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。     

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。     

Saponins of Chlorophytum Species

The genus Chlorophytum (Liliaceae) owing to the presence of pharmacologically important saponins has attracted interest of the scientific community to investigate the chemistry of the saponins and study their cytotoxicity. Chloromaloside-A having cytotoxicity against cancer cell lines has been isolated from C. malayense, while saponins from C. borivilianum are gaining popularity as substitute for viagra. The paper presents a review of different saponins isolated from the Chlorophytum species and their pharmacological importance.     

皂苷类药物代谢实验方法研究进展

许多皂苷类天然产物具有医疗保健作用。本文主要从皂苷药代体内外研究方法、皂苷药代生物样品预处理方法和检测方法等方面,概述了皂苷成分药物代谢实验方法的研究进展情况。     

广东冬青中的三萜及三萜皂甙成分

从广东冬青（Ｉｌｅｘ ｋｗａｎｇｔｕｎｇｅｎｓｉｓ）的叶中分离得到四个三萜皂甙和三个三萜成分,通过光谱解析及化学方法,三个三萜成分分别鉴定为齐墩果酸（１）、熊果酸（２）和常春藤皂甙元（３）;四个三萜皂甙成分分别鉴定为齐墩果酸３－Ｏ－β－Ｄ－吡喃葡萄糖基－（１→３）－α－Ｌ－吡喃阿拉伯糖甙（４）、齐墩果酸３－Ｏ－β－Ｄ－吡喃葡萄糖基－（１→２）－α－Ｌ－吡喃阿拉伯糖甙（５）、齐墩果酸３－Ｏ－β－Ｄ－     

大孔吸附树脂对苦瓜皂甙的吸附研究

试验通过静态吸附对几种树脂进行筛选,结果表明D-101对苦瓜皂甙有较大的吸附率和解吸率,适合用来提取纯化苦瓜皂甙.进一步对D-101进行动态吸附研究,结果表明,浓度为95%的乙醇,3个柱体积可以洗脱几乎所有的苦瓜皂甙.苦瓜皂甙粗提物的上样浓度为2.8～5.6 ms/mL之间.     

Effect of Quillaja saponaria saponins and Yucca schidigera plant extract on growth of Escherichia coli

Escherichia coli K-12 was exposed to Quillaja saponaria saponins from various commercial firms (Sigma, Roth and Nor-feed) and to an extract of Yucca schidigera plant powder (DK Sarsaponin 30) at different concentrations (0·05–1·0% w/v). A concentration-dependent response was observed. Quillaja saponaria saponins from Sigma increased growth up to 0·1% (w/v) level, whereas Nor-feed and Roth saponins produced maximum growth at a much higher level (0·5 and 0·75%, w/v, respectively). These results suggest that quillaja saponins from various sources differ in their biological activity, although all three saponins had the same content of vanillin-sulphuric acid reactive moieties. The lyophilized water extract from the DK Sarsaponin powder showed maximum growth at 0·1% (w/v) level. The levels at which maximum growth was observed did not change on subjecting the quillaja or yucca saponins to heat treatment in an autoclave (121 °C for 30 min). All the saponins and the plant extract increased growth of Escherichia coli up to a certain concentration and thereafter decreased growth. In spite of the decreased growth at higher levels of saponins, it was higher compared to the control (without saponin) up to levels of 1% (w/v) for all saponins except Quillaja saponins from Sigma, for which the growth was lower at levels of 0·25% (w/v) and higher. Saponins have the potential to modulate microbial growth in natural and artificial fermenters.     

番茄中皂苷类成分研究进展

皂苷因其在人体中具有重要的生理及药理活性一直是人们研究的热点.番茄是我们日常生活中最常食用的蔬菜,其主要活性物质除了人们熟知的番茄红素外尚含有含量并不低的水溶性番茄皂苷,目前国内有关番茄皂苷的研究报导较少.本文主要对上世纪70年代以来国外研究人员在番茄皂苷研究方面所取得的进展进行综述.     

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.     

甾体皂苷生物转化研究进展

甾体皂苷是中药中一类较为复杂的糖苷类化合物,具有多方面的药理活性。生物转化是利用各种酶系或微生物对天然活性化合物进行生物合成与结构修饰。利用生物转化技术可以对甾体皂苷类化合物完成化学法难以进行的结构改造和修饰,从而获得具有更高药用价值的目标化合物。本文对近几年利用微生物和酶法转化对甾体皂苷结构修饰的研究进展进行了综述,并分析了甾体皂苷生物转化研究中存在的问题,展望了其研究的前景。     

Metabolite profiling of saponins in <Emphasis Type="Italic">Balanites</Emphasis><Emphasis Type="Italic">aegyptiaca</Emphasis> plant tissues using LC (RI)-ESI/MS and MALDI-TOF/MS

Saponins are a major family of secondary metabolites which consist of a sugar moiety glycosidically linked to a hydrophobic aglycone (sapogenin). In recent years the interest in saponins has increased significantly because of their diverse properties as natural detergents and foaming agents, their cardiac, immunostimulating, and anti-cancer activity, as well as other health promoting functions. This study deals with metabolitic analysis of saponins from methanolic extracts of fruit mesocarp (ME), seed kernel (KE) and root (RE) of Balanites aegyptiaca (L.) Del. (desert date) plant grown in Israel using LC (RI)-ESI/MS and MALDI-TOF/MS. The structural assignment was carried out by fragmentation experiments of LC (RI)-ESI/MS and literature data. The study has revealed that, all together, twenty-four furostanol saponins were found in ME, KE and RE. Of these, four saponins are found only in ME, five only in KE and six only in RE. Diosgenin was found to be the sole aglycone in all the saponins. The smallest saponin (MW 740 Da) was found with two sugar units (glucose) and the largest saponin (MW 1678 Da) was found with eight sugar units (5 glucose, 2 rhamnose and 1 xylose) attached to diosgenin. The results suggest that MALDI-TOF/MS with positive ion mode is particularly effective for determining the metabolites of saponins in B. aegyptiaca plant tissues. MALDI-TOF/MS not only verified the results of the LC (RI)-ESI/MS, but also identified additional saponins that are now systematically organized in a database of B. aegyptiaca saponins. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Triterpenoid saponins from the stem bark of Caryocar villosum

Five triterpenoid saponins, caryocarosides II-22 (3), III-22 (4), II-23 (5), III-23 (6), and II-24 (7), have been isolated from the methanol extract of the stem bark of Caryocar villosum, along with two known saponins (1-2). The seven saponins are glucuronides of hederagenin (II) or bayogenin (III). Caryocaroside II-24 (7) is an unusual galloyl ester saponin acylated on the sugar chain attached to C-28, the 3-O-alpha-L-rhamnopyranosyl-(1-->3)-beta-D-galactopyranosyl-(1-->3)-beta-D-glucuronopyranosyl hederagenin-28-O-[2-O-galloyl-beta-D-glucopyranosyl] ester. The structures of the saponins were established on the basis of extensive NMR ((13)C, (1)H, COSY, TOCSY, HSQC, HMBC and ROESY) and ESI-MS studies. The cytotoxic activity of saponins 2 and 3 was evaluated in vitro against human keratinocytes. The DOPA-oxidase inhibition and the lipolytic activities were evaluated ex vivo using an explant of human adipose tissue.     

Saponin contents in the starfish Echinaster sepositus: Chemical characterization,qualitative and quantitative distribution

In this study, we report the inter-organ, the sexual and the seasonal variability, of saponins contained in the common Mediterranean starfish Echinaster (Echinaster) sepositus. Saponins were extracted from five distinct body components namely the stomach, the pyloric caeca, the gonads, the oral body wall and aboral body wall. Of both sexes (males and females) collected at different seasons, the saponins mixtures were analyzed by Mass spectrometry (HR-ESI-MS and HR-ESI- MS/MS). Semi-quantitative approach was performed to estimate the variability of the saponin amounts. Our results demonstrated that the diversity of saponins in E. sepositus is higher than previously reported. We highlighted 11 different saponins, including 9 new congeners. Presumptive molecular structures are proposed for 6 molecules on the basis of key-fragmentations identified by HR-ESI-MS/MS. The comparison of the saponin contained in the five different body components revealed that minimum 3 saponins are common in all tissues. In addition, qualitative and quantitative variability of saponins compounds were linked to the organ, sex and the collecting season. The relative highest level of saponins was found in the stomach on the period of active feeding (winter). The significant higher levels of saponins were found in the gonads and oral body wall on the spawning period (summer). Generally, a great inter-organ, sexual and seasonal variability was found in both sexes. These results suggest that saponins probably fulfill several biological functions in E. sepositus.     

百合总皂苷提取工艺及抗抑郁活性研究

本文研究百合总皂苷最佳提取工艺,继而采用AB-8大孔吸附树脂富集纯化百合总皂苷,并测试其抗抑郁活性。采用正交实验,考察乙醇浓度、提取次数、固液比及提取时间四个因素对该工艺的影响;采用小鼠悬尾实验和小鼠强迫游泳实验评价百合总皂苷的抗抑郁活性。确立了百合总皂苷的最佳提取工艺为:提取时间3h,乙醇浓度80%,固液比1∶10,提取次数为3次。在最佳提取工艺条件下,总皂苷提取率为1.24%。经过AB-8大孔树脂富集纯化总皂苷的含量达到62%以上。药理实验表明,百合总皂苷中剂量、小剂量能明显缩短小鼠悬尾的不动时间和游泳时间(P<0.05或者P<0.01),百合富集纯化的总皂苷部位具有较好的抗抑郁活性。     

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。     

Effects of Gypsophila saponins on bacterial growth kinetics and on selection of subterranean clover rhizosphere bacteria

Plant secondary metabolites, such as saponins, have a considerable impact in agriculture because of their allelopathic effects. They also affect the growth of soil microorganisms, especially fungi. We investigated the influence of saponins on rhizosphere bacteria in vitro and in soil conditions. The effects of gypsophila saponins on the growth kinetics of rhizosphere bacteria were studied by monitoring the absorbance of the cultures in microtiter plates. Gypsophila saponins (1%) increased the lag phase of bacterial growth. The impact of gypsophila saponins on subterranean clover rhizosphere was also investigated in a pot experiment. The addition of gypsophila saponins did not modify clover biomass but significantly increased (twofold with 1% saponins) the weight of adhering soil. The number of culturable heterotrophic bacteria of the clover rhizosphere was not affected by the addition of gypsophila saponins. Nevertheless, the phenotypical characterization of the dominant Gram-negative strains of the clover rhizosphere, using the Biolog system, showed qualitative and quantitative differences induced by 1% saponins. With the addition of saponins, the populations of Chryseomonas spp. and Acinetobacter spp., the two dominant culturable genera of control clover, were no longer detectable or were significantly decreased, while that of Aquaspirillum dispar increased and Aquaspirillum spp. became the major genus. Aquaspirillum dispar and Aquaspirillum spp. were also the dominant rhizosphere bacteria of Gypsophila paniculata, which greatly accumulates these saponins in its roots. These results suggest that saponins may control rhizosphere bacteria in soil through rhizodeposition mechanisms.     

Cytotoxic and anti-colorectal tumor effects of sulfated saponins from sea cucumber Holothuria moebii

BackgroundWhether sulfated saponins from Holothuria moebii inhibit the proliferation of colorectal cancer cells and have anti-colorectal tumor effects in animal model has not been investigated.PurposeTo evaluate the cytotoxic and anti-colorectal tumor effects of sulfated saponins from sea cucumber Holothuria moebii.Method(1) Column chromatography was used to prepare the total and individual saponins and HPLC was applied to define the components of the total saponins; (2) the activity of the total and individual saponins inhibiting the proliferation of human colorectal cancer cells was determined by SRB assay and the apoptosis induced by the saponins was qualified using cytometric analysis with Annexin V-FITC/PI double staining; and (3) the antitumor effects of the sulfated saponins on colorectal CT-26 tumor-bearing Balb/c mice were tested.ResultsThe total and individual sulfated saponins significantly inhibited the proliferation of four different human colorectal cancer cells with IC₅₀ values ranging from 1.04 to 4.08 μM (or 1.46 to 3.24 μg/ml for total saponins) and induced late apoptosis at an early treatment time in cancer cells. The total saponins (120 mg/kg) had antitumor activity in colorectal CT-26 tumor-bearing Balb/c mice.ConclusionThe sulfated saponins from H. moebii remarkably inhibited the proliferation of different human colorectal cancer cells and had significant anti-colorectal tumor activity in animal model.     

Three-liquid-phase extraction of diosgenin and steroidal saponins from fermentation of Dioscorea zingibernsis C. H. Wright

Diosgenin is an important starting material in the steroidal hormone industry. The yield of diosgenin obtained from the fermentation of Dioscorea zingibernsis C. H. Wright (DZW) by Trichoderma harzianum is higher than that typically obtained from acid hydrolysis. In this paper, the extraction of steroids in the culture broth was studied. A novel three-liquid-phase system (TLPS) consisted of petroleum ether, ethanol, ammonium sulphate and water was used to separate diosgenin and steroidal saponins in the culture broth. The partition behaviors of various steroidal saponins, diosgenin and glucose were investigated. From this, an optimized TLPS was obtained, which composed of 30% ethanol (w/w), 17% (NH₄)₂SO₄ (w/w) and 40% (w/w) petroleum ether. In the optimized TLPS, almost all of the diosgenin was extracted into the top phase giving a recovery of 97.24%, whereas the steroidal saponins were mainly extracted into the middle phase, with recoveries of zingibernsis newsaponin, deltonin and diosgenin-diglucoside reaching almost 100%. The recoveries of trillin and diosgenin-triglucoside were 96.03% and 98.82%, respectively. Glucose tended to remain in the bottom phase, giving a recovery of 72.01%. The three-liquid-phase extraction (TLPE) successfully resulted in the simultaneous separation of diosgenin, untransformed steroidal saponins and glucose.     

Inhibition of herbivory on young holly leaves: evidence for the defensive role of saponins

Summary Response of the southern red mite, Oligonychus ilicis McGregor, to young and one year old leaves of Ilex opaca Aiton was studied on three dates during the period of leaf expansion in the spring. Young foliage, which is rich in nutrients but also contains high levels of saponins, was found to be unsuitable for colonization by this oligophagous herbivore until the leaves had matured and levels of saponins had declined. Mites preferentially colonized and had higher survival and reproduction on sclerophyllous, one-year old leaves than on young leaves in early spring. High levels of saponins in young, second-flush leaves of shoots that had earlier been damaged by frost were again correlated with low mite survival in June. Laboratory preference tests with the fall webworm, Hyphantria cunea Drury, and the eastern tent caterpillar, Malacosoma americanum (F.), indicated that young, saponin-rich holly foliage is especially unpalatable to these highly polyphagous caterpillars. Fifth instar fall webworms required significantly longer to complete their development, attained lower weights, and had greater mortality on artificial diet amended with low concentrations of purified holly saponins than on control diet. These results support the hypothesis that the high levels of saponins in young holly leaves provide protection from herbovores until the leaves have matured and their structural defenses are developed.The investigation reported in this paper (No. 88-7-8-196) is in connection with a project of the Kentucky Agricultural Experiment Station and is published with the approval of the Director