摘要
绞股蓝(Gynostemma pentaphyllum Thunb.Makion)为葫芦科(Cucurbitaceae)多年生草质藤本植物,系葫芦科绞股蓝属模式种植物,为葫芦科绞股蓝属内分布最广、资源最丰富的主要药用植物种类。绞股蓝皂甙是绞股蓝的主要有效成份,在药材中含量高,容易获得,其在神经系统疾病、肿瘤的治疗与防治等方面发挥着重要的作用。绞股蓝总皂甙属于四环三萜皂甙,其皂甙元在C-3、C-12和C-20位有β羟基存在。成甙的位置通常在C-3、C-6、C-20位,由于甙键属缩醛结构,易受酸、碱、酶的降解,水解后,不仅脱去糖生成次级甙,而且甙元的结构会发生变化,特别是侧链发生重排、环化等。本研究通过对皂甙的水解,分离纯化水解产物,鉴定结构,活性测定,以求发现结构新颖的化合物和活性先导物,丰富“类天然产物”化合物库和化学多样性。通过硅胶、ODS、Sephadex LH-20 RP-18,MCI等柱层析方法色谱手段,我们从绞股蓝总皂甙酸水解产物中分离得到了38个化合物,采用1H-NMR、13C-NMR、1H-1H COSY、HMQC、HMBC和NOESY等1D、2D-NMR波谱学测试手段及数据库,结合EI-MS、ESI-MS和HR-ESI-MS等技术,鉴定了35个化合物的结构,其中包括10个新的化合物:(3β,23S)-3–hydroxy- dammar- 20,24-dien-21-oic acid 21, 23-lactone(1-3),(3β,23R)-3- hydroxydammar- 20,24- dien-21-oic acid-21, 23-lactone(1-4),(3β, 23R)-3,25-dihydroxydammar -20-en-21-oic acid 21,23-lactone(1-5),3β,20β-dihydroxydammar-22,24-dien-21-oic acid 21,23- lactone (1-6),3β,20β,25-trihydroxydammar -21-oic acid 21, 23-lactone(1-7),gypegenin D(1-8),3β-hydroxy -dammar -24-en-23- carboxyl-21-oic acid(1-9),3β,20,23ξ,25 -tetrahydroxydammar-21-oic acid(1-10),3β,20,21,25- tetrahydroxydammar -21-O-β-D-glucopyranosyl(1-11),3β,21ξ,25- trihydroxydammar -20-ene- 21-O-β-D-glucopyranoside(1-12),(20S)-3β, 21ξ, 22ξ,24,25- pentahydroxy-21,24ξ- cyclodammarane (1-14),其结构均为达玛烷性骨架的三萜化合物。采用MTT法测定了化合物对乳腺管癌细胞(MDA-MB-435),肝癌细胞株(Hepg-2),人宫颈癌细胞(HeLa)三种细胞株的细胞毒活性,化合物1-3,1-4,1-8,1-32对乳腺管癌细胞(MDA-MB-435)增殖有较好的抑制作用;化合物1-11,1-6,1-5对肝癌细胞株(Hepg-2)增殖有较好的抑制作用;化合物1-6,1-7对人宫颈癌细胞(HeLa)增殖有较好的抑制作用。以Orlistat为阳性对照,测定了绞股蓝总皂苷酸水解产物对脂肪酶的抑制活性,大多数化合物的抑制活性较弱,只有化合物1-11,1-12表现了中等强度的脂肪酶抑制活性。
由于高等真菌次生代谢产物结构类型和生理活性的多样性,近年来高等真菌的研究已引起了国内外学者的广泛关注,但Cortinarius purpurascens(紫色丝膜菌)化学成分和抗氧化活性的研究尚未见报道。Cortinarius purpurascens为丝膜菌科(Cortinariaceae),丝膜菌属(Cortinarius)大型真菌子实体,分布于欧洲、北美洲、日本及中国的黑龙江、吉林、湖南、四川等地。以采自贺兰山自然保护区森林中的的Cortinarius purpurascens为研究对象,利用DPPH法测定了不同提取部位的抗氧化活性,结果显示,乙酸乙酯相活性较好,然后从乙酸乙酯萃取相中,利用硅胶柱层析、葡聚糖凝胶LH-20柱层析、RP-18柱层析等方法,分离得到18个单体化合物,并借助质谱(EI-MS, FAB-MS)、氢谱(1H-NMR)、碳谱(13C-NMR)等现代波谱技术对各个化合物进行了结构鉴定,确定了14个化合物的结构,其中包括有9个蒽醌类色素,1个脑苷脂,4个麦角甾类化合物,均为首次从该种真菌中分离得到,其中化合物Verbindung cr11(2-6)和Verbindung cr60(2-7)为首次从该属真菌中分离得到。利用DPPH法我们测定了乙酸乙酯相中分离得到的单体化合物的的抗氧化活性,测定结果表明化合物ufoolivacin(2-2),rufoolivacin D(2-3),rufoolivacin E(2-4),Leucorufoolivacin(2-5)具有较强的清除DPPH自由基能力。
Gynostemma pentaphyllum (Thunb.) Makino, also called Jiaogulan in China, is a perennial herbaceous vine that belongs to the Gynostemma genera in Cucurbitaceae family. As an important medicinal plant, Jiaogulan distributed widely in China and is a prolific resource. Gynosaponins are believed to be the main active components and play the crucial role for diverse pharmacological properties, such as nervous system diseases, cancer treatment and prevention. Gypenosides can be classified as etracyclic triterpenoid saponins, which haveβ-hydroxyl group at sites of C-3, C-12 and C-20. Glycosides normally located at site of C-3, C-6, C-20-bit, the rearrangement or cyclization of side-chain may easily arise and change into sub-glucoside after hydrolysis , for the internal acetal glucoside structure is vulnerable to acid, alkali and enzyme degradation.
In order to discover novel compounds and study the active substance of sub-glucoside, this paper dealt with the ethyl acetate extracts after hydrolysis of gynosaponins. Silica gel column chromatography, reversed-phase chromatography and Sephadex LH-20 were employed for isolation and purification of hydrolysates. In this study , 38 compounds from Acid hydrolysates were afforded, 35 compounds were elucidated by means of spectroscopic techniques including 1D and 2D-NMR (1H-NMR, 13C-NMR, 1H-1H COSY, HMQC, HMBC and NOESY) as well as mass spectrometry (EI-MS, ESI-MS and HR-ESI-MS) in combination with the advanced database, including 10 new compounds, dammarane-type triterpen. They are:(3β, 23S) -3 -hydroxydammar-20, 24-dien-21-oic acid 21, 23-lactone(1-3),(3β, 23R)-3-hydroxydammar-20, 24-dien-21-oic acid-21, 23-lactone(1-4),(3β, 23R)-3 , 25-dihydroxydammar-20-en-21-oic acid 21, 23-lactone(1-5) , 3β, 20β-dihydroxydammar-22, 24-dien-21-oic acid 21, 23-lactone ( 1-6 ) ,3β,20β,25-trihydroxydammar -21-oic acid 21, 23-lactone(1-7) , gypegenin D(1-8) ,3β-hydroxy- dammar-24-en -23-carboxyl-21-oic acid (1-9),3β,20,23ξ,25-tetrahydroxy dammar-21-oic acid(1-10),3β,20, 21,25-tetrahydroxydammar -21-O-β- D-glucopyranosyl (1-11),3β,21ξ,25-trihydroxy -dammar-20-ene -21-O-β-D-glucopyranoside (1-12),(20S)-3β, 21ξ, 22ξ,24,25-pentahydroxy -21,24ξ- cyclodammarane (1-14). All the compounds were tested for their cytotoxicity assay of cell strain of MDA-MB-435, Hepg-2, HeLa with the method of MTT. The result showed that compound 1-3,1-4,1-8,1-32 have better inhibititory effect on MDA-MB-435 proliferation, compound 1-11,1-6,1-5 have better inhibititory effect on Hepg-2 proliferation, compound 1-6,1-7 have better inhibititory effect on HeLa proliferation. With Orlistat as a positive control, acid hydrolysates gypenosides were tested by inhibitory activity of the lipase, most of the compounds shows inhibit weak activity, just compounds 1-11,1-12 showed moderate inhibitory activity of lipase.
Due to a wide variety of secondary metabolites from higher fungi and their biological activities, extensive attention has been paid to the researches of higher fungi both in China and abroad. However, there is no report on the chemical constituents and antioxidation activity of Cortinarius purpurascens. Cortinarius purpurascens, belongs to the family of Cortinariaceae and Cortinarius, is macrofungi fruiting bodies, distributed widely in Europe, North America, Japan and China's Heilongjiang, Jilin, Hunan, Sichuan and other places. This study tested anti-oxidant activity for different extracts of Cortinarius purpurascens, sampling at HeLanShan Natural Reserve by means of DPPH methods, result shows that ethyl acetate extracts have better activity. Pass through silica gel, Sephadex LH-20 and reversed-phase RP-18 column chromatography to afford 18 compounds from ethyl acetate extracts, 14 compounds were elucidated by means of spectroscopic techniques including mass spectrometry (EI-MS, and FAB-MS), as well as 1H-NMR. Including 9 of anthraquinone pigment, 1 Cerebroside, 4 ergot steroids compounds, they were first isolated the fungi. All the compounds were tested for their anti-oxidant assay with the method of DPPT, the result showed that compounds ufoolivacin (2-2), rufoolivacin D (2-3), rufoolivacin E (2-4), Leucorufoolivacin (2-5) has a strong DPPH free radical scavenging ability.
引文
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