甜菜树属——我国云南产山柚子科一原始新属及其植物地理学意义

报道了产于我国云南红河流域山柚子科的一个原始新属——甜菜树属,该属具大型圆锥花序,两性,是Lepionurus, Melientha和Champereia 3个单型属的祖型,无疑起源于康滇古陆即今之云南高原,其发现对研究山柚子科的起源与分化具重要意义。     

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)。     

青灰叶下珠内生菌Phomopsis sp.TJ507A的化学成分及生物活性研究

为探究药用植物青灰叶下珠(Phyllanthus glaucus)来源内生真菌拟茎点霉(Phomopsis sp. TJ507A)的化学成分,本实验联合运用硅胶柱色谱、ODS柱色谱、凝胶柱色谱(Sephadex LH-20)、半制备型高效液相色谱(HPLC)等分离技术,从该菌株大米固体发酵产物的乙酸乙酯提取物中分离得到4个倍半萜化合物phomophyllin O(1)、phomophyllin P(2)、7-hydroxy-10-methoxydehydrodihydrobotrydial(3)、plorantinone D(4)和8个甾体化合物fortis-terol(5)、dankasterone B(6)、(14α,22E)-14-hydroxy-ergosta-7,22-diene-3,6-dione(7)、(14α,22E)-14-hydroxyerg-osta-4,7,22-triene-3,6-dione(8)、calvasterol B(9)、isocyathisterol(10)、ergosta-4,6,8(14),22-tetraen-3-one(11)和ganodermaside D(12)。化合物1和2为新化合物,运用现代波谱分析技术、[Rh2(OCOCF3)4]络合诱导ECD法及与文献对比等方法,鉴定了化合物1和2的结构和绝对构型。化合物1～5、7、8和10均为首次从该属真菌中分离得到。通过体外生物活性评价,发现化合物9具较强的NO生成抑制活性(IC508. 7μM)。     

An improved synthesis of (20R,22R)-cholest-5-ene-3beta,20,22-triol, an intermediate in steroid hormone formation and an activator of nuclear orphan receptor LXR alpha.

Asymmetric dihydroxylation of (20(22)E)-cholesta-5,20(22)-dien-3beta-ol acetate (2a), prepared from pregnenolone, gave a 1:1 mixture (67% yield) of (20R,22R)-cholest-5-ene-3beta,20,22-triol 3-acetate (3a) and its 20S,22S isomer 3b. Highly purified 3a and 3b were obtained by semipreparative silver ion high performance liquid chromatography. Saponification of 3a and 3b gave (20R,22R)-cholest-5-ene-3beta,20,22-triol (4a) and its 20S,22S isomer 4b. This simple approach provided the natural isomer 4a more efficiently than previously described chemical or enzymatic syntheses. Full 1H and 13C nuclear magnetic resonance data were presented for triols 4a and 4b and their synthetic precursors. Side-chain conformations of 2a, its 20(22)Z isomer, 4a, and 4b were studied by molecular mechanics and nuclear Overhauser effect difference spectroscopy.     

Massarilactones E-G, new metabolites from the endophytic fungus Coniothyrium sp., associated with the plant Artimisia maritima

Three new massarilactones E-G (1-3) and the massarilactone acetonide (4) were isolated from the ethyl acetate extract of the endophytic fungus Coniothyrium sp., associated with the plant Artimisia maritima. Their structures were determined by analysis of the 1D and 2D NMR and mass spectroscopic data. The structure of massarilactones E (1) was confirmed by X-ray diffraction analysis, and its absolute configuration determined by the solid-state CD/TDDFT method.     

Triamcinolone acetonide regulates glucocorticoid-receptor levels by decreasing the half-life of the activated nuclear-receptor form

Glucocorticoid-receptor activation in GH1 cells results from the conversion of a 10 S oligomeric cytosolic form to a 4-5 S nuclear-binding species (Raaka, B. M., and Samuels, H. H. (1983) J. Biol. Chem. 258, 417-425). In this study, we report that triamcinolone acetonide (9 alpha-fluoro-11 beta, 16 alpha, 17 alpha, 21-tetrahydroxypregna-1,4-diene-3,20-dione 16,17-acetonide) elicits a time- and dose-dependent reduction of total-cell (nuclear + cytoplasmic) receptor. The mechanism of receptor regulation was studied by dense amino acid labeling of receptor using media containing 2H, 13C, and 15N-labeled amino acids. Total cell receptor was extracted with 0.4 M KCl and newly synthesized dense receptor was separated from pre-existing receptor of normal density by centrifugation in gradients of 15-30% sucrose (w/v) in D2O. Receptor levels in cells grown without [3H]triamcinolone acetonide was 260 +/- 19 fmol/100 micrograms of DNA (16,000 molecules/cell), and, with 10 nM [3H]triamcinolone acetonide, this decreased to 130 +/- 14 fmol/100 micrograms of DNA after 30 h. Receptor half-life was 19 +/- 1.9 h in the absence and 9.5 +/- 0.3 h in the presence of triamcinolone acetonide and accounted for the decrease in steady-state receptor levels. Receptor synthesis was 9.7 +/- 0.3 fmol/100 micrograms of DNA/h (580 molecules/cell/h) both in the presence and absence of 10 nM [3H]triamcinolone acetonide. Triamcinolone acetonide reduced the half-life in proportion to the extent of receptor occupancy and activation. During the approach to steady-state conditions, 10 nM [3H]triamcinolone acetonide shortened receptor half-life almost immediately to the value in cells grown with [3H]triamcinolone acetonide for 24 h or longer. Cycloheximide did not prevent the triamcinolone acetonide-mediated decrease in receptor half-life and the shortening of receptor half-life is rapidly reversed by removal of hormone. These studies support a model of receptor regulation in which triamcinolone acetonide converts the unactivated 10 S receptor to the activated 4-5 S form which is degraded at an increased rate by the cell.     

Nuclear Overhauser effect studies of the conformations of MgATP bound to the active and secondary sites of muscle pyruvate kinase

MgATP binds both at the active site (site 1) and at a secondary site (site 2) on each monomer of muscle pyruvate kinase as previously found by binding studies and by X-ray analysis. Interproton distances on MgATP bound at each site have been measured by the time-dependent nuclear Overhauser effect in the absence and presence of phosphoenolpyruvate (P-enolpyruvate), which blocks ATP binding at site 1. Interproton distances at site 2 are consistent with a single conformation of bound ATP with a high antiglycosidic torsional angle (chi = 68 +/- 10 degrees) and a C3'-endo ribose pucker (delta = 90 +/- 10 degrees). Interproton distances at site 1, determined in the absence of P-enolpyruvate by assuming the averaging of distances at both sites, cannot be fit by a single adenine-ribose conformation but require the contribution of at least three low-energy structures: 62 +/- 10% low anti (chi = 30 degrees), C3'-endo; 20 +/- 8% high anti (chi = 55 degrees), O1'-endo; and 18 +/- 8% syn (chi = 217 degrees), C2'-endo. Although a different set of ATP conformations might also have fit the interproton distances, the mixture of conformations used also fits previously determined distances from Mn2+ to the protons of ATP bound at site 1 [Sloan, D. L., & Mildvan, A. S. (1976) J. Biol. Chem. 251, 2412] and is similar to the adenine-ribose portion of free Co(NH3)4ATP, which consists of 35% low anti, 51% high anti, and 14% syn [Rosevear, P. R., Bramson, H. N., O'Brian, C., Kaiser, E. T., & Mildvan, A. S. (1983) Biochemistry 22, 3439].(ABSTRACT TRUNCATED AT 250 WORDS)     

2'(3')-O-L-Phenylalanyl derivatives of N2,5'-anhydroformycin and N4,5'-anhydroformycin: new substrates for ribosomal peptidyltransferase with a fixed anti and syn conformation of the base

The 2'(3')-O-L-phenylalanyl-N2,5'-anhydroformycin (1c) and 2'(3')-O-L-phenylalanyl-N4,5'-anhydroformycin (2c), obtained by chemical synthesis, are substrates for ribosomal peptidyltransferase from Escherichia coli. Nucleoside 1c, which mimics an anti conformation of antibiotic formycin, has 80% of the acceptor activity of puromycin at 5 x 10(-4) M determined by the release of N-Ac-Phe residue from the 70 S ribosome-poly(U)-N-Ac-[14C]Phe-tRNA complex. The reaction product, 2'(3')-O-(N-acetyl)-L-phenylalanyl-L-phenylalanyl-N2,5'-anhydroformyc in (1d), was characterized by paper electrophoresis before and after alkaline hydrolysis. By contrast, nucleoside 2c, which resembles a syn conformation of formycin, exhibited only 20% of the acceptor activity of puromycin at 5 x 10(-4) M. The results which are in accord with previous models have shown that a substrate with its base in an anti conformation is preferable for the acceptor site of peptidyltransferase than the corresponding syn counterpart. Nevertheless, it is possible that an intermediate conformation, for example, high anti (amphi-minus), is an optimal arrangement for acceptor site substrates.     

石山巴豆枝叶的化学成分研究

石山巴豆( Croton euryphyllus)为大戟科( Euphorbiaceae)巴豆属( Croton)植物,主要分布于西南各省的岩溶石山地区,民间用于杀虫和治疗跌打损伤。为了阐明其化学物质基础,该研究采用硅胶柱层析、Sephadex LH-20、HPLC等方法对石山巴豆枝叶醇提物进行分离纯化。结果表明：共分离得到16个化合物,分别鉴定为异毛叶巴豆萜(1), jatrophoidin (2),山藿香定(3),异山藿香素(4),山藿香素(5),赖百当-13-烯-8,15-二醇(6),7-酮基-β-谷甾醇(7),(22E)-5α,8β-表二氧麦角甾-6,22-二烯-3β-醇(8),豆甾烷-4-烯-6β-醇-3-酮(9),齐墩果烷-12-烯-2α,3β-二醇(10),东莨菪内酯(11),催吐萝芙木醇(12), lyratol F (13),罗布麻酚A (14),芹菜素(15),金色酰胺醇酯(16)。所有化合物均为首次从该植物中分离得到,其中化合物8－16为首次从巴豆属中发现。     

Phytoecdysteroids from the juice of Serratula coronata L. (Asteraceae).

Seven phytoecdysteroids have been isolated from Serratula coronata L. One of them is a new phytoecdysteroid, 3-epi-20-hydroxyecdysone. Two further ecdysteroids, 20-hydroxyecdysone 22-acetate and taxisterone, are isolated from this species for the first time in addition to the typical S. coronata ecdysteroids, 20-hydroxyecdysone, ecdysone, ajugasterone C and polypodine B. The juice squeezed from aerial parts of fresh plants of S. coronata was extracted with ethyl acetate. The ecdysteroids were isolated by a combination of chromatographic techniques (mainly HPLC) and identified by 1D and 2D (1)H and (13)C NMR experiments and mass-spectrometry. The biological activities of 3-epi-20-hydroxyecdysone (EC(50)=1.6 x 10(-7) M), taxisterone (EC(50)=9.5 x 10(-8) M) and ajugasterone C (EC(50)=6.2 x 10(-8) M) have been determined in the Drosophila melanogaster B(II) bioassay for ecdysteroid agonist activity.     

Regulation of 24-hydroxylase activity in mouse skin fibroblast by cholecalciferol derivatives, triamcinolone acetonide and a calcium modulating agent, nicardipine

Mouse skin fibroblasts in culture were used to study the regulation of 1,25-dihydroxycholecalciferol (1,25(OH)2D3) induced 24 hydroxylase (24-OH-ase) under the influence of 3 agents: (1) 24,25-Dihydroxycholecalciferol (24,25(OH)2D3), 62.5 10(-9) M, which led to a significant decrease in the 1,25(OH)2D3-induced 24-OH-ase, probably acted through a nuclear effect mediated by the 1,25(OH)2D3 receptor protein. (2) Triamcinolone acetonide (10(-6)M) which was found to increase the 24-OH-ase enhancement induced by 1.25 and 6.25 nM 1,25(OH)2D3 whereas it did not alter the effect of 31.2 nM 1,25(OH)2D3. (3) A factor which is likely to induce changes in the cell calcium transport or in the Ca pool sizes, i.e. a calcium channel blocker, nicardipine. The effect of 1.25 nM 1,25(OH)2D3 on 24-OH-ase activity was increased by nicardipine (20 microM) which was found to reduce the effect of 6.25 nM 1,25(OH)2D3. The rate of DNA synthesis (measured by [3H]thymidine incorporation) was increased after incubation of fibroblasts with 1,25(OH)2D3 (1.25 nM) plus triamcinolone acetonide (10(-6) M), although it was reduced by nicardipine in comparison with 1,25(OH)2D3 alone. So the effects of these agents on the 1,25(OH)2D3 induced 24-hydroxylase were shown to be independent of the rate of DNA synthesis.     

Glucocorticoids Increase Tyrosine Hydroxylase Activity in Cultured Murine Neuroblastoma

Cyclic AMP and glucocorticoids appear to have a role in regulating the activity of tyrosine hydroxylase (TH), as well as the expression of "morphological differentiation" in murine neuroblastoma. Monolayer cultures of C-1300 murine neuroblastoma (clone NBP2) were treated with the following compounds in ethanol: dexamethasone, triamcinolone acetonide, hydrocortisone, cortexolone, androstenedione, testosterone, estradiol-17 beta; or with the phosphodiesterase inhibitor Ro20-1724 [4-(3-butoxy-4-methoxybenzyl)-2-imidazolidinone]. Treatment with either 200 micrograms/ml Ro20-1724 or 50 micrograms/ml dexamethasone produced significant increases in TH activity compared to alcohol controls (1.44 vs. 0.82 nmol 14CO2/mg protein/hr compared to 0.095). Triamcinolone acetonide or hydrocortisone also produced smaller, but significant, increases in TH activity compared to dexamethasone. When steroid activities were compared at 25 microM concentration and after 60 min of incubation (to maximize TH activity), triamcinolone acetonide was not as effective (62%) as dexamethasone. The relatively inactive glucocorticoid cortexolone produced a slight but significant increase, while the androgens androstenedione and testosterone and the estrogen estradiol-17 beta were without effect.     

Comparison of glucocorticoid-binding proteins in normal and neoplastic mammary tissues of the rat.

Kinetic and molecular properties of components binding [3H]triamcinolone acetonide were studied using 105,000g supernatants of lactating mammary gland, R3230AC, and dimethylbenz[a]anthracene (DMBA) induced mammary tumors of the rat. Using a dextran-coated charcoal adsorption procedure, the relationship between specific glucocorticoid binding and protein concentration was linear in the range of 0.5-4.0 mg/reaction. These cytoplasmic macromolecules bound [3H]triamcinolone acetonide with limited capacity (50-400 fmol/mg of cytosol protein) and high affinity, Kd approximately 10(-8)-10(-9) M. Optimal binding was obtained when homogenizations were made in Tris buffers, at pH 7.4, containing monothioglycerol. Time course of association of [3H]triamcinolone acetonide and its binding sites showed maximal binding by 6-8 hr at 3 degrees which remained unchanged up to 24 hr. The rate constant of association at 3 degrees was in the range of 2-4 x 10(5) M-1 min-1. The rate constant of dissociation of bound [3H]triamcinolone acetonide could not be calculated accurately since the reaction was essentially irreversible for 5 hr at 3 degrees. Estimation of the half-life of the steroid-binding protein complexes from the Kd and the rate constant for association gave a value of 11-12 hr. From ligand specificity studies, the glucocorticoids, triamcinolone acetonide, corticosterone, cortisol, and dexamethasone competed well for [3H]triamcinolone acetonide binding sites. Progesterone, aldosterone, and the anti-glucocorticoid, cortexolone, were also good competitors while androgens and estrogens were weak inhibitors of binding. The binding compenents sedimented at 7-8 S in sucrose gradients of low ionic strength and dissociated into lower molecular weight components sedimenting at 4-5S in high ionic strength gradients. Studies in vivo using animals bearing the DMBA-induced tumor demonstrated that [3H]triamcinolone acetonide binding complexes were present in cytoplasmic and nuclear compartments. Sedimentation coefficients of the cytoplasmic and nuclear forms of these receptors labeled in vivo were 7-8S and 4-5S, respectively. These studies suggest that the molecular and kinetic binding properties of glucocorticoid receptors in neoplastic mammary tissues are similar to those of the normal mammary gland.     

乳孔硫磺菌的化学成分和抗氧化活性

对乳孔硫磺菌子实体不同极性提取物进行了DPPH和ABTS自由基清除能力的测定,并对氯仿和乙酸乙酯提取物进行了分离纯化。结果表明,乳孔硫磺菌的石油醚、氯仿、乙酸乙酯和甲醇提取物均有一定的抗氧化活性,各提取物对两种自由基的清除能力均表现为甲醇提取物＞乙酸乙酯提取物＞氯仿提取物＞石油醚提取物,甲醇提取物对DPPH自由基的清除率最高可达到93.78%;对ABTS自由基的清除率最高可达到62.06%;从氯仿和乙酸乙酯提取物中分离得到10个化合物,分别是：(22E,24R)-5α,8α-过氧麦角甾-6,22-二烯-3β-醇（1）,阿里红酸 A（2）,麦角甾-7,22-二烯-3β-醇（3）,啤酒甾醇（4）,硫色多孔菌酸（5）,(4E,8E)-N-d-2′-hydroxypalmitoyl-1-O-β-d-glycopyranosyl- 9-methyl-4,8-sphingadienine（6）,麦角甾醇（7）,N-(2′-羟基二十四碳酰基)-1,3,4-三羟基-2-氨基-十八烷（8）,烟酸（9）和齿孔酸（10）。其中,化合物2、6、8和9为首次从硫磺菌属真菌中分离得到。     

Taraxastane-type triterpenoids from Saussurea petrovii.

Two taraxastane triterpenoids, i.e. taraxast-20-ene-3beta,30-diol (1) and 20alpha,21alpha-epoxy-taraxastane-3beta,22alpha-diol (2), as well as four known triterpenes taraxast-20(30)ene-3beta,21alpha-diol (3), taraxast-20(30)-ene-3beta-ol (4), taraxast-20-ene-3beta-ol (5) and taraxastane-3beta,20alpha-diol (6) were isolated from the Chinese medicinal plant Saussurea petrovii. Their structures were elucidated by spectroscopic methods. These compounds, especially 1 and 2, exhibit significant antitumor and antibacterial activity.     

Parallel double stranded helices and the tertiary structure of nucleic acids

Thermal denaturation of four oligonucleotides, viz. 3'-d(AT)5pO(CH2)6Opd(AT)5-3'(par(AT], 3'-d(AT)5pO(CH2)6Opd(AT)5-5'(anti(AT],3'-d(A)10pO(CH2) 6Op(T)10-3'(par(A-T], and 3'-d(A)10pO(CH2)6Opd(T)10-5' (anti(A-T], was studied in 0.01 M phosphate buffer, pH 7, in the presence of 0.1, 0.25, 0.5 and 1.0 M NaCl. All the oligomers were found to exist at a lower temperature (0 to 20 degrees C) as complexes composed either of two oligomer molecules (a canonical duplex) or of more oligomer molecules whereas, at a higher temperature (30 to 70 degrees C), they formed hairpins with a parallel (par(AT) and par(A-T] or antiparallel (anti(AT) and anti(A-T) orientation of the chains. Melting curves (A260(T] were used to calculate thermodynamic parameters for the formation of hairpins and "low-temperature" duplexes. Experiments on ethidium bromide binding to the oligonucleotides have shown that the oligomer anti(A-T) exists, at a low ionic strength, as a four stranded complex ("quadruplex") contains two antiparallel helices, d(A).d(T), which have a parallel orientation and are bound to one another owing to the formation of additional hydrogen bonds between nucleic acid bases. The possible biological function of quadruplexes is discussed.     

朱红栓菌提取物抗氧化、抗肿瘤活性评价及相关化学成分分析

采用石油醚、乙酸乙酯、乙醇浸提朱红栓菌 Trametes cinnabarina 子实体干粉,得到不同极性提取物;采用清除DPPH 自由基、羟自由基、超氧阴离子自由基能力,测定提取物的体外抗氧化活性;MTT法检测提取物对人肝癌细胞株HepG2细胞增殖的抑制作用。结果表明,朱红栓菌石油醚、乙酸乙酯、乙醇提取物均具有一定的抗氧化、抗肿瘤活性;各提取物在浓度为4-5mg/mL时,对DPPH自由基、羟自由基和超氧阴离子自由基清除能力大小依次为乙酸乙酯提取物>乙醇提取物>石油醚提取物;乙酸乙酯提取物对3种自由基的最高清除率分别为60.23%、74.49%、63.84%。各提取物对人肝癌细胞株HepG2细胞增殖抑制作用大小依次为乙酸乙酯提取物>乙醇提取物>石油醚提取物;乙酸乙酯提取物的抑制率最高达55.93%。采用硅胶和凝胶等柱色谱方法结合核磁、波谱和质谱等技术对乙酸乙酯提取物的化学组分进行分析,共分离纯化出11种化合物,分别鉴定为：麦角甾醇（1）,邻苯二甲酸二丁酯（2）,对羟基苯甲酸甲酯（3）,麦角甾-7,22,二烯-3-酮（4）,1-[(12E,16E)-12,16-二十碳二烯酰基]-2-[(E,E)-7,11-十八碳二烯酰基]-3-硬脂酰基甘油（5）,cinnabarin（6）,过氧麦角甾醇（7）,尿嘧啶（8）,甘露醇（9）,腺嘌呤核苷（10）,豆甾-7,22-二烯-3β,5α,6β-三醇（11）。除化合物6外均为首次从朱红栓菌子实体中分离得到。研究结果为开发利用朱红栓菌子实体提供了科学依据。     

Effects of B-retinyl acetate on human breast epithelium in explant culture

Explants of human breast (obtained aseptically from ten women ages 18-37) were examined and the vitamin A compound B-retinyl acetate was tested (at 3 X 10(-5) and 3 X 10(-6) M) for its effects on the fine structure and growth of the epithelium. In the absence of B-retinyl acetate, cells growing out from the explant (outgrowth cells) underwent squamous metaplasia, began to accumulate many intermediate filaments (tonofilaments), and revealed large desmosomes after 2 weeks in culture. In the presence of either concentration of B-retinyl acetate, the epithelial cells were largely prevented from undergoing squamous metaplasia. The glandular epithelium inside the explant maintained a typical secretory appearance for 2 weeks in control cultures (without the retinoid) and then began to show increased numbers of lysosomes and a loss of secretory granules. These glandular epithelial cells did not undergo squamous metaplasia, but they contained increased numbers of intermediate filaments. In contrast, glandular epithelium cultured in either concentrations of B-retinyl acetate appeared secretory for as long 6 weeks in culture, and intermediate filaments were not obvious. Autoradiographs demonstrated that both concentrations of B-retinyl acetate inhibited cell division in the outgrowth epithelium and in the (internal) glandular epithelium. The ability of B-retinyl acetate to reverse squamous metaplasia in the outgrowth cells was also tested. Outgrowth cells reversed to a more normal ductlike appearance after 6 weeks culture in standard medium followed by only 1 week in 20 micrograms/ml B-retinyl acetate. After 7 weeks in standard medium and 1 week in 10 micrograms/ml B-retinyl acetate, the cells showed a partial reversal of the squamous metaplasia.     

Usefulness of Glucokinase from Bacillus stearothermophilus for the Enzymatic Measurement of Magnesium in Human Serum

(22R,23R,24S)-3α,5-Cyclo-22,23-diacetoxy-5a-ergostan-6-one (2b) is a new key intermediate of some naturally occurring brassinosteroids such as brassinolide (la), castasterone (lb), teasterone (lc) and typhasterol (Id). The cycloketone 2b was prepared in 10 steps via (22R,23R,24S)-6p- benzyloxy-3a,5-cyclo-22,23-dihydroxy-5a-ergostane (5) from stigmasterol. 2b was treated with a catalytic amount of /7-toluenesulfonic acid and sodium bromide to give an enone (7b), which was oxidized with osmium tetroxide and derived to give a 2a,3a-acetonide (8b). 8b was easily separated from its isomer by the use of silica gel column chromatography. 8b was oxidized with tri- fluoroperacetic acid and deacetylated to give la. 8b was deacetylated and deacetonized to give lb. 2b was treated with dilute sulfuric acid in acetic acid to give a 3/^-acetate (10). 10 was treated with sodium hydroxide to give lc. 2b was treated with hydrobromic acid to give a 3/i-bromide (12), which was treated with silver acetate to give a 3a-acetate (13). 13 was treated with sodium hydroxide to give Id.     

钮子瓜化学成分研究

从民间药物钮子瓜全草95%乙醇提取物中首次分离得到14个化合物,应用波谱方法及与已知品对照的手段鉴定它们为(2S,3S,4R,10E)2[(2R)2-羟基二十四烷酰氨基]10十八烷-1,3,4-三醇(1)、(2S,3S,4R)2-二十四烷酰胺基十八烷-1,3,4-三醇(2)、胡萝卜苷(3)、swertish(4)、苯甲酸(5)、水杨酸(6)、loliolide(7)、胸腺嘧啶(8)、尿嘧啶(9)、(23Z)-9,19-环阿尔廷-23-烯-3β,25-二醇(10)、(20S,22E,24R)5α,8α-表二氧麦角甾6,22二烯3β醇(11)、十六烷酸1甘油酯(12)、大豆脑苷Ⅰ(13)、(22E,24S)24甲基5α胆甾7,22二烯3β,5α,6β三醇(14)。