小花草玉梅化学成分研究

目的:研究银莲花属植物小花草玉梅的化学成分。方法:采用硅胶柱色谱,凝胶柱色谱,反相柱色谱并结合制备高效液相色谱等技术分离纯化单体化合物,并根据理化性质及光谱数据鉴定结构。结果:分离并鉴定了4个化合物,分别是常春藤皂苷元-28-O-β-D-吡喃葡萄糖酯苷(1)、3-O-β-D-吡喃葡萄糖-(1→2)-α-L-吡喃阿拉伯糖-齐墩果酸皂苷元-28-O-α-L-吡喃鼠李糖-(1→4)-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯苷(2)、3-O-β-D-吡喃葡萄糖-(1→2)-α-L-吡喃阿拉伯糖-常春藤皂苷元-28-O-α-L-吡喃鼠李糖-(1→4)-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯苷(3)和3-O-β-D-吡喃核糖-(1→3)-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖-常春藤皂苷元-28-O-α-L-吡喃鼠李糖-(1→4)-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯苷(4)。结论:化合物1为首次从银莲花属植物中分离得到,2-4为首次从小花草玉梅中分离得到。     

A squalene epoxidase from Nigella sativa participates in saponin biosynthesis and mediates terbinafine resistance in yeast

Squalene epoxidase catalyzes the formation of 2,3-oxidosqualene from squalene and in plants is the last enzyme common to all biosynthetic pathways leading to an array of triterpene derivatives like phytosterols, brassinosteroid phytohormones or saponins. In this work, we present a squalene epoxidase gene (NSSQE1) from the triterpene saponin producing plant Nigella sativa. The gene product showed a high degree of homology to functional squalene epoxidases (SQEs) from Arabidopsis thaliana and was able to complement SQE deficient yeast that harboured a knockout mutation in the underlying erg1 gene. Moreover, the expression of the NSSQE1 gene in ERG1 wild type yeast revealed that NSSQE1 conferred resistance towards terbinafine, an inhibitor of fungal SQEs. The latter suggested that a terbinafine-dependent NSSQE1 selection marker system can be developed for yeast. The gene NSSQE1 was ubiquitously expressed in all plant tissues analysed, including roots where no triterpene saponins are produced. Therefore, we argue that NSSQE1 is a housekeeping gene for triterpene metabolism in Nigella sativa. Similar to triterpene saponins, NSSQE1 was up-regulated by methyl jasmonate in leaves and should also be functionally involved in saponin biosynthesis in Nigella sativa.     

Cycloartane-type glycosides from Astragalus amblolepis

Five cycloartane-type triterpene glycosides were isolated from the methanol extract of the roots of Astragalus amblolepis Fischer along with one known saponin, 3-O-β-D-xylopyranosyl-16-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane. Structures of the compounds were established as 3-O-β-D-xylopyranosyl-25-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane, 3-O-[β-D-glucuronopyranosyl-(1 → 2)-β-D-xylopyranosyl]-25-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane, 3-O-β-D-xylopyranosyl-24,25-di-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane, 6-O-α-L-rhamnopyranosyl-16,24-di-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane, 6-O-α-L-rhamnopyranosyl-16,25-di-O-β-D-glucopyranosyl-3β,6α,16β,24(S),25-pentahydroxy-cycloartane by using 1D and 2D-NMR techniques and mass spectrometry. To the best of our knowledge, the glucuronic acid moiety in cycloartanes is reported for the first time.     

HBsAg颗粒表面的“尾巴”现象

乙型肝炎表面抗原(HBsAg)可引起保护性抗体,故对其结构的研究十分重视。已知HBsAg颗粒由子粒组成,对它的氨基酸序列亦有不少了解。然而子粒之间是怎样连结着,未见报道。我们用皂素等处理使HBsAg颗粒松散,以观察子粒间的结构,结果发现处理后,HBsAg颗粒上可裂解出像条尾巴的丝状物,暂称为尾巴现象。从典型的尾巴上香出,子粒之间有着线性连结。现作如下报道。     

The stromacentre inAvena plastids: an aggregation ofβ-glucosidase responsible for the activation of oat-leaf saponins

The stromacentre, a particular structure in the plastids of mostAvena species, was isolated from etioplasts ofAvena sativa and then characterized to determine its biological function. When comparing differentAvena species with or without stromacentre, it was shown that the stromacentre, a 63-kDa protein, and saponins (characteristic compounds ofAvena sativa) either occur together or not at all. This linkage was confirmed by demonstrating a transformation of saponins by the isolated stromacentre protein: avenacosides were hydrolyzed to 26-desgluco-avenacosides. Therefore, the stromacentre protein had to be regarded as a-glucosidase. Enzyme assays usingp-nitrophenyl--d-glucopyranoside as substrate showed that this-glucosidase has a pH optimum at pH 6.0. The calculatedK _m value for this substrate was 2.2·10^-3 M. Antibodies against the stromacentre protein inhibited-glucosidase activity. The determination of the molecular weight of the-glucosidase by sodium dodecyl sulfate-gel electrophoresis showed that it consists of subunits of 63 kDa. After gel electrophoresis under non-denaturing conditions, enzymatically active molecules were shown to consist of at least two of these subunits. Molecules aggregated up to about 10⁶ Da also had enzyme activity. Enzyme assays using avenacosides as substrate showed a pH optimum at pH 6.0. The calculatedK _m value for this substrate was 1.2·10^-5 M. The high affinity to the avenacosides and the high specificity for the C-26 bound glucose indicate that avenacosides are the natural substrates for this-glucosidase. Assuming that the avenacosides in oat leaves play a role as preformed chemical inhibitory substances against phytopathogenic microorganisms, a model is presented showing the stromacentre with a central role in activating the fungitoxicity of avenacosides.     

西洋参化学成分——皂甙的含量测定

本文采用Shibata提取方法,以人参皂甙Re为标准品,通过对样品提取液的薄层分离,用香草醛—高氯酸比色法对不同产地、不同年生、不同规格的西洋参及其不同部位中的总皂甙和分组皂甙作了含量测定。结果表明:各种西洋参样品总皂甙含量差异较大;三醇型与二醇型皂甙含量比为1:2.93～1:3;花蕾皂甙含量最高。     

羽叶三七根茎的三萜皂甙成分及其化学分类学意义

羽叶三七(Panax japonicus C. A. Meyer var. bipinnalifidus (Scem.) Wu et Feng)又称疙瘩七,产我国西北部至西南部山区,是人参届植物中分布海拔和纬度均较高的一个种类。在陕西省秦岭地区主要产于南北坡海拔2100—2900米的针叶林下阴湿处。民间以其根茎入药,具有清热解毒、顺气健胃、活血祛瘀、滋补强壮之效。作为国产人参属植物皂甙成分系统研究的一个部分,本文报告秦岭产羽叶三七根茎的皂甙成分,并讨论其化学分类学意义。     

Triterpenoid-biosynthetic UDP-glycosyltransferases from plants

Triterpenoid saponins are naturally occurring structurally diverse glycosides of triterpenes that are widely distributed among plant species. Great interest has been expressed by pharmaceutical and agriculture industries for the glycosylation of triterpenes. Such modifications alter their taste and bio-absorbability, affect their intra?/extracellular transport and storage in plants, and induce novel biological activities in the human body. Uridine diphosphate (UDP)-glycosyltransferases (UGTs) catalyze glycosylation using UDP sugar donors. These enzymes belong to a multigene family and recognize diverse natural products, including triterpenes, as the acceptor molecules. For this review, we collected and analyzed all of the UGT sequences found in Arabidopsis thaliana as well as 31 other species of triterpene-producing plants. To identify potential UGTs with novel functions in triterpene glycosylation, we screened and classified those candidates based on similarity with UGTs from Panax ginseng, Glycine max, Medicago truncatula, Saponaria vaccaria, and Barbarea vulgaris that are known to function in glycosylate triterpenes. We highlight recent findings on UGT inducibility by methyl jasmonate, tissue-specific expression, and subcellular localization, while also describing their catalytic activity in terms of regioselectivity for potential key UGTs dedicated to triterpene glycosylation in plants. Discovering these new UGTs expands our capacity to manipulate the biological and physicochemical properties of such valuable molecules.     

A saponin tolerant and glycoside producer xylariaceous fungus isolated from fruits of <Emphasis Type="Italic">Sapindus saponaria</Emphasis>

The plant Sapindus saponaria is a good producer of terpenoidal and sesquiterpenoidal saponins, which are accumulated in its fruits. Although saponins usually act as antifungal compounds, a fungus was found living on the internal part of its pericarp. Tentative identification of the fungus, based on micro and macro-morphological aspects inspection, as well as on the secondary metabolite production, suggested the fungus to be a Xylariaceous microorganism. When the fungus is placed in contact with glycosides extracted from the host plant, or exogenous glycosides and other terpenoid compounds, it showed ability to transform them in another compounds. Analysis of these products using liquid chromatography and mass spectrometry showed that these biotransformations are mainly monohydroxylation and glycosilation. These findings contrasts most of the reports found in the literature which shows that hydrolysis at sugar chain are frequently observed during glycoside biotransformation by fungi.     

镧对华重楼生长及皂苷含量的影响

本研究以4年生华重楼（Paris polyphylla Smith var. chinensis（Franch.）Hara）为实验材料,分别采用0、5、20、80、160 mg/L的加镧营养液培养华重楼植株,通过比较不同营养生长指标及采用HPLC法测定根茎皂苷组分,研究不同施镧水平对华重楼生长及皂苷含量的影响。结果显示,镧对华重楼生长及皂苷含量均有显著影响,随着镧溶液浓度的增加,华重楼皂苷含量呈上升趋势,但当镧含量达到160.00 mg/L时,则会对华重楼的生长产生抑制作用,导致株高降低、比叶面积升高。研究结果表明80.00 mg/L的施镧水平最有利于华重楼的营养生长及根茎皂苷积累。