木通科植物的化学分类

木通科为双子叶植物纲中较原始的一个小科,多为寡种属和单种属,主要分布于东亚地区。我国共有7属29种,其中很多种为传统的药用植物。本文简要综述木通科植物近几十年的化学研究状况,并从化学分类学的角度探讨木通科属间和与其近缘科之间的系统关系。结果表明齐墩果烷型三萜皂甙作为木通科的特征化学成分在该科的系统分类中具有一定的意义。齐墩果烷型三萜皂甙不仅提示木通科与毛茛科的毛茛亚科的系统联系,而且甙元骨架的氧化水平与科内各属的系统进化也有一定的相关性。     

黄花远志的新齐墩时烷型三萜皂甙

从云南产远志科药用植物黄花远志茎皮的乙醇提取物中何妨以４个新的齐墩果烷型三萜皂甙,人花远志皂甙Ａ－Ｄ。同时还分离得到１个已知的三萜皂甙远志甙ＸＸＸＶ。它们的结构通过波谱方法推定。     

木通科植物的化学分类

木能科为双子叶植物纲中较原始的一个小科,多为寡种属和单种属,主要分布于东亚地区。我国共有7属29种,其中很多种为传统的药用植物。本文简要综述木通科植物近几十年的化学研究状况,并从化学分类学 的角度探讨木通科属间和与其近缘科之间的系统关系。结果表明齐墩果烷型三匝皂甙作为木通科的特征化不成发在该科的系统分类中具有一定的意义。齐墩果烷型三萜皂甙不仅提示木通科与毛莨科的毛莨亚科的系统联系,而且甙元骨架的氧化水平与科内各属的系统进货也有一定的相关性。     

黄花远志的新齐墩果烷型三萜皂甙

从云南产远志科药用植物黄花远志(PolygalaarillataBuchHamexDDon)茎皮的乙醇提取物中分离得到4个新的齐墩果烷型三萜皂甙,命名为黄花远志皂甙(arillatanoside)A～D。同时还分离得到1个已知的三萜皂甙远志甙(polygalasaponin)XXXV。它们的结构通过波谱方法推定。     

金铁锁的三萜化合物

金铁锁(Psammosilene tunicoides W.C.Wu et C.Y.Wu)为石竹科金铁锁属植物,该属仅此一种,特产于我国西南部,是云南民间重要药用植物,常用于止血止痛,活血祛瘀等。其根部富含皂甙,有镇痛、抗炎和抑菌等生理活性。我们将金铁锁根总皂甙用酸水解后分离到多种皂甙元成分,本文报告其中六个皂甙元的分离和结构鉴定,它们均为齐墩果烷型五环三萜化合物。     

珍珠菜属植物三帖类化合物研究进展

对珍珠菜属(Lysimachia)植物中已报道的三萜类化合物化学结构和生物活性研究进行了综述。本属中的三萜皂苷均以齐墩果烷型五环三萜为苷元基本骨架,根据皂苷元结构,可将皂苷分为13β,28-环氧-齐墩果烷型(Ⅰ型)和12-烯-齐墩果烷型(Ⅱ型),同时论述了Ⅰ型和Ⅱ型皂苷元化学结构转换。     

鼠李科达玛烷型三萜皂甙的化学研究进展

本文对国内外有关鼠李科达玛烷型三萜皂甙的类型、结构以及物理性质的研究进行了综述,并对此类化合物的分离以及化学反应和波谱方法在其结构鉴定中的应用作了较详细的介绍。     

二杈狗牙花的化学成分

从二杈狗牙花（Ｅｒｖａｔａｍｉａｄｉｖａｒｉｃａｔａ（Ｌ．）Ｂｕｒｋ）中共分离出８个已知化合物,分别为３个环菠萝蜜烷型三萜：ｃｙｃｌｏａｒｔ－２３－ｅｎｅ－３β,２５－ｄｉｏｌ（１）,３β－ｈｙｄｒｏｘｙｃｙｃｌｏａｒｔ－２５－ｅｎｅ－２４－ｏｎｅ（２）,ｃｙｃｌｏｅｕｃａｌｅｎｏｌ（３）;２个吲哚生物碱ｅｒｖａｔａｍｉｎｅ（４）和ｔａｂｅｒｎａｅｍｏｎｔａｎｉｎｅ（５）;其他是β－谷甾醇,３β－乙酰－香树脂醇和胡萝卜甙。它们均由波谱方法鉴定。其中环菠萝蜜烷型三萜系首次被发现存在于狗牙花属植物中     

五味子科药用植物亲缘学初探

五味子科Schisandraceae隶属于双子叶植物门木兰亚纲Magnoliidae八角目Illiciales, 全球分布约60种, 包括两个属: 五味子属Schisandra和南五味子属Kadsura, 间断分布于亚洲东南部和北美东南部。本文归纳了中国五味子科植物两大类活性成分--木脂素和三萜的分布规律、传统疗效和现代药理活性, 并对中国五味子科的药用植物亲缘学进行了初探。联苯环辛烯类木脂素(I)集中分布于五味子科植物, 可以被认为是五味子科植物的特征性化学成分, 除了传统的保肝作用外, 这类化合物中很多具有潜在的抗氧化、抗肿瘤和抗HIV活性, 一些联苯环辛烯类的木脂素, 尤其是在八元环C-6、C-9位上具有羟基或者酯化取代具有更好的抗HIV和抗肿瘤活性; 而螺苯骈呋喃型联苯环辛烯类木脂素(II)绝大多数存在于南五味子属, 其特殊的螺苯骈呋喃环及其钙拮抗、抗凝血和抑制血小板聚集的活性, 不仅初步说明了民间南五味子属药用植物藤茎具有较强活血化瘀药理作用的活性物质基础, 也提示在对南五味子属的药材质量标准研究中, 可以考虑以此类成分作为定性定量指标。五味子科植物中木脂素成分的分布规律提示, 在演化程度上五味子属植物较南五味子属植物更原始。环菠萝蜜烷类三萜在五味子属和南五味子属均有分布, 尤其是A环开环的环菠萝蜜烷类三萜(II)在抗HIV和抗肿瘤活性方面具有很好的潜力, 而结构更进化的7/7/5/6型三萜内酯(IV)显示了很强的细胞毒活性, 目前只在南五味子属的长梗南五味子K. longipedunculata中发现。从五味子属的小花五味子S. micrantha和狭叶五味子S. lancifolia中分离得到的多个成环复杂且高度氧化的类三萜内酯中也发现具有抗肿瘤和抗HIV潜力。     

碳谱在甙结构测定中的应用

本文以齐墩果烷型五环三萜皂甙为例,较为详细地总结归纳了~(13)C-NMR谱在糖的数目,构型、构象、连结位置以及糖链数目等方面的应用规律,以及~(13)C-NMR谱在甙键稳定性、糖的连接顺序等方面的研究概况。     

Antimelanogenic Activity of Ocotillol‐Type Saponins from Panax vietnamensis

The ocotillol (OCT)‐type saponins have been known as a tetracyclic triterpenoid, possessing five‐ or six‐membered epoxy ring in the side chain. Interestingly, this type saponin was mostly found in Panax vietnamensis Ha et Grushv ., Araliaceae (VG), hence making VG unique from the other Panax spp. Five OCT‐type saponins, majonoside R2, vina‐ginsenoside R2, majonoside R1, pseudoginsenoside RT4, vina‐ginsenoside R11, together with three protopanaxadiol (PPD)‐type saponins and four protopanaxatriol (PPT)‐type saponins from VG were evaluated for their antimelanogenic activity. All of isolates were found to be active. More importantly, the five OCT‐type saponins inhibited melanin production in B16‐F10 mouse melanoma cells, without showing any cytotoxicity. Besides ginsenoside Rd and ginsenoside Rg3 in PPD and notoginsenoside R1 in PPT‐type saponins, majonoside R2 was the most potent melanogenesis inhibitory activity in OCT‐type saponins. In this article, we highlighted antimelanogenic activity of OCT‐type saponins and potential structure–activity relationship (SAR) of ginsenosides. Our results suggested that OCT‐type saponins could be used as a depigmentation agent.     

UPLC-Q-TOF-MS快速鉴定黄山野生绞股蓝中皂苷类物质

为鉴定黄山野生绞股蓝中皂苷类成分,为黄山野生绞股蓝的开发利用提供理论基础。实验选取超高效液相色谱串联四级杆飞行时间质谱联用技术(UPLC-Q-TOF-MS),采用waters Acquity HSS T3色谱柱(2.1 mm×100 mm,1.8μm),以0.1%甲酸水溶液(A)-乙腈(B)为流动相,梯度洗脱。质谱采用电喷雾(ESI)离子源,在正离子模式下采集数据,首先选取4种具有达玛烷型结构的皂苷标准品进行分析,总结达玛烷型皂苷类物质质谱裂解规律及特征离子碎片信息,再依据这些规律快速鉴定黄山野生绞股蓝中的皂苷类物质。从黄山野生绞股蓝中共鉴别出25种皂苷类物质,其中有6个化合物在该植物中属首次发现。     

Saponins from Swartzia langsdorffii: biological activities

The presence of saponins and the molluscicidal activity of the roots, leaves, seeds and fruits of Swartzia langsdorffii Raddi (Leguminosae) against Biomphalaria glabrata adults and eggs were investigated. The roots, seeds and fruits were macerated in 95% ethanol. These extracts exerted a significant molluscicidal activity against B. glabrata, up to a dilution of 100 mg/l. Four mixtures (A2, B2, C and D) of triterpenoid oleanane type saponins were chromatographically isolated from the seed and fruit extracts. Two known saponins (1 and 2) were identified as beta-D-glucopyranosyl-[alpha-L-rhamnopyranosyl-(1->3)- beta-D-glucuronopyranosyl-(1->3)]-3beta-hydroxyolean-12-ene-28 -oate, and beta-D-glucopyranosyl-(1->3)-beta-D-glucuronopyranosyl-(1 ->3)]-3beta-hydroxyolean-12-ene-28-oate, respectively. These two saponins were present in all the mixtures, together with other triterpenoid oleane type saponins, which were shown to be less polar, by reversed-phase HPLC. The saponin identifications were based on spectral evidence, including H- H two-dimensional correlation spectroscopy, nuclear Overhauser and exchange spectroscopy, heteronuclear multiple quantum coherence, and heteronuclear multiple-bond connectivity experiments. The toxicity of S. langsdorffii saponins to non-target organisms was prescreened by the brine shrimp lethality test.     

Naturally occurring triterpenoid saponins

Naturally occurring new triterpenoid saponins reported from mid-1996 to March, 2007 are reviewed including their physical constants and plant sources, and are compiled in Table 1. New saponins are arranged in Table 1 on the basis of the skeletal structures of their aglycones, e.g., oleanane type, ursane type, lupane type, hopane type, taraxastane type, cycloartane type, lanostane type, tirucallane type, dammarane type, cucurbitane type, and holostane type. The known triterpenoid saponins and prosapogenins of the new saponins, the biological and pharmacological activities of which were published during 1996-2007, are also reviewed together with their plant sources listed in Table 2 according to the skeletal structures of their aglycones in the same fashion as in Table 1. The plant and animal sources of both new and known bioactive triterpenoid saponins are collected in Table 3 in alphabetical order. The biological and pharmacological activities such as antiallergic, antiatherosclerosis and antiplatelet, antibacterial, anticomplementary, antidiabetic, contraceptive, antifungal, anti-inflammatory, antileishmanial, antimalarial/antiplasmodial, anti-obesity, anti-proliferative, antipsoriatic, antispasmodic, antisweet, antiviral, cytotoxic/antitumor, detoxication, gastroprotective, haemolytic, hepatoprotective, immunomodulatory, anti-enzyme, anti-osteoporotic, insecticidal, insulin-like, membrane-porosity, molluscicidal, neuropharmacological, anti-endothelial dysfunction, snake venom antidote, and sweet activities of these saponins or derived prosapogenins are discussed briefly after Table 3.     

Real-time analysis of membrane permeabilizing effects of oleanane saponins

Saponins are a group of plant and marine derived glycosides with numerous biological functions. Two important characteristics of certain plant saponins are their ability to enhance cytotoxicity of type I ribosome inactivating proteins and stimulation of the immune system. The main objective of the present study was to investigate in real-time the permeabilizing effects of saponins on cell membrane. A set of oleanane saponins (glycyrrhizinic acid, Gypsophila, Saponaria and Quillaja saponins) and a steroid saponin (digitonin) were tested. The effects of these saponins on lysosomal membranes and hemolysis, along with their charge were also studied. Real-time monitoring of cell membrane permeabilization facilitated a highly sensitive analysis of the cellular kinetics. Saponins showed variable permeabilizing effects on cellular and lysosomal membranes at concentrations from 6 μM and hemolysis from 3 μM. Further, the results suggest that charge of the saponin may be relevant for permeabilizing effects of oleanane saponins.     

Triterpenoid saponins from Echinopsis macrogona (Cactaceae)

Triterpene saponins, pachanosides C1, E1, F1 and G1 (1-4), and bridgesides A1, C1, C2, D1, D2, E1 and E2 (5-11) were isolated from Echinopsis macrogona. Compounds 1-4 were saponins with pachanane type triterpene saponins, while the others (5-11) were oleanane type triterpene saponins. While the aglycones of 2-4 and 8-11 were hitherto unknown, the structure of pachanol C was revised in this paper. Their structures were elucidated on the basis of chemical and physicochemical evidence.     

Metabolic switching of astringent and beneficial triterpenoid saponins in soybean is achieved by a loss‐of‐function mutation in cytochrome P450 72A69

Triterpenoid saponins are major components of secondary metabolites in soybean seeds and are divided into two groups: group A saponins, and 2,3‐dihydro‐2,5‐dihydroxy‐6‐methyl‐4H‐pyran‐4‐one (DDMP) saponins. The aglycone moiety of group A saponins consists of soyasapogenol A (SA), which is an oxidized β‐amyrin product, and the aglycone moiety of the DDMP saponins consists of soyasapogenol B (SB). Group A saponins produce a bitter and astringent aftertaste in soy products, whereas DDMP saponins have known health benefits for humans. We completed map‐based cloning and characterization of the gene Sg‐5, which is responsible for SA biosynthesis. The naturally occurring sg‐5 mutant lacks group A saponins and has a loss‐of‐function mutation (L164*) in Glyma15g39090, which encodes the cytochrome P450 enzyme, CYP72A69. An enzyme assay indicated the hydroxylase activity of recombinant CYP72A69 against SB, which also suggested the production of SA. Additionally, induced Glyma15g39090 mutants (R44* or S348P) lacked group A saponins similar to the sg‐5 mutant, indicating that Glyma15g39090 corresponds to Sg‐5. Endogenous levels of DDMP saponins were higher in the sg‐5 mutant than in the wild‐type lines due to the loss of the enzyme activity that converts SB to SA. Interestingly, the genomes of palaeopolyploid soybean and the closely related common bean carry multiple Sg‐5 paralogs in a genomic region syntenic to the soybean Sg‐5 region. However, SA did not accumulate in common bean samples, suggesting that Sg‐5 activity evolved after gene duplication event(s). Our results demonstrate that metabolic switching of undesirable saponins with beneficial saponins can be achieved in soybean by disabling Sg‐5.     

甾体皂甙研究新进展

本文介绍近年来（１９８１－１９９１）甾体皂甙研究的一些新进展,包括新发现的结构新颖和具有显著生理活性的化合物,及其现代分离方法和结构鉴定中所采用的新技术。     

Enhancement of saporin cytotoxicity by Gypsophila saponins—More than stimulation of endocytosis

Saporin is a type I ribosome-inactivating protein with N-glycosidase activity. It removes adenine residues from the 28S ribosomal RNA resulting in inhibition of protein synthesis. Recently we have shown that saporin exerts no cytotoxicity on seven human cell lines. However, the combination of saporin with a special mixture of Gypsophila saponins (Soapwort saponins) from Gypsophila paniculata L. (baby's breath) rendered saporin to a potent cytotoxin comparable to viscumin, a highly toxic type II ribosome-inactivating protein.In this study we investigated whether the enhancement of the saporin-cytotoxicity by Gypsophila saponins is mediated by a saponin-triggered modulation of endocytosis, exocytosis or impaired degradation processes of his-tagged saporin (^hissaporin) in ECV-304 cells. For this purpose ^hissaporin was labelled with tritium and cytotoxicity of the toxin alone and in combination with Gypsophila saponins was scrutinized. The transport and degradation processes of ^hissaporin were not different in Gypsophila saponin-treated and control cells. However, after ultracentrifugation of a post-nuclear supernatant the amount of cytosolic ^hissaporin was significantly higher in saponin-treated cells than in cells, which were only incubated with ^hissaporin. This indicates a saponin mediated endosomal escape of saporin.     

Saponins in Tribulus terrestris – Chemistry and Bioactivity

Tribulus terrestris is a valuable herb known for its application in the folk medicine in many parts of the world. Furostanol and spirostanol saponins of tigogenin, neotigogenin, gitogenin, neogitogenin, hecogenin, neohecogenin, diosgenin, chlorogenin, ruscogenin and sarsasapogenin type are frequently found in this plant. Four sulphated saponins of tigogenin and diosgenin type are also isolated. Extracts and steroidal saponins have been found to possess various pharmacological activities. Preparations based on the saponin fraction of T. terrestris are used for treatment of infertility and libido disorders in men and women, as well as for treatment of cardiac diseases. Food supplements containing T. terrestris extracts are on sale in USA and Europe with claim of a general stimulating action. In this review the steroidal saponins found in T. terrestris are presented, covering the literature up to 2004. The data reveal clear difference in the saponin composition of samples from this plant species collected from different geographical regions. A comprehensive account on the biological activity of extracts and individual saponins is also included.