三七中达马烷型皂甙的热不稳定性及酸水解产物

前人已证明人参和三七中富含的达马烷型人参皂甙在通常酸性水解下甙元即发生变化,而在弱酸(如50％醋酸,0.1N盐酸)条件下则形成次级皂甙。本文报道人参甙(ginseno-sides)和三七甙(notoginsenosides)的水溶液在水浴上加热亦分别形成相应的C-20位去糖基的次级皂甙。联系到人参和三七均有在蒸煮加工后C-20位去糖基皂甙收率增大的趋势,似可认为人参和三七中的这类皂甙有相当一部分是在生药的加工泡制以及提取过程中形成的次级皂甙,而不一定是植物体的原生成分。将人参甙Rb_1单体以酸水解,不仅得到主产物人参二醇(3),还分离到异去氢原人参二醇(5)、达马烷-20(22)-烯-3β,12β,26-三醇(6)、20(R)-达马烷-3β,12β,20,25-四醇(7)以及20(S)-和20(R)-原人参二醇(1、2)的混合物,从而认为这些微量成分与人参二醇一样均为达马烷型人参皂甙在酸性水解条件下C-20位糖基断裂后由真甙元的侧链转化形成的工作产物。     

盾叶薯蓣地上部分的三个新甾体皂甙

从盾叶薯蓣Dioscorea zingiberensis Wright地上部分分离鉴定了四个甾体皂甙,经鉴定甙A为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙;甙B为24α-羟基约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)]β-D-葡萄吡喃糖甙;甙C为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)][β-D-葡萄吡喃糖基(1→4)]-β-D-葡萄吡喃糖基;甙D为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)][β-D-葡萄吡喃糖基(1→3)]-β-D-葡萄吡喃糖甙。前三者为新化合物,分别命名为盾叶皂甙A_1、A_2、A_3(zingiberoside A_1、A_2、A_3),其中盾叶皂甙A_2的甙元为一新甾体皂甙元,命名为盾叶皂甙元(zingiberogenin)。     

滇产植物皂素成分的研究——Ⅹ.五指莲的两个新甾体皂甙(1)

从重楼属植物五指莲Paris axialis H.Li.根茎中分离到三个甾体皂甙,经化学降解,质谱,核磁共振谱分析,证明其中两个甙为新的化合物,即偏诺皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙(Ⅰ)和24α-羟基偏诺皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)][α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖(Ⅲ);另一个鉴定为薯芋皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙(Ⅱ)。     

人参茎叶总皂苷酶水解产物成分研究

人参茎叶提取物经β-糖苷酶催化水解后,经硅胶柱和RP-18柱反复层析纯化得8个化合物。通过波谱图分析及结合文献数据,分别鉴定为20(S)-达玛烷-3β,6α,12β,20,25-五醇(1)、人参皂苷compound K(2)、人参皂苷F1(3)、人参皂苷Rh13(4)、人参皂苷Rg2(5)、3β,20(S)-二羟基达玛烷-24-烯-12β,23β-环氧-20-O-β-D-吡喃葡萄糖苷(6)、人参皂苷Rg1(7)和人参皂苷Re(8)。其中化合物1为新的达玛烷皂苷元。化合物2为分离到仅有的原人参二醇型皂苷,表明该β-糖苷酶高效转化人参茎叶的原人参二醇型皂苷为人参皂苷compound K。     

五指莲重楼的甾体皂甙(2)

从五指莲重楼根中(Paris axialis)分离鉴定了七个甾体皂甙,其中有一新甙Ⅶ,经MS、~1H NMR、~(13)C NMR和化学降解方法证明其化学结构为:24α-羟基偏诺皂甙元-3-O-α-L-鼠李吡喃糖基1→2[α-L-阿拉伯呋喃糖基1→4]-β-D-葡萄吡喃糖甙。     

滇产植物皂素成分的研究——Ⅷ.禄劝花叶重接的甾体皂甙

从禄劝花叶重楼Paris Luquanensis H.Li.的干燥根中分离鉴定了二个甾体皂甙:甙Ⅰ称重楼甙H,其化学结构为偏诺皂甙元-3-O-α-阿拉伯呋喃糖(1←4)-[α-L-鼠李吡喃糖(1→2)]-β-D-葡萄吡喃糖甙;甙Ⅱ为偏诺皂甙元-3-O-α-L-鼠李吡喃糖(1→4)-α-L-鼠李吡喃糖(1→4)-α-L-鼠李吡喃糖(1→2)]-β-D-葡萄吡喃糖甙,即我们从滇重楼中分得的重楼甙Ⅶ。二者均具有很有趣的生理活性。此外,从该种植物中还分得胡萝卜甙及β-蜕皮激素。     

攀援孔药花化学成分研究

从攀援孔药花全草95%乙醇提取物中首次分离得到19个化合物,通过波谱数据或与已知物对照,它们分别鉴定为:(2S,3S,4R)-2-[(2R)-2-羟基-二十一酰胺基]-二十一烷-1,3,4-三醇(1)、(2S,3S,4R)-2-二十四酰胺基-十八烷-1,3,4-三醇(2)、胡萝卜甙(3)、β-谷甾醇(4)、(20S,22E,24R)-5α,8α-表二氧-麦角甾-6,22-二烯-3β-醇(5)、6β-羟基-豆甾-4-烯-3-酮(6)、十六烷酸-1-甘油酯(7)、桦木酸(8)、大黄素(9)、二十二烷酸-1-甘油酯(10)、对羟基苯甲醛(11)、十七烷酸-1-甘油酯(12)、金色酰胺醇乙酸酯(13)、十九烷酸-1-甘油酯(14)、棕榈酸(15)(、E)-p-香豆酸(16)、(22E,24S)-24-甲基-5α-胆甾-7,22-二烯-3β,5α,6β-三醇(17)、2-去氧-β-蜕皮激素(18)和auranamide(19)。     

中华青荚叶的一个新果糖酯

从山茱萸科中华青荚叶( Helwingia chinensis )的乙醇提取物中分离得到一个新果糖酯和十个已知化合物.通过现代波谱技术分别鉴定为:2- O -(E)-咖啡酰-3- O -(3, 5-二甲氧基香豆酰)-α-D-呋喃果糖甙(1),2- O -β-D-呋喃果糖基α-D-异吡喃糖酯(2),甘草甜素(3),4′-羟基-7- O -葡萄糖-2, 3-二羟黄酮甙(4),黄豆甙(5),5-葡萄糖芹菜甙(6),7- O -葡萄糖芹菜甙(7),4- O -葡萄糖香豆酸(8), 葡萄糖咖啡酸(9), 3β-赤杨醇(10), 薯蓣皂甙3- O -{α-L-鼠李糖吡喃糖基(1→2)-[α-L-阿拉伯呋喃糖基(1→3)]-β-D-葡萄糖吡喃糖} (11).     

滑桃树茎皮的化学成分

从大戟科植物滑桃树的茎皮中分离得到七个化合物,通过波谱分析或与已知化合物进行薄层层析对比,分别鉴定为β-谷甾醇(1)、胡萝卜甙(2)、蒲公英赛酮(3)、苔色酸乙酯(4)、苔色酸乙酯和甲酯混合物(4和5)、麦角甾-5α,8α-二环氧-22E,24R-6,22-二烯-3β-醇(6)和(2S,3S,4R,12E,2’R)-2-(2’-羟基-二十二碳酰胺基)二十碳-1,3,4-三羟基-12-烯(7)。其中化合物4、5、6和7为首次从该种植物中分离得到。     

滇产植物皂素成分的研究——Ⅵ.滇重楼皂甙(2)

从滇重楼干根粉中分离出三个甾体皂甙,鉴定为薯芋皂甙元-3-O-α-L-鼠李吡喃糖(1→2)-β-D-葡萄吡喃糖甙V,偏诺皂甙元-3-O-α-L-鼠李吡喃糖(1→2)-β-D-葡萄吡喃糖甙Ⅵ,偏诺皂甙元-3-O-α-L-鼠李吡哺糖(1→4)-α-L-鼠李吡喃糖(1→4)-〔α-L-鼠李吡喃糖(1→2)〕-β-D-葡萄吡喃糖甙Ⅶ.皂甙Ⅵ和Ⅶ已显示出有趣的生理活性。     

Structures of ascaroside aglycones

Free and derivatized aglycones and parent ascarosides of Ascaris lumbricoides and A. columnaris (Nematoda) were isolated by thin-layer and gas chromatography and analyzed by mass spectrometry and polarimetry. Results for monol aglycones confirmed previous chain-length assignments and the location of the l-hydroxyl group at C-2. The major monols of even carbon number possessed a methyl branch on the penultimate carbon (ω ? 1). Diol alycones were entirely unbranched homologues, mainly 31 and 33 carbons long, and had hydroxyl groups on C-2 and C-(ω ? 1). These aglycones were truly symmetrical, for they were optically inactive with the center bearing the glycone in diol ascaroside (C-2), being mostly or entirely the l configuration. Three major features of ascaroside structure—chain length composition of the aglycones, molecular weight of the unusual glycone (a dideoxyhexose), the kind and position of acyl groups—were clearly discernible in the spectra of intact ascarosides.     

Studies on the biosynthesis of avermectins

To elucidate the pathway of avermectin biosynthesis, the biosynthetic relationships of avermectins A1a, A2a, B1a, B2a, and their respective monosaccharides and aglycones were studied. 14C-labeled avermectin compounds prepared from [1-14C]acetate were fed to Streptomyces avermitilis strain MA5502 and their metabolites were determined. Two furan ring-free aglycones, 6,8a-seco-6,8a-deoxy-5-keto avermectin B1a and B2a, have been isolated from the fermentation broth of a blocked mutant of S. avermitilis. Addition of the compounds and a semisynthetic compound, 5-keto avermectin B2a aglycone, to the fermentation medium of a second blocked mutant established that the two compounds are intermediates in the avermectin biosynthetic pathway immediately preceding avermectin aglycones.     

Prediction of intestinal absorption and metabolism of pharmacologically active flavones and flavanones

Three glycosilated flavonoids (diosmin, hesperidin and naringin) and respective aglycones were characterized in terms of their apparent ionisation constants and bidirectional permeability using the cellular model Caco-2 as well as the artificial membrane model PAMPA. Ionisation curves were established by capillary electrophoresis. It was confirmed that significant amounts of the aglycones are ionised at physiological pH whereas the glycosides are in the neutral form. Permeation was not detected for the glycosides in either the apical-to-basolateral or basolateral-to-apical directions confirming the need for metabolism before absorption through the intestinal membrane. The aglycones permeated in both directions with apparent permeabilities (P(app)) in the range of 1-8x10(-5) cm/s. The results from both in vitro methods correlated providing some evidence of passive transport; however, the hypothesis of active transport cannot be excluded particularly in the case of diosmetin. Metabolism of the aglycones was detected with the cell model, more extensively when loading in the apical side. Some of the metabolites were identified as glucuronide conjugates by enzymatic hydrolysis.     

Triaminotricarboxylic amino acid oxidation productions of actinoidin and ristomycin]

Aromatic acids with three benzene nuclei bound through oxygen were obtained from actinoidin and ristomycin on their oxydation with permanganates of methylated aglycones and peptides. The structures of the methyl esters of these acids were determined by spectral methods. They are the following: methyl-3,5-bis-(4-methoxycarbonyl-phenoxy)-4-methoxybenzoate (from ristomycin) and methyl-3-(2-chlor-4-methoxycarbonyl-phenoxy)-5-(4-methoxycarbonyl-phenoxy)-4-methoxybenzoate (from actinoidin). The compounds are the aromatic parts of the molecules of the unusual triaminotricarboxylic amino acids present in the aglycones of all antibiotics of the group of polycyclic glycopeptides.     

Biological activities of unique isoflavones prepared from Apios americana Medik

Four unique isoflavone aglycones (barpisoflavone A (1), 2′-hydroxygenistein (2), 5-methylgenistein (3), and gerontoisoflavone A (4)) whose structures were related to genistein were prepared from the tuber of Apios americana Medik. We examined the estrogen receptor and androgen receptor binding activities, estrogen agonistic activities, antioxidant activities, and α-glucosidase inhibitory activities of 1–4. The results obtained showed that 2 possessed potent and 1, 3, and 4 possessed moderate estrogen partial agonistic activities, 1 and 2 possessed moderate antioxidant activities, and 2 and 3 possessed moderate α-glucosidase inhibitory activities.     

Triterpene saponins from Chenopodium quinoa Willd

Twenty triterpene saponins (1-20) have been isolated from different parts of Chenopodium quinoa (flowers, fruits, seed coats, and seeds) and their structures have been elucidated by analysis of chemical and spectroscopic data including 1D- and 2D-NMR. Four compounds (1-4) were identified: 3beta-[(O-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl)oxy]-23-oxo-olean-12-en-28-oic acid beta-d-glucopyranoside (1), 3beta-[(O-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl)oxy]-27-oxo-olean-12-en-28-oic acid beta-d-glucopyranoside (2), 3-O-alpha-l-arabinopyranosyl serjanic acid 28-O-beta-d-glucopyranosyl ester (3), and 3-O-beta-d-glucuronopyranosyl serjanic acid 28-O-beta-d-glucopyranosyl ester (4). The following known compounds have not previously been reported as saponin constituents from the flowers and the fruits of this plant: two bidesmosides of serjanic acid (5,6), four bidesmosides of oleanolic acid (7-10), five bidesmosides of phytolaccagenic acid (11-15), four bidesmosides of hederagenin (16-19), and one bidesmoside of 3beta,23,30-trihydroxy olean-12-en-28-oic acid (20). The cytotoxicity of these saponins and their aglycones was tested in HeLa cells. Induction of apoptosis in Caco-2 cells by bidesmosidic saponins 1-4 and their aglycones I-III was determined by flow cytometric DNA analysis. The saponins with an aldehyde group were most active. The relationships between structure and cytotoxic activity of saponins and their aglycones are discussed.     

Modelling, synthesis and biological evaluation of novel glucuronide-based probes of Vibrio cholerae sialidase

The development of sialidase inhibitors is an area of continuing interest due to their potential use as therapeutic agents to combat viral and bacterial infections. Herein, we report our studies involving the sialidase from the pathogen Vibrio cholerae, through the modelling, synthesis and biological evaluation of mimetics of 5-acetamido-2,6-anhydro-3,5-dideoxy-D-glycero-D-galacto-non-2-enonic acid (Neu5Ac2en, 1), a naturally occurring sialidase inhibitor. These mimetics are O- and S-glycosides of N-acetyl-D-glucosaminuronic acid in which the aglycone portion effectively replaces the C-6 glycerol side chain of Neu5Ac2en (1). The choice of aglycones was aided by use of the X-ray crystal structure of V. cholerae sialidase complexed with Neu5Ac2en (1). All Neu5Ac2en mimetics tested were found to inhibit V. cholerae sialidase as determined using a standard fluorometric assay.     

On the relationship of OSW-1 to the cephalostatins

Antineoplastic bis-steroidal (cephalostatin-type) analogues of the saponin OSW-1 were produced from a dihydroaglycone of OSW-1. The key aglycone 6H was obtained from 5alpha-androstan-3beta-ol-17-one in 8 steps (38% yield). The SAR of the aglycones, intermediates, and hybrid analogues provide insights regarding the proposed common role of C22-oxocarbenium ions in the bioactivity of both OSW-1 and cephalostatins.     

Biosynthesis of yeast mannan : Diversity of mannosyltransferases in the mannan-synthesizing enzyme system from yeast

1. A microsomal enzyme preparation from the yeast Saccharomyces cerevisiae catalyzes the transfer of mannosyl units from GDPmannose to mannose and a number of mannose-containing oligosaccharides and glycosides whereby different glycosidic bonds are formed.2. Of the compounds tested besides mannose, only those containing an α-linked mannosyl unit at the nonreducing position of their moleculae were effective as receptors. Monodeoxyanalogues of mannose as well as α-mannose phosphates did not serve as receptors in the above reaction.3. The structure of the product formed with mannose as receptor was determined to be O-α-D-mannosyl-(1→2)-mannose; with αMan(1→Man(1→6)mannose as the acceptor, the product was αMan(1→6)αMan(1→6)mannose and with αMan-(1→2)mannose the product was tentatively characterized as a mixture of αMan-(1→3)αMan(1→2)mannose and αMan(1→2)αMan(1→2)mannose.4. The enzymes catalyzing the formation of different types of glycosidic bonds differed in their acceptor specificity, pH-activity curves and rates of heat denaturation.5. Radioactive disaccharids were unable to enter the mannan protein molecule in the cell-free system while free radioactive mannose did incorporate into polysacchride to a minor extent under the same conditions.     

An alternative explanation of hypertension associated with 17α-hydroxylase deficiency syndrome

The syndrome of 17α-hydroxylase deficiency is due to the inability to synthesize cortisol and is associated with enhanced secretion of both corticosterone and 11-deoxy-corticosterone (DOC). In humans, corticosterone and its 5α-Ring A-reduced metabolites are excreted via the bile into the intestine and transformed by anaerobic bacteria to 21-dehydroxylated products: 11β-OH-progesterone or 11β-OH-(allo)-5α-preganolones (potent inhibitors of 11β-HSD2 and 11β-HSD1 dehydrogenase). Neomycin blocks the formation of these steroid metabolites and can blunt the hypertension in rats induced by either ACTH or corticosterone. 3α,5α-Tetrahydro-corticosterone, 11β-hydroxy-progesterone, and 3α,5α-tetrahydro-11β-hydroxy-progesterone strongly inhibit 11β-HSD2 and 11β-HSD1 dehydrogenase activity; all these compounds are hypertensinogenic when infused in adrenally intact rats.Urine obtained from a patient with 17α-hydroxylase deficiency demonstrated markedly elevated levels of endogenous glycyrrhetinic acid-like factors (GALFs) that inhibit 11β-HSD2 and 11β-HSD1 dehydrogenase activity (>300 times greater, and >400 times greater, respectively, than those in normotensive controls). Thus, in addition to DOC, corticosterone and its 5α-pathway products as well as the 11-oxygenated progesterone derivatives may play a previously unrecognized role in the increased Na⁺ retention and BP associated with patients with 17α-hydroxylase deficiency.