宽筋藤化学成分研究

发布时间：2018-09-13 13:56

【摘要】：本论文分为三个部分第一部分:文献综述对宽筋藤化学成分、药理活性及临床应用进行了综述,并对其今后的研究方向进行了展望,引用文献34篇;对反式丁香苷植物分布、药理活性及含量分析方法进行了综述,并对其今后的研究方向进行了展望,引用文献168篇。第二部分:宽筋藤化学成分研究采用多种分离纯化方法和结构鉴定手段(如ESI-MS、1H-NMR、13C-NMR等波谱学技术),对宽筋藤化学成分进行了研究。共分离得到23个化合物,鉴定出22个化合物,包括6个苯丙素类,3个萜类,3个脑苷脂类,2个生物碱类,2个肽和氨基酸类和6个其他类成分。6个苯丙素类成分分别是反式丁香苷(trans-syringin),tinosinen,丁香脂素-4-O-β-D-葡萄糖苷(syringaresinol-4-O-β-D-glucopyranoside),tinosposide,开环异落叶松脂素-9-O-β-D-葡萄糖苷(secoisolariciresinol-9-O-β-D-glucopyranoside)和异落叶松脂素-9-O-β-D-葡萄糖苷(isolariciresinol-9-O-β-D-glucopyranoside),3 个萜类分别是倍半萜tinocordiside,二萜tinosineside A 和三萜cycloeucalenone,3 个脑苷脂分别是 2-(2'-羟基二十四碳酰氨基)十八碳-1,3,4-三醇(2-(2'-hydroxytetracosanoylamino)octadecane-1,3,4-triol),soya-cerebroside Ⅰ 和 soya-cerebroside Ⅱ,2 个生物碱分别是反式-N-咖啡酰酪胺(trans-N-caffeoyltyramine)和伪巴马丁(pseudopalmatine),1 个肽类环(酪氨酸-酪氨酸)(cyclo(tyrosyl-tyrosyl))和1个氨基酸L-焦谷氨酸(L-pyroglutamic acid),以及 6 个其他类成分 5-羟甲基-2-呋喃丙烯酸(5-hydroxymethyl-2-furanacrylic acid),邻苯二甲酸-二(2-乙基-己基)酯(bis(2-ethylhexyl)phthalate),1,2-di-O-palmitoyl-3-Oβ-D-galactopyranosyl glycerol,3,4-二甲氧基苯基-β-D-葡萄糖苷(3,4-dimethoxyphenyl-β-D-glucoside),β-谷甾醇(β-sitosterol)和胡萝卜苷(daucosterol)。经SciFinder 检索,5-羟甲基-2-呋喃丙烯酸(5-hydroxymethyl-2-furanacrylic acid)是首次从自然界分离得到的一个新天然化合物。化合物开环异落叶松脂素-9-O-β-D-葡萄糖苷(secoisolariciresinol-9-O-β-D-glucopyranoside),cycloeucalenone,2-(2'-羟基二十四碳酰氨基)十八碳-1,3,4-三醇(2-(2'-hydroxytetracosanoylamino)octadecane-1,3,4-triol),soya-cerebroside Ⅰ,soya-cerebroside Ⅱ,反式-N-咖啡酰酪胺(trans-N-caffeoyltyramine),伪巴马丁(pseudopalmatine),环(酪氨酸-酪氨酸)(cyclo(tyrosyl-tyrosyl)),L-焦谷氨酸(L-pyroglutamic acid),邻苯二甲酸-二(2-乙基-己基)酯(bis(2-ethylhexyl)phthalate),1,2-di-O-palmitoyl-3-O-β-D-galactopyranosyl glycerol和3,4-二甲氧基苯基-β-D-葡萄糖苷(3,4-dimethoxyphenyl-β-D-glucoside)12个化合物是首次从宽筋藤中分离得到的。本研究结果丰富了宽筋藤中化学成分内涵,为宽筋藤的药效物质基础研究和质量控制研究奠定基础。第三部分:宽筋藤化学成分定量分析建立宽筋藤中反式丁香苷和Tinosinen的含量测定方法。采用HPLC法测定反式丁香苷和Tinosinen的含量,对提取工艺进行单因素考察,优选出最佳提取方法,并采用该方法测定不同地区市售宽筋藤药材中反式丁香苷和Tinosinen的含量,结果确定宽筋藤药材提取方法为,80倍量的30%甲醇回流提取90 min。不同地区市售宽筋藤药材反式丁香苷和Tinosinen的含量分别在0.0076%～0.0248%、0.0562%～0.1427%之间,表明不同来源的药材中两个成分的含量存在一定差异,其规律性需要进行大样本分析。采用石油醚提取宽筋藤中的脂肪酸,经甲酯化处理,采用GC-MS方法分离和鉴定脂肪酸,峰面积归一化法定量分析。共分离鉴定出饱和脂肪酸成分13种,总含量达到检出物的44.38%,其中棕榈酸含量最高为16.17%,其次是十七烷酸含量为7.85%。不饱和脂肪酸有4种,总含量达到检出物的28.43%,其中亚油酸含量为19.48%,11-十八烯酸含量为7.19%。特色与创新1.从宽筋藤中分离得到一个新天然化合物,5-羟甲基-2-呋喃丙烯酸(5-hydroxymethyl-2-fUranacrylic acid)。2.首次建立了宽筋藤中两个苯丙素类成分反式丁香苷和Tinosinen的含量测定方法。
[Abstract]:This paper is divided into three parts: the first part of the literature review on the chemical constituents, pharmacological activities and clinical applications of Caulis Spatholobi, and its future research directions were prospected, 34 references were cited; the distribution of trans-syringin plants, pharmacological activities and content analysis methods were reviewed, and its future research directions were also discussed. Part 2: Chemical constituents of Caulis Spatholobi were isolated and purified by ESI-MS, 1H-NMR, 13C-NMR and other spectroscopic techniques. 23 compounds were isolated and 22 compounds were identified, including 6 phenylpropanoids, 3 terpenoids and 3 terpenoids. 6 phenylpropanoids are trans-syringin, tinosinen, syringaresinol-4-O-beta-D-glucopyranoside, tinosposide, ring-opening isolaricin-9-O-beta-D-glucoside, respectively. Resinol-9-O-beta-D-glucopyranoside and isolariciresinol-9-O-beta-D-glucopyranoside are sesquiterpene tinocordiside, diterpenoid tinosineside A and triterpenoid cycloeucalenone, and three cerebrosides are 2-(2'-hydroxy-tetracarbonyl amino) octadecanol-1,3,4-triol (2'-hyd-hyd-hyd-glucopyranoside). Roxytetracosanoylamino) octadecane-1,3,4-triol, soya-cerebroside I and soya-cerebroside II, two alkaloids are trans-N-caffeoyltyramine and pseudopalmatine, one peptide ring (tyrosine-tyrosine) (cyclo (osyl-tyrosyl)) and one amino acid L-pyroglutamic acid (L-pyroglutlutlutamic acid), respectively. Amic acid, 5-hydroxymethyl-2-furanacrylic acid, bis (2-ethylhexyl) phthalate, 1,2-di-O-palmitoyl-3-O-beta-galactopyranosyl glycerol, 3,4-dimethoxyphenyl-beta-D-glucoside Ide, beta-sitosterol and daucosterol. According to SciFinder, 5-hydroxymethyl-2-furanacrylic acid (5-hydroxymethyl-2-furanacrylic acid) is a new natural compound isolated from nature for the first time. Pyranoside, cycloeucalenone, 2-(2'-hydroxytetracosanoylamino) octadecane-1,3,4-triol, soya-cerebroside I, soya-cerebroside II, trans-N-caffeyltyramine, pseudopalmatine, cyclo-tyrosine Twelve compounds, namely, syl-tyrosyl, L-pyroglutamic acid, bis (2-ethylhexyl) phthalate, 1,2-di-O-palmitoyl-3-O-beta-D-galactopyranosyl glycerol and 3,4-dimethoxyphenyl-beta-D-glucoside, were isolated for the first time from Caulis spatholobi. The results of this study enriched the connotation of the chemical constituents in Caulis Spatholobi and laid a foundation for the study of the pharmacodynamics and quality control of Caulis Spatholobi. Part III: Quantitative analysis of the chemical constituents of Caulis Spatholobi was carried out to establish a method for the determination of trans-syringin and Tinosinen in Caulis Spatholobi. The contents of trans-syringin and Tinosinen The content of trans-syringin and Tinosinen were determined by this method. The results showed that the extraction method was 80 times of 30% methanol reflux extraction for 90 minutes. The contents of Tinosinen and Petroleum ether were 0.0076%-0.0248% and 0.0562%-0.1427% respectively, which indicated that there were some differences in the contents of the two components from different sources, and the regularity needed large sample analysis. A total of 13 kinds of saturated fatty acids were isolated and identified by normalized quantitative analysis. The content of palmitic acid and heptadecanoic acid reached 44.38%, 16.17% and 7.85% respectively. There were 4 kinds of unsaturated fatty acids, the total content of which reached 28.43%, of which linoleic acid and 11-octadecanoic acid were 19.48% and 7.19% respectively. A new natural compound, 5-hydroxymethyl-2-fUranacrylic acid, was isolated from Caulis Spatholobi. 2. A method for the determination of trans-eugenoside and Tinosinen was established for the first time.
【学位授予单位】：北京中医药大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：R284.1

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