【作者】 王继彦；

【导师】 李向高；

【作者基本信息】 吉林农业大学 ， 作物栽培学与耕作学， 2003， 博士

【摘要】 中药材的质量评价是中药现代化的重要组成部分，也是本学科专业的研究方向之一，其中人参的研究一直为本领域的重点研究课题。人参果为五加科植物人参（Panax ginseng C.A.Meyer）的成熟果实。进年来，随着人参地上部分利用的研究进展，人参果具有高含量的人参皂苷和显著的生理活性，已引起国内外学者的广泛关注。人参果的化学成分研究报道较少且不深入。到目前为止从人参果中仅分离鉴定了十余种人参皂苷。而文献报道从人参根及其它部位已分离鉴定了五十余种人参皂苷。现代医学和药理研究证明，人参皂苷为人参的主要有效成分之一，它具有人参根的主要生理活性。因此，系统深入研究人参果化学成分，特别是人参皂苷类成分，很有现实意义，而且有可能籍此研究发现新的活性成分或生物活性先导化合物。 为了给系统研究人参增添新的内容，扩大人参的药用范围，给正确评价人参果的质量提供理论依据，作者对人参果中的化学成分进行了系统研究。 本项研究采用有机溶剂提取、萃取、大孔吸附树脂层析、ODS柱层析、硅胶柱层析和低压硅胶干柱层析等常规的植物化学方法和技术手段并结合先进仪器制备型高效液相等方法，通过多种不同的提取、分离工艺路线，从人参果中分离得到了四大类化学成分——皂苷类、生物碱类、植物甾醇类和有机酸类共17个单体化合物。通过物理常数、化学方法和波谱分析[质谱（MS）、红外光谱（IR）、旋光谱（ORD）、核磁共振NMR（包括多种2D NMR技术：）]的方法鉴定了其中13个单体化合物。它们分别为十个皂苷、一个生物碱、一个植物甾醇和一个有机酸。皂苷类十个单体分别为人参皂苷-Rb₁、-Rb₂、-Rc、-Rd、-Re、-Rg₁、-Rh₁、-Rh₂、（Ginsenoside-Rb₁、-Rb₂、-Rc、-Rd、-Re、-Rg₁、-Rh₁、-Rh2、）异人参皂苷Rh₃（3-O-β-D-glucopyranosyl-dammarane-（E）-20（22），24-diene-3β，12β-diol．）和人参皂苷compound K（Ginsenoside compound K），生物碱单体为Ginsenine Ⅰ，甾醇类单体为β一谷甾醇（β-sitosterol）。有机酸类为苯甲酸。其中异人参皂苷Rh₃和生物碱为新化合物；人参皂苷compound K为新天然化合物。苯甲酸为首次从人参吉林农业大学博士学位论文人参果化学成分的研究果中分离得到。 到目前为止，从人参属植物中发现并获得生物碱类单体化合物的报道琦民少。本项研究从人参果中发现并分离得到了一生物碱单体化合物，且为新化合物。这将为进一步全面正确的评价人参的药用功能，临床药效提供新的基拙依据。另外，本项研究还发现并分离得到了一新的天然化合物一扰肿瘤活性成分人参皂普comPoundK，并对其进行了含量浏定。这一化合物过去一直普遍认为只有在进行生物代谢的研究过程中，人参皂普经生物转化，即在土壤细菌类水解、特殊酶的水解及生物的肠内菌代谢作用的条件下，才能产生。此物质在天然化学成分的分离研究中未见报道，它的分离将为人参的基拙研究增加新的内容，提供新的依据。 本项研究还采用Agilent noo高效液相色谱仪对人参果中的人参皂普comPoundK进行了含量测定，结果表明人参果中的人参皂普compoundK的含量约为0.029%。 应用Aghent 6890G一c一5973MsD色谱一质谱一计算机联用仪提取分离鉴定了人参果挥发油中的26个化合物。 应用日立一835型氛基酸自动分析仪对人参果中总氨基酸进行了的分析，结果表明:人参果中存在16种以上的氨基酸;人参果中总氛基酸含量约为10.42%。 采用美国JARRALL-一ASH800系列Mark一n型电热藕合等离子发射光谱仪配同PDPSA计算机，对人参果中无机元素进行了测定分析。结果表明:人参果中存在24种以上的无机元素，各元素的相对含量各有不同。 综合各项研究结果，本文初步系统研究分析了人参果的化学成分，为正确评价人参果的质量提供了理论依据。为各类型化合物的结构鉴定提供了光谱学依据。为扩大人参的药用范围，给系统研究人参增添了新的内容，也为人参果的药用前景莫定了基础。 本文的创新点是: ·用不同的提取、分离工艺路线，从人参果中发现并分离得到了两个新的单体化合物。一个为皂普;一个为生物碱。通过物理常数、化学方法和波谱分析的方法对其进行了鉴定，分别命名为:异人参皂普Rh3;伍nseninel。用ZDNMR的多种技术对新化合物进行了碳氢全归属，为该类化合物波谱学提供了理论依厂吉林农业大学博士学位论文人参果化学成分的研究据。 ·从人参果中发现并分离得到了一新的天然化合物一杭肿瘤活性成分人参皂普comPoundK，并采用HPLC的方法对其进行了含量测定。还对H卫LC的测定方法进行了方法学考察。表明该法简便、灵敏和准确、可作为评价人参果质量的可靠有效分析方法。该研究结果不仅为其提取、分离、纯化、鉴定和测定提供了理论依据，莫定了基础。而且可能为解释人参皂普类的生物合成提供新的依据。 ·应用现代化仪器首次对人参果中挥发油、无机元素及总氨基酸进行了测定分析。为人参果的基础研究，提供了理论依据。更多还原

【Abstract】 The quality evaluation of Chinese Medicinal Materials is an important part of traditional Chinese medicine modernization, and also the one of the research areas in the professional studies. Among them ginseng research still plays an important role in the field. The fruits of Panax ginseng C. A. Meyer, with the high ginsenosides content and the evidently pharmacological activity, has been studied extensively along with the research development on the other part of the Ginseng’s plant except the root.But up to now, there were a few reports on the chemical studies of the fruits of Panax ginseng C. A. Mey ,and no more than thirteen ginsenosides were isolated and identified from the fruits of Ginseng, while there more than fifty saponins were isolated and identified from the root of Ginseng and other part of the Ginseng’s plant. Ginseng saponins(ginsenosides), isolated from the Ginseng, have been regarded as the principal components responsible for the pharmacological activity of Ginseng Radix by the many reports on the pharmacological, chemical, biochemical studies. Therefore, it is necessary to systematically extensive study the chemical constituents of the fruits of Ginseng in order to discover new biologically active constituents, and give the evaluation evidence about the quality of the fruits of Ginseng.For this purpose, we have systematically studied the different kinds of chemical constituents of the fruits of Ginseng by the phytochemistry method and technique, and the modern instruments.Four kinds of compound categories, saponins, alkaloids, sterols and organic acids, seventeen compounds were isolated from the fruits of Ginseng by the different process of the extraction and isolation ,and with the extraction of organic solvent, Macro-reticular resins, ODS column chromatography, silica gel column chromatography, and other isolation measures .On the basis of the physical constants, chemical evidence and spectrum analysis [ MS, IR, ORD, NMR ( including JH NMR,13C NMR, gCOSY, gHSQC .gHMBC and NOESY)], thirteen compounds were characterized as benzoic acid, isoginsenoside-Rhs, ginsenoside-Rha, ginsenoside-Rhi, ginsenosid-Rgi, ginsenoside-Re, ginsenoside-Rd, ginsenoside-Rc, ginsenoside-Rb2, ginsenoside-Rbi, 3 -sitosterol, ,ginsenoside compound K, ginsenine I .They were substantiated as ten saponins, one alkaloid, one sterol and one organic acid.Among them, isoginsenoside-Rh3(3-O-p-D-glucopyranosyl-dammarane-(?-20 (22), 24-diene-3p, 12f3-diol.) and ginsenine I ( alkaloid) are new compounds; ginsenoside compound K is novel nature compound; benzoic acid was isolated from the fruits of Ginseng for the first time.It should be mentioned that so far, there were a few reports on the alkaloid isolationfrom the Panax genus. It was the first time to obtain the alkaloid compound, ginsenineI, from the fruits of Ginseng. And, the alkaloid is a novel compound. It will give thenew evaluation evidence for the pharmacological activity and medicine efficacy ofGinseng.In addition, It was the first time to obtain a novel nature compounds, ginsenoside compound K which is an anticancer constituents, from the fruits of Ginseng. Until now, the ginsenoside compound K was still thought as the transformation product of the ginsenosides on the experiment of the ginsenosides decomposition by the soil bacterial hydrolysis, the enzymatic hydrolysis and the intestine metabolism. There has been no report about isolation compound K from the nature organism on the nature chemical constituents research.Besides, the content of compound K in the fruits of Ginseng was determined by HPLC. The result showed that the content was about 0.029%.By the GC-MS instrument, the twenty-six compounds in the volatile oils of the fruits of Ginseng was first isolated and determined .Used ICP-AES instrument, the inorganic elements in the fruits of Ginseng was first detected. The result showed that there are 24 kinds of the inorganic elements in the fruits of Ginseng,and the relative content are diffirent among them.By the 835更多还原