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。     

葫芦科植物三萜皂甙研究十年进展（1980—1992）

综述了２９８０年至１９９２年以来葫芦科盒子草属,土贝母属Ｃａｙａｐｏｎｉａ属,南瓜属,Ｆｅｖｉｌｌｅａ属,纹股蓝属,雪胆属,丝瓜属,苦瓜属,棒锤瓜属,罗汉果属,赤ｂａｏ属,Ｗｉｌｂｒａｄｉａ等１３属２４种植物２００多个三萜类新化合物的研究概况。其中值得注意的是五环三匝齐墩果烷型大环皂甙,四环三萜葫芦烷型甜味甙,非葫芦烷型三萜皂甙,达玛烷型皂甙和巴查烷型三萜皂甙的发现。文末附参考文献８３篇。     

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。     

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。     

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。     

四川木通科药用植物资源与综合利用研究

四川木通科药用植物资源与综合利用研究陈兴芳李江陵尹国萍（四川省中药研究所,重庆６３００６５）木通科Ｌａｒｄｉｚａｂａｌａｃｅａｅ约８属,５０种,主产东亚和南美智利。我国有６属４０余种,分布于长江南各省区。本科植物主要化学成分为三萜皂甙及酚类物质,果实...     

蓣知子的化学成份研究（Ⅲ）

从木通科木通属植物白木通[Akebia trifolinta (Thunb.) Koidz. var. australis(Dies)Rehd]的种子(蓣知子)抗肿瘤活性的乙醇提取物中以硅胶层析等方法分得一种三萜皂甙。经波谱分析及酸碱水解确定了其化学结构,命名为:3-O-α-L-吡喃阿拉伯糖常春藤皂甙元-28-O-β-D吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖甙(即Saponin D),为首次自该植物中获得。     

木通科、大血藤科种子的研究，(1)种皮的扫描电镜观察

利用种皮扫描特征进行分类学和系统演化研究,这在木通科,大血藤科研究中尚属 空白。本文就5属15种木通科植物及大血藤科植物的种皮进行了扫描电镜观察。 从种皮雕纹类型看,大血藤科与木通科存在很大差异。Akebia,Holboellia,Stauntonia属植物通常具条纹状种皮雕纹,Sinofranchetia属植物也具条纹状种皮雕纹,但其条纹上具众多疣状凸起, 在 形态上较特殊。Decaisnea属植物的种皮具嵌合型雕纹,这在木通科十分罕见。以上,进一步印证了Stapf等人关于大血藤科分类学处理的正确性,说明了Decaisnea属和Sinofranchetia属在木通科的孤立地位;以及Akebia,Holboellia,Stauntonia属之间较密切的亲缘关系。     

金铁锁皂甙的研究

从金铁锁(Psammoslene tunicoides)根中分离到二个新的齐墩果烷型五环三萜皂甙Ⅰ、Ⅱ,经光谱测定和化学降解证明它们的化学结构为齐墩果烷-3α,16α-二羟基-12烯-23-酸-28-O-β-D-葡萄吡喃糖基(1—3)-β-D-葡萄吡喃糖基(1—6)-β-D-葡萄吡喃糖甙(Ⅰ)和齐墩果烷-3α,16α-二羟基-12烯-23-酸-28-O-β-D-葡萄吡喃糖基1—6[-β-D-葡萄吡喃糖基1—3]-β-D-葡萄吡喃糖甙(Ⅱ)。上述两个化合物的母核配基均为同一的物质,差异是糖的连接位置不相同。     

First results on the insecticidal action of saponins

In the search for new, natural insecticides, numerous scientists are currently trying to obtain useful compound from plants. A possibly interesting class of molecules are the saponins, a group of steroidal or triterpenoidal secondary plant metabolites with divergent biological activities. In this study, we investigated the activity of saponins against living caterpillars Spodoptera littoralis) and aphids (Acyrthosiphon pisum) via treatment on artificial diets containing different concentrations of saponins. We conclude that saponins have insecticidal activity, causing mortality and/or growth inhibition in the tested insects, although from our experiments the mode of action could not be identified.     

Triterpenoidal saponins from Gleditsia sinensis

Six bisdesmosidic triterpenoidal saponins, gleditsiosides H-K and gleditsia saponins C' and E', were isolated from the anomalous fruits of Gleditsia sinensis. Their structures were established by a combination of extensive NMR (DEPT, DQF-COSY, HETCOR, HOHAHA, HMBC and ROESY) studies and chemical degradation.     

Development of a novel method for triterpenoidal saponins in rat plasma by solid-phase extraction and high-performance liquid chromatography tandem mass spectrometry

A novel method using high-performance liquid chromatography tandem mass spectrometry (HPLC–MS/MS) has been developed for the quantification of four triterpenoidal saponins (anemoside B4, pulsatilloside B, anemoside A3, and 23-hydroxybetulinic acid) in rat plasma following solid-phase extraction (SPE). The optimized procedure utilized off-line extraction of the analytes from plasma using polymeric (Strata-X) SPE cartridges. Detection and quantitation were performed by MS/MS using electrospray ionization (ESI) and multiple reaction monitoring (MRM) in a novel multiswitching monitoring mode. The analytes and internal standard (scutellarin) were analyzed using a Sapphire C18 column (250 × 4.6 mm, 5 μm) with a linear gradient elution. The mass transition ion pairs of the triterpenoidal saponins were executed as follows: m/z 1219.7/749.4 for anemoside B4, m/z 819.4/347.2 for pulsatilloside B, m/z 749.6/471.2 for anemoside A3, m/z 471.4/471.4 for 23-hydroxybetulinic acid, and m/z 461.1/285.0 for the internal standard. The specificity, linearity, accuracy, precision, recovery, matrix effect, and stabilities were validated for all analytes in the plasma samples. In conclusion, the validation results demonstrate that this method is robust and specific. This validated method is a novel technique for sample preparation and quantitation and was successfully applied to estimate the pharmacokinetics of triterpenoidal saponins.     

Quality control of Pulsatilla koreana based on the simultaneous determination of triterpenoidal saponins by HPLC‐ELSD and principal component analysis

Introduction – Pulsatilla koreana Nakai, with triterpenoidal saponins as its main pharmacological effective compounds, is known to have several biological activities, including hypoglycaemic, antitumour, cognition‐enhancing, neuroprotective, cytotoxic and antiangiogenic activities. However, few analytical methods have been reported on the quality assessment of P. koreana roots. Obejective – To establish a high‐performance liquid chromatography coupled with evaporative light scattering detection for the simultaneous determination of five triterpenoidal saponins, including pulsatilloside E (1), pulsatilla saponin H (2), anemoside B₄ (3), hederacolchiside E (4) and cussosaponin C (5) in P. koreana. Methodology – The chromatographic separation was performed on a Shiseido CapCell PAK C₁₈ analytical column efficiently using gradient elution with acetonitrile and water. Results – All calibration curves showed excellent linear regressions (R² > 0.9996) within the range of tested concentrations. The intra‐ and inter‐day variations were below 4.78% in terms of RSD. The recoveries were 94.82–102.97% with RSD of 0.27–3.92% for spiked P. koreana samples. Conclusion – The validated method was successfully used for the analysis of five saponins in P. koreana from different locations. Moreover, the different samples were clustered in accordance with contents of triterpenoidal saponins based on aglycon type by a principal component analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Saponins in Pollen

Phosphate buffered saline (PBS) extracts of pollen of 34 out of 95 angiosperm species (in 40 families) tested, lysed human and/or snake head fish (Channa striatus Bloch) erythrocytes during assay for lectins in pollen. The bitter taste of the pollen extracts of these 34 species, the formation of a stable foam on shaking and the ability to lyse erythrocytes, suggested the presence of saponins, which have not, so far, been reported from pollen. Thin Layer Chromatography (TLC) and Mass Spectrum (MS) of the erythrocyte-lysing extracts of pollen of the garden gladiolus (Gladiolus gandavensis Van Hout.) confirmed that the pollen contained both triterpenoidal and steroidal saponins. The implications for the presence of saponins in pollen inhaled from the atmosphere, in the diagnosis and management of pollen allergy are discussed.     

Phytochemical and molluscicidal investigations of Fagonia arabica

The aqueous methanolic extract of the aerial parts of Fagonia arabica L. (family Zygophyllaceae) was successively fractionated using certain organic solvents. From the ethyl acetate fraction, two flavonoid glycosides were isolated and identified as kaempferol-7-O-rhamnoside and acacetin-7-O-rhamnoside. Four triterpenoidal glycosides were isolated from the butanolic layer. Their structures were elucidated on the basis of the spectral and chemical data as 3-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinopyranoside oleanolic acid (1), 3-O-alpha-L-arabinopyranosyl quinovic acid 28-O-beta-D-glucopyranoside (2), 3-O-[beta-D-glucopyranosyl-(1-->2)]-beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinosyl oleanolic acid (3) and 3-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-arabino-pyranosyl quinovic acid 28-O-beta-D-glucopyranoside (4). The two monodesmosidic saponins 1 and 3 were found to possess strong molluscicidal activity against Biomphalaria alexandrina snails, the intermediate host of Schistosoma mansoni in Egypt (LC90 = 13.33 and 16.44 microM), whereas the other two bidesmosidic saponins 2 and 4 as well as the two flavonoid glycosides were inactive up to 50 microM.     

Triterpenoidal saponins from Madhuca butyracea.

Two new triterpenoidal saponins, butyrosides A and B, were isolated from the seeds of Madhuca butyracea, along with two known saponins, Mi-saponin A and 16 alpha-hydroxy Mi-saponin A. On the basis of chemical and spectroscopic evidence, the structures of butyrosides A and B were established to be 3-O-beta-D-glucopyranosyl protobassic acid 28-O-beta-D-apiofuranosyl(1----3)-beta-D-xylopyranosyl (----4)-alpha-L-rhamnopyranosyl(1----2)-alpha-L-arabinopyranoside and 3-O-beta-D-glucopyranosyl 16 alpha-hydroxy protobassic acid 28-O-beta-D-apiofuranosyl(1----3)-beta-D-xylopyranosyl (1----4)-alpha-L-rhamnopyranosyl(1----2)-alpha-L-arabinopyranoside , respectively.     

Triterpenoidal saponins from Hydrocotyle sibthorpioides

Oleanane-type triterpenoidal saponins, hydrocosisaponins A-F (1-6), along with a known saponin, hydrocotyloside VII (7), were isolated from Hydrocotyle sibthorpioides. Their structures were established on the basis of spectroscopic analyses including NMR spectroscopic techniques ((13)C, (1)H, COSY, HMQC, HMBC, TOCSY and NOESY). Biological evaluation established that saponins possessing four sugar units (three d-glucoses and one l-arabinose) (4-7) exhibited moderate cytotoxicity against KB, Daoy and WiDr human tumor cell lines.     

Diastereoisomeric saponins from Albizia julibrissin

The structures of four new diastereoisomeric triterpenoidal saponins Julibroside J5, J8, J12 and J13 (1-4) isolated from Albizia julibrissin Durazz. (Leguminosae) have been determined on the basis of comprehensive spectroscopic analysis and chemical degradation. Julibroside, J8 and J13 showed marked cytotoxic activities against Bel-7402 cancer cell line at 100 microg/mL.