranoside (15), longiflorone (16), and ethyl glucoside (17). Among them, 6, 7, 10, and 11 are new compounds. 15, 16 and 9 were isolated from this plant for the first time. The absolute configuration of compound 11, an unusual iridoid bearing a C-10 chlor-group and an oxo-bridge connecting C-3 and C-8 resulting in a rigid skeleton, was confirmed. The second chapter is about the semi-permeable microcapsule of carboxymethyl konjac glucomannan-chitosan for L-asparaginase immobilization. Carboxymethyl konjac glucomannan-chitosan (CKGM-CS) microcapsules, which have good biocompatibility, prepared under very mild conditions via polyelectrostatic complexation, were used for immobilize L-asparaginase-a kind of drug for acute lymphoblastic leukemia (ALL). The activity and stability under different temperature and pH of the enzyme loaded-microcapsules were studied. The results indicated the immobilized enzyme has better stability and activity contrasting to the native enzyme. The study illustrates that the L-asparaginase could be protected in CKGM-CS microcapsules, the substrate and product could pass through the system freely.

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.

厚朴中α-葡萄糖苷酶抑制活性成分研究

本论文由三章组成。 第一章是关于厚朴中具有α-葡萄糖苷酶抑制活性成分的研究。凹叶厚朴的乙醇提取物显示了较强的α-葡萄糖苷酶抑制活性。为了确定其活性成分，在活性测试的指导下，通过溶剂萃取、树脂吸附和反复硅胶柱层析等分离方法从凹叶厚朴乙醇提取物中分离得到6 个生物碱，并用质谱和核磁共振等波谱方法分别鉴定为：木兰箭毒碱，木兰花碱，鹅掌楸碱，蕃荔枝碱，罗默碱和Lysicamine。应用小肠α-葡萄糖苷酶模型测定了它们对α-葡萄糖苷酶的抑制作用。其中，番荔枝碱和木兰箭毒碱对α-葡萄糖苷酶相对抑制活性最好，分别为60%和62%；其它四个生物碱成分对α-葡萄糖苷酶的抑制活性几乎相当，鹅掌楸碱为46%，罗默碱为51%，Lysicamine 为49%，木兰花碱为51%。 第二章报道了厚朴酚的衍生物及其对α-葡萄糖苷酶的抑制活性。根据糖苷酶抑制剂的结构特点，设计合成了一系列厚朴酚的衍生物。厚朴酚经过Mannich 反应和环氧化及开环反应制备了一系列衍生物，经活性测试发现衍生物活性与取代基关系较大，其中5,5′-diallyl-3-((bis(2-hydroxyethyl)amino)methyl)biphenyl-2,2′-diol 的抑制活性最高，为72%。 第三章综述了厚朴的化学成分及药理活性两个方面的研究进展。 The dissertation consists of three chapters. The first chapter is about the study on the constituents with α-glycosidase inhibitory activity from Magnolia officinalis. The EtOH extracts of M. officinalis Rehd. et Wils showed good inhibitory activity against α-Glucosidase. In order to determine the active compounds, bio-assay was used to guide the isolation. Six known alkaloids were isolated by solvent extraction and repeated silica gel column chromatography, and their structures were identified as liriodenine, anonaine, roemerine, lysicamine, magnoflorine and magnocurarine by spectroscopic methods. The inhibitory activity against α-Glucosidase of these alkaloids was measured with alvine screening model of α-glucosidase. Among them, lysicamine and liriodenine have the best inhibitory activity at 60% and 62%, respectively. The other four alkaloids have close inhibitory activity, from 46% to 51%. The second chapter is about the derivation of magnolol and the inhibitory a ctivity of the derivatives. Seven derivatives of magnolol were prepared by Manni-ch reaction, epoxidation followed by ring-opening reaction. Biological activity as say indicated the inhibitory activity was related to substituting groups. Among them, 5,5′-diallyl-3-((bis(2-hydroxyethyl)amino)methyl)biphenyl-2,2′-diol had the highest activity at 72%. The third chapter is a review on the progress of M. officinalis including chemical constituents and pharmacological activity.

一株放线菌发酵产物抗肿瘤活性的研究

本学位论文主要研究一株放线菌发酵产物的抗肿瘤活性。先对该株放线菌进行活化培养，然后进行大批量发酵，发酵液经过冷冻离心，对离心得到的沉淀和上清液用不同极性的有机溶剂进行萃取，得到六个浸膏样品。对六个样品进行初步抗肿瘤活性检测。 然后对活性浸膏进行分离纯化和活性跟踪。本论文主要进行了如下的工作： 1、对菌种进行活化培养，利用该菌株在280C，200r.min-1条件下进行发酵实验，发酵时间为72h,发酵总量为15L。发酵液经过离心得到上清液和沉淀两部分。 2、分别用石油醚、乙酸乙酯、正丁醇萃取沉淀和上清液，得到编号为1—6的六个浸膏样品，对六个浸膏样品进行初步的细胞毒性和抗HepG2肿瘤活性实验，得出结论为5号样品活性最高。在没有分离纯化的情况下GI50达到0.76µg/mL。 3、对5号样品进行TLC实验，找出能够较好分离5号样品中各组分的溶剂组合，最后得出在氯仿：甲醇=8：1时分离效果较好。然后利用氯仿：甲醇=8：1的溶剂组合作为洗脱剂对5号样品进行过硅胶柱分离纯化并进行活性跟踪分离。 4、对分离纯化后得到的样品进行活性跟踪和结构分析。分离后得到样品A，在其浓度为10µg/ml时，抗肿瘤实验细胞的生长率为73.5%。在浓度为1.0mg/ml时，抗单纯疱疹病毒率（HSVⅡ）为74.5%。结构分析得知其分子式最可能为C41H43N8O4. This dissertation studied about the anti-tumor activity of an actinomycete fermentation product. First, we cultured the actinomycete. Second, we fermented it in large quantities, and then centrifuged the fermentation fluid; the next step is that we extract sedimentation and supernatant in different polar organic solvents, in turn to obtained six samples, which were detected about anti-tumor activity. Last, we purified active sample and tracked activity of it. We carried out the following research work: 1. Activation, culture and screening of the actinomyces was carried on. We used the screening strain to carry on the fermentation when the conditions are 280C，200r.min-1,the fermentation time is 72h. Fermentation fluid volume is 15L.And we obtained sedimentation and supernatant after fermentation fluid was centrifuged. 2. We used Petroleum ether, ethyl acetate, n-butanol separately to extract sedimentation and supernatant, and obtained six samples that were numbered 1-6. From the preliminary cell toxicity and the anti-tumor（HepG2） bioactivity experiment, we found that No.5 sample has the highest activity in the samples; the GI50 was 0.76µg/ml which has not been purified. 3. We Carried on TLC experiment on the No.5 sample, found the solvent composition that can separate each component of the No.5 sample. At last, we found that when the proportions are tri-chloromethane: methyl alcohol = 8:1, the Separation result was the best, and then we used the Solvent composition which proportion are tri-chloromethane: methyl alcohol = 8:1 as eluant to Purify No.5 sample by silica gel column. 4. We tracked the activity of pure sample obtained from Purification and analyzed structure of these substances. We got a compound A after separation, and the cell growth rate was 73.5% when its concentration was 10µg/ml. The anti-virus（HSVⅡ） rate was 74.5% when its concentration was 1.0mg/ml. We analyzed the Structure of A, and informed its molecular formula that was the most likely for C41H43N8O4.

链霉菌S227抗耐药菌活性成分的研究

本论文以从四川峨嵋山森林土壤中分离筛选获得的一株产抗耐药性活性化合物的链霉菌S227为材料，对发酵液中活性物质的分离纯化及抗耐药性活性进行了研究。 建立了抗耐药性活性的定性、定量检测方法。建立的管蝶法活性定量检测的标准回归方程为：D=4.8229Ln(C)+3.6326 R=0.9972 ；纸片法活性定量检测的标准回归方程为：D=5.5Ln(C)-12.794 R=0.999。 根据建立的样品活性的检测方法，测定了发酵液的初始活性。实验证明活性物质的温度、pH稳定性好。 通过活性的定性、定量追踪方法，分别利用等体积的石油醚、乙酸乙酯、正丁醇在不同的pH梯度下萃取，确定了pH3条件下正丁醇能最大程度的萃取活性物质，说明活性物质极性很大。对正丁醇萃取相经过两次硅胶柱层析及薄层层析分离得到具有抗耐药菌活性的纯化样品S227-4。 经过核磁共振氢谱、碳谱数据分析初步确定S227-4为四聚糖，通过糖的水解实验初步确定S227-4由葡萄糖和半乳糖组成。 纸片法活性检测表明S227-4具有抗耐药菌活性。采用MIC测定法对该样品抗耐药活性进行研究。在证明该样品本身不具有抗菌活性的基础上，以临床分离的耐药性金黄色葡萄球菌为指示菌，考察了该样品与抗生素联合使用时对耐药菌抗生素MIC（最小抑菌浓度）值的影响，结果表明在不影响菌体生长的浓度条件下，该样品能明显降低多株耐药菌对多种抗生素的MIC值，不同程度地恢复所测试耐药菌对相应抗生素的敏感性。如S227-4与青霉素钠联用可以使S. aureus 12352的MIC降低8倍，而与红霉素联用可以使S. aureus 12334的MIC降低128倍。 The purification process and the activity of the anti bacterial drug resistance compounds produced by Streptomyces S227 isolated from the forest soil sample of the Mountain E’MEI in Sichuan Province were studied in this thesis. Quantitative and qualitative activity assay methods of the active compounds were established. The regression equation of the tube method was D=4.8229Ln(C)+3.6326, R=0.9972. The regression equation of the paper method was D=5.5Ln(C)-12.794, R=0.999. According to the established activity assay method, the incipient activity of the broth was evaluated. And it was proved that the stability of the active compounds was good. By quantitative and qualitative activity tracing method, petroleum ether, ethyl acetate and butanol were used to extract the active compounds at different pH. The result showed that butanol was the most effective agent for active component recovery at pH3. From the butanol extraction a purified sample, S227-4, was isolated by silica gel column chromatography and thin-layer chromatography . S227-4 was proved to be a tetra- saccharide by 1H-NMR and 13C-NMR. And its monosaccharides include glucose and galactose by hydrolysate analysis. The anti-drug resistant activity of S227-4 was tested in vitro by MICs assay using different drug resistant Staphylococcus aureus strains isolated clinically. The sample itself showed no anti-microbial activity in growth inhibitory experiment, but when it was used together with different antibiotics, it could remarkably decrease the MICs of different clinically isolated drug-resistant bacterial strains to these antibiotics. For example, when S227-4 was used with penicillin, the MIC of S. aureus 12352 decreased 8 times compared with that when penicillin was used alone. Meanwhile when it was used with erythromycin the MIC of S. aureus 12334 deceased 128 times compared with erythromycin alone.

Using HPLC retention parameters to estimate fish bioconcentration factors of organic compounds

Reversed-phase high performance liquid chromatography (RP-HPLC) was employed to develop predictive models for fish bioconcentration factors (BCF) of organic compounds. Estimation of BCF from RP-HPLC retention parameters on octadecyl-bonded silica gel (ODS), cyanopropyl-bonded silica gel (CN), and phenyl-bonded silica gel (Ph) columns were investigated. The results show that, for a set of compounds belonging to different chemical classes, the CN stationary phase is the best one among the three columns and better than n-octanol/water model for BCF estimation. A multi-column RP-HPLC model, using the retention parameters on the CN and Ph columns as the variables of multiple linear regression equations, was further evaluated to estimate BCF of organic compounds belonging to different chemical classes, and the results show that the multi-column RP-HPLC model is better than that of any single RP-HPLC column for BCF estimation.

AgBiVMo oxide catalytic membrane for selective oxidation of propane to acrolein

A metal ions (Ag, Bi, V, Mo) modified sol-gel method was used to prepare a mesoporous Ag0.01Bi0.85V0.54Mo0.45O4 catalytic membrane which was used in the selective oxidation of propane to acrolein. By optimizing the preparation parameters, a thin and perfect catalytically active membrane was successfully prepared. SEM results showed that the membrane thickness is similar to5 mum. XRD results revealed that Ag0.01Bi0.85V0.54Mo0.45O4 with a Scheelite structure, which is catalytically active for the selective oxidation of propane to acrolein, was formed in the catalytic membrane only when AgBiVMoO concentrations were higher than 40%. Catalytic reaction results demonstrated that the selective oxidation of propane could be controlled to a certain degree, such as to acrolein, in the catalytic membrane reactor (CMR) compared to the fixed bed reactor (FBR). For example, a selectivity of 54.85% for acrolein in the liquid phase was obtained in the CMR, while only 8.31% was achieved in the FBR. (C) 2003 Elsevier B.V. All rights reserved.

Biosorption of Cd2+, Cu2+, Ni2+ and Zn2+ ions from aqueous solutions by pretreated biomass of brown algae

In this paper, marine brown algae Laminaria japonica was chemically modified by crosslinking with epichlorohydrin (EC1 and EC2), or oxidizing by potassium permanganate (PC), or crosslinking with glutaraldehyde (GA), or only washed by distilled water (DW). They were used for equilibrium sorption uptake studies with Cd2+, Cu2+, Ni2+ and Zn2+.

Hyperbranched polymer-assisted hydrothermal in situ synthesis of submicrometer silver tubes

We produced silver tubes with an outer diameter of 1 mu m, wall thickness of 200 nm, and length of hundreds of micrometers by hydrothermal treatment of aqueous solutions of AgNO3 and hyperbranched polyglycidol (HPG) at 165 degrees C. The surfaces of the silver tubes were chemically modified by HPG, which was confirmed by FTIR of the silver tubes.