苦玄参酮Ⅰ的结构

前已报道了从苦玄参(Picria fel-tarrae Lour)提取液 B 部份分离出的苦玄参甙元Ⅰ(1)、Ⅱ、Ⅲ和Ⅳ的结构。本文报道从 A 部份所得的苦玄参酮(picfeltarraenone)Ⅰ(2)的结构。苦玄参酮Ⅰ(2)含量约为全草的0.002%。它是无色针状结晶,熔点218—219℃,分子式为 C_(30)H__(42)O_5。它的各种谱学数据与苦玄参甙元Ⅰ(1)基本相似,但是,在质谱中2的分子离子正好比1的分子离子少2,即2的分子中比1少2个氢原子;在~1H)(nmr)中,2缺     

红根草内酯的化学结构

前文曾报道从红根草(Salvia prionitis Hance)中分得新二萜醌类化合物去氢丹参新酮,红根草对醌,3-羰基红根草对醌及新天然产物红根草邻醌等成分。在进一步研究红根草的活性成分时,又分得一新的二萜醌类化合物——红根草内酯(Ⅰ)。红根草内酯为浅黄色棱形结晶,熔点205—206℃,分子式 C_(15)H_(14)O_3(~1H RMS M~+242.0938)。红外光谱示 v-内酯(1750cm~(-1)),芳香环(1505,1485 cm~(-1))以及酚羟基     

变色马兜铃化学成分的研究

从变色马兜铃块根乙醇提取物的石油醚溶解部分中分得一个倍半萜内酯(B_2),分子式C_(15)H_(20)O_2,熔点94—95℃,[α]_D~(36)-49°(C=1.8,EtOH)。通过光谱分析和化学反应测定了结构,并证明它与异马兜铃内酯(isoaristolactone)为同一化合物,从而使异马兜铃内酯的结构得以明确。B_2系首次从植物中分到。另从石油醚不溶部分中分得12个成分(D_1—D_3,D_(4f),D_(4y),D,—D_(10)和 C_2)。其中7个分别鉴定为6-甲氧基去硝基马兜铃酸甲酯(D_1)、去硝基马兜铃酸(D_3)、6-甲氧基去硝基马兜铃酸(D_(4f))、6-甲氧基马兜铃酸甲酯(D_(4y))、马兜铃酸A(D_5)、β-谷甾醇-D-葡萄糖甙(D_(10))和尿囊素(C_2)。D_(4f)亦系首次从植物中分到。动物试验表明,D_1、D_3和 D,均有明显的抗生育活性。     

云南翠雀碱的结构

毛茛科翠雀属植物小草乌(Delphinium yunnanense(Fr.)Fr.)在云南、四川、贵州皆有分布。民间常以水煮或酒泡后内服治疗跌打损伤,有止痛及补虚、止咳作用。在研究它的有效成份时,我们得到一个新的牛扁碱型二萜生物碱,定名云南翠雀碱yunnadel-phininc. 云南翠雀碱C_(24)H_(35)O_6N,熔点217—219℃。由核磁共振谱δ3.37,3.31(各3H,s)示有两个甲氧基;δ5.60,5.15(各1H,s)示有一个次甲二氧基;δ1.06(3H,t,J=7Hz)示有氮乙基。红外光谱1750cm~(-1)和3475cm~(-1)示有羰基和羟基。由此,分子式展开符合C_(19)二萜生物碱骨架,且知羰基及δ0.95(3H,s)所示的叔甲基皆在骨架上。     

苦绳甙甲的结构

从苦绳(Dregea sinensis var. corrugata)的根茎中分得一个新的C_(21)-甾体甙成分,命名为苦绳甙甲(dregeoside A)。经光谱分析和化学反应证明,其结构为:苦绳甙元甲3-O-3-O-甲基-6-去氧-β-D-阿洛吡喃糖(1→4)-β-D-夹竹桃吡喃糖(1→4)-β-D-磁麻吡喃糖,(1→4)-β-D-磁麻吡喃糖甙(drevogenin A 3-O-3-O-methyl-6-deoxy-β-1)-allopyranosyl-(1→4)-β-D-oleandropyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-β-D-cymaropyranoside).     

裂冠牛奶菜中一新奇C_(21)甾体甙(英文)

Besides a series of normal C_(21) steroids from Marsdenia incisa incisa P.T.Li et Y.P.Li, it small amount of novel C_(21) steroidal glycoside (Ⅱ) had been isolated. The mild acidic hydrolysis of (Ⅱ) afforded genin-(Ⅰ). By spectroscopic analyses of IR, ELMS, FDMS, ~1H NMR, ~(13)C NMR (DEPT, PRFT), ~1H-~1H COSY, ~1H-~(13)C COSY for (Ⅰ) and (Ⅱ), (Ⅰ) had been deduced as B-nor (7) -6β-formyl-pregnane-3β, 5β, 8β, 12β, 14β, 17β, 20-heptatol, named neomarinogenin; (Ⅱ) had been deduced as neomarinogenin 3-O-β-D-thevetopyranosyl-(1→-4)-β-Dcymaropyranosyl-(1→4)-β-D-cymaropyranoside, named neomarinoside. Their physical and spectral data were as follows. Neomarinogenin (Ⅰ). A colorless prism from Me_2 CO, mp 202—205℃, 〔α〕_D~(17) 28.81°(MeOH, c0.05), C_(21)H_(34)O_8 (Found: C, 60.76; H, 8.19, C_(21)H_(34)O_8, requires C, 60.87. H, 8.21％); IRv_(max)~(KBr)cm~(-1): 3450 (OH), 1700 (C=O), 1050(C-O-C); EIMS m/z: 397 (M-OH), 380 (397-OH), 379, 378 (M-2H_2O), 36; (M-3H_2O), 342 (M-4H_2O), 333, 315     

苦玄参药材中苦玄参苷ⅠA和ⅠB的含量分析

采用HPLC法对不同产地的苦玄参药材主成分苦玄参苷ⅠA和ⅠB的含量进行分析,发现苦玄参苷ⅠB含量高于苦玄参苷ⅠA;色谱条件:Waters C18(4.6mmi.d.×250mm,5μm)色谱柱,流动相∶乙睛∶水=36?64(体积比),流速为0.8mL/min,检测波长为264nm。苦玄参苷ⅠA、ⅠB分别在0.05～0.50mg/mL和0.072～0.720mg/mL与峰面积有良好的线性关系。苦玄参苷ⅠA的线性回归方程Y=13658X-92.72(r=0.9993),平均回收率为100.58%(n=5),相对标准偏差(RSD)为1.86%;苦玄参苷ⅠB的线性回归方程Y=5258.9X-41.01(r=0.9994),平均回收率为101.15%(n=5),相对标准偏差(RSD)为1.31%。该研究为制定苦玄参药材质量检测标准提供了简便、快速、准确的方法。     

茅膏菜中的一种新茚满酮成分

茅膏菜系茅膏菜科(Droseraceae)植物茅膏菜(Drosera pellata Smith Lunata(Buch-Ham.)C. B. Clarke)以全草人药。民间常用于祛风除湿,治疗跌打损伤及结核病。又为一常用藏药,在西藏地区民间用于治疗月经不调、瘰疠等症,又作为滋补药。文献报道含有萘醌成分。 样品采于西藏。全草干燥细粉重5.5kg,用乙醇提取,粗提物的乙醚溶解部分经反复硅胶柱层析,得到一种新的茚满酮,命名为:泊尔酮A(peltatone A)(Ⅰ)50 mg;0.00091％。 根据元素分析和质谱数据,相应分子式为C_(10)H_8O_5,Ω=7,IR提示含有苯环、羟基及羰基,三氯化铁-铁氰化钾显蓝色。~1H NMR提示存在2个芳氢(δ7.38,s),1个甲基(δ1.70,s),乙酰化物~1H NMR提示Ⅰ含有2个酚羟基,1个醇羟基。IR说明有β—双酮结构(V_(max)~(KBr) cm~(-1):1730,1693),~(13)C NMR及DEPT谱也说明分广内存在对称结构,确定Ⅰ的结构为2—甲基,2,4,7—三羟基—1,3—茚二酮。     

通光藤甙元甲的化学结构

通光藤[Marsdenia tenacissima(Roxb.)Wight et Arn.]为云南民间抗癌药用植物。从其藤茎提取的粗甙经水解、皂化后得到一个新的主要甙元,称通光藤甙元甲(tenacigenin A)。通光藤甙元甲分子式 C_(21)H_(32)O_5,熔点255—260℃,属 C_(21)-甾体化合物,能用常法制得二乙酰化合物(Ⅲ),三乙酰化物(Ⅳ)需在剧烈条件下才能得到。三个羟基中有两个可被氧化成六元环酮(Ⅵ)。另两个氧原子则以环氧的形式存在。通光藤甙元甲用醋酐和对甲苯磺酸于100℃加热30小时后得到3β、12β、14β-三乙酰-5α-甾烷-7(8)、9(11)-二烯-20-酮(Ⅸ),后者用铂黑在醋酸中氢化得(Ⅹ)。据上述化学反应和红外光谱、紫外光谱、核磁共振谱及质谱数据,作者提出通光藤甙元甲的结构为(Ⅰ)。     

8-羟基喹啉-水杨酸-镧配合物对细菌、酵母及肿瘤细胞抑制效应的初步研究

采用杯碟法、微量生物量热法,研究了8-羟基喹啉-水杨酸-镧配合物(La(C_7H_5O_3)_2·(C_9H_6NO))对金黄色葡萄球菌(Staphylococcus aureus,CICC10384)、枯草芽孢杆菌(Bacillus subtilis,CICC10012)、大肠杆菌(Escherichia coli,s ATCC8739)、粟酒酵母(Schizosaccharomyces pombe)及K562和He La-60肿瘤细胞的抑制活性。结果表明:La(C_7H_5O_3)_2·(C_9H_6NO)对3种细菌的最小杀菌浓度分别为0.45~0.90 g/L、1.2~1.5 g/L和1.2~1.5 g/L,而且浓度1.5 g/L以上的稀土配合物对3种细菌的抑制作用存在极显著差异(P0.01),其中3.6 g/L以上浓度的稀土配合物对3种细菌的抑菌达到了强、中、强的效果;对S.pombe、K562细胞、He La-60细胞也都具有较强的抑制作用,且IC50分别为26.77 mg/L、1.62 mg/L和1.68 mg/L。以上结果说明,La(C_7H_5O_3)_2·(C_9H_6NO)具有较强的抑菌和抗肿瘤效果。     

杜鹃属植物区系的研究

已知世界杜鹃属(Rhododendron)植物约967种（种下分类等级未计算在内）。本文基于植物区系学的观点,讨论了属内8个亚属：常绿杜鹃亚属、杜鹃亚属、马银花亚属、映山红亚属、羊踯躅亚属、云间杜鹃亚属、纯白杜鹃亚属、异蕊杜鹃亚属的系统位置、分布式样。分析了系统发育和地理分布上的时间、空间关系。认为常绿杜鹃亚属和杜鹃亚属是在本属植物起源后的早期阶段就沿不同途径迁徙、繁衍的两个演化枝。自第三纪以来,它们的性状发展多样,种系高度分化。在现存类群中最具原始性状的亚属是常绿杜鹃亚属,这个亚属的云锦杜鹃亚组Subsect.Fortunea,耳叶杜鹃亚组Subsect.Auriculata 保持较多原始性状。种的分布遍及欧洲、北美洲、亚洲、大洋洲(有1种),东亚种类最多,马来西亚次之。中国-喜马拉雅地区既是多度中心又是多样化中心,马来西亚仅是多度中心。大多数种为地方特有性分布,特有现象十分突出,东亚和马来西亚的特有种共约862种,占种总数的89%以上中国有6个亚属(Candidastrum,Mumeazalea不产)约562种,其中特有种约405种。分析第三纪的化石记录,杜鹃属在全球分布的时间、地点,杜鹃属保持原始或古老性状的类群的现代适生地,认为中国西南至中国中部最有可能是杜鹃属植物的起源地,始祖类群起源的时间会是在晚白垩纪至早第三纪。讨论了杜鹃属在第三纪至第四纪向北半球北部的传布,向亚洲西南、亚洲东南和向东亚的传布以及向大洋洲的传布。从杜鹃属在全球传布的现象和途径,看来现代分布格局形成的原因取决于三方面的因素：时间和窨历史对植物繁衍、传播有着重要制约作用,并受制于植物种系自身具有的遗传性和对环境强烈变化的反应能力。     

Anti-adipogenic chromone glycosides from Cnidium monnieri fruits in 3T3-L1 cells

Seven new chromone glycosides, monnierisides A (3), B (10), C (11), D (12), E (13), F (15) and G (16) were isolated from Cnidium. monnieri, together with ten known chromone derivatives, undulatoside A (1), cnidimol C (2), saikochromoside A (4), cnidimoside A (5), cnidimoside B (6), 2-methyl-5-hydroxy-6-(2-butenyl-3-hydroxymethyl)-7-(β-d-glucopyranosyloxy)-4H-1-benzopyran-4-one (7), cnidimol D (8), hydroxycnidimoside A (9), umtatin (14) and 6'-hydroxylangelicain (17). The structures of isolated compounds were determined on the basis of spectroscopic analysis including 1D, 2D NMR and HR-MS. Among the compounds isolated, compounds 5, 6, 9 and 10 significantly inhibited adipocyte differentiation as measured by fat accumulation in 3T3-L1 cells using Oil Red O staining.     

Biotransformations of anthracyclinones inStreptomyces coeruleorubidus andStreptomyces galilaeus

The ability to transorm biologically exogenous daunomycinone, 13-dihydrodaunomycinone, aklavinone, 7-deoxyaklavinone, epsilon-rhodomycinone, epsilon-isorhodomycinone and epsilon-pyrromycinone was studied in submerged cultures of the following strains: wild Streptomyces coeruleorubidus JA 10092 (W1) and its improved variants 39-146 and 84-17 (type P1) producing glycosides of daunomycinone and of 13-dihydrodaunomycinone, together with epsilon-rhodomycinone, 13-dihydrodaunomycinone and 7-deoxy-13-dihydrodaunomycinone; in five mutant types of S. coeruleorubidus (A, B, C, D, E) blocked in the biosynthesis of glycosides and differing in the production of free anthracyclinones; in the wild Streptomyces galilaeus JA 3043 (W2) and its improved variant G-167 (P2) producing glycosides of epsilon-pyrromycinone and of aklavinone together with 7-deoxy and bisanhydro derivatives of both aglycones; in two mutant types S. galilaeus (F and G) blocked in biosynthesis of glycosides and differing in the occurrence of anthracyclinones. The following bioconversions were observed: daunomycinone leads to 13-dihydrodaunomycinone and 7-deoxy-13-dihydrodaunomycinone (all strains); 13-dihydrodaunomycinone leads to 7-deoxy-13-dihydrodaunomycinone (all strains); daunomycinone or 13-dihydrodaunomycinone leads to glycosides of daunomycinone and of 13-dihydrodaunomycinone, identical with metabolites W1 and P1 (type A), or only a single glycoside of daunomycinone (type E); aklavinone leads to epsilon-rhodomycinone (types A and B); aklaviinone leads to 7-deoxyaklavinone and bisanhydroaklavinone (type C); epsilon-rhodomycinone leads to zeta-rhodomycinone (types C, E); epsilon-rhodomycinone leads to glycosides of epsilon-rhodomycinone (types W2, P2); epsilon-isorhodomycinone leads to glycosides of epsilon-isorhodomycinone (types W2, P2); epsilon-pyrromycinone leads to a glycoside of epsilon-pyrromycinone (types W1, P1). 7-Deoxyaklavinone remained intact in all tests. Exogenous daunomycinone suppressed the biosynthesis of its own glycosides in W1 and P1; it simultaneously increased the production of epsilon-rhodomycinone in P1.     

The preparation of carbohydrate-protein conjugates: cyanuric trichloride coupling of 2-aminoethyl glycosides,and mixed-anhydride coupling of 8-carboxyoctyl glycosides to bovine serum albumin

Preparation of the following glycosides is described: 2-aminoethyl β-d-glycosides of (A) 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-d-glucopyranose, (B) 2-acetamido-4-O-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-d-glucopyranosyl)-3,6-di-O-acetyl-2-deoxy-β-d-glucopyranose (N,N′-diacetylchitobiose pentaacetate), (C) 4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-2,3,6-tri-O-acetyl-β-d-glucopyranose (cellobiose heptaacetate); 8-carboxyoctyl glycosides of (D) cellobiose, and (E) N,N′-diacetylchitobiose. Conjugates were prepared from (A), (B), and (C) by coupling to bovine serum albumin by cyanuric trichloride and subsequent deacetylation; (D) and (E) were coupled to bovine serum albumin by the mixed-anhydride reaction. Conjugates (A) and (B) were insoluble; conjugates (C), (D), and (E) functioned as artificial antigens and gave rise to precipitating antibodies in rabbits. Specificities of the antisera were determined by inhibition studies.     

通光藤甙F,G,H和I结构

从通光藤(Marsdeniatenacissima)的茎中分离得到4个新的C21甾体甙———通光藤甙F(3),G(4),H(5)和I(6),以及2个已知化合物通光藤甙A(1)和B(2)。根据光谱数据和化学方法推定了其结构。同时,通过COLOC谱和二维核磁共振谱指定了这些化合物中甙元上11和12位的酯基确切连接位置。     

nor-Oleanene type triterpene glycosides from the leaves of Acanthopanax japonicus

Three new (1-3) and two known (4-5) triterpene glycosides were isolated from the leaves of Acanthopanax japonicus (Araliaceae) and elucidated structurally by mass, 1D, and 2D NMR spectroscopy. All the compounds possessed a nor-oleanene triterpene skeleton as the aglycone. The structures of 1-5 were established as 28-O-alpha-L-rhamno-pyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester of 3beta-hydroxy- 30-nor-olean-12,20(29)-diene-23,28-dioic acid, designated as acanjaposide A, 3beta- hydroxy-23-oxo-30-nor-olean-12,20(29)-diene-28-oic acid, named acanjaposide B, 3beta,20alpha-dihydroxy-23-oxo-30-nor-olean-12-en-28-oic acid, named acanjaposide C, and nipponoside E, a known saponin, respectively.     

Leishmanicidal cycloartane-type triterpene glycosides from Astragalus oleifolius

Two new cycloartane-type glycosides oleifoliosides A (1) and B (2) were isolated from the lower stem parts of Astragalus oleifolius. Their structures were identified as 3-O-[beta-xylopyranosyl-(1 --> 2)-alpha-arabinopyranosyl]-6-O-beta-xylopyranosyl-3beta,6alpha,16beta,24(S),25-pentahydroxycycloartane and 3-O-[beta-xylopyranosyl-(1 --> 2)-alpha-arabinopyranosyl]-6-O-beta-glucopyranosyl-3beta,6alpha,16beta,24(S),25-pentahydroxycycloartane, respectively, by means of spectroscopic methods (IR, 1D and 2D NMR, ESI-MS). Three known cycloartane glycosides cyclocanthoside E (3), astragaloside II (4) and astragaloside IV (5) were also isolated and characterized. All five compounds were evaluated for in vitro trypanocidal, leishmanicidal and antiplasmodial activities as well as their cytotoxic potential on primary mammalian (L6) cells. Except for the compound 5, all compounds showed notable growth inhibitory activity against Leishmania donovani with IC50 values ranging from 13.2 to 21.3 microg/ml. Only weak activity against Trypanosoma brucei rhodesiense was observed with the known compounds astragaloside II (4, IC50 66.6 microg/ml) and cyclocanthoside E (3, IC50 85.2 microg/ml), while all compounds were inactive against Trypanosoma cruzi and Plasmodium falciparum. None of the compounds were toxic to mammalian cells (IC50's > 90 microg/ml). This is the first report of leishmanicidal and trypanocidal activity of cycloartane-type triterpene glycosides.     

Three New Flavone Glycosides from Drymaria diandra B1.

In order to find new structural and biologically active compounds, the constituents from the whole plant of Drymaria diandra B1. （Caryophyllaceae） were investigated and three new flavone glycosides, named drymariatins B （1）, C （2）, and D （3）, were isolated by solvent partition, Si gel, sephadex LH-20, and Rp- 18 column chromatography. Using spectroscopic methods, including two-dimensional nuclear magnetic resonance analysis, the structures of these compounds were elucidated as 6-C-（2-deoxy-β-D-fucopyranosyl）- 5,7,4＇-trihydroxyl-flavone, 6-C-（2-deoxy-β-D-fucopyranosyl）-7-O-（β-D-glucopyranosyl）-5,4＇-dibydroxyl- flavone, and 6-C-（3-keto-β-digitoxopyranosyl）-7-O-（β-D-glucopyranosyl）-5,4＇-dihydroxyl-flavone.     

Oleanane glycosides from Glycyrrhiza yunnanensis roots.

From the roots of Glycyrrhiza yunnanensis, collected in Yunnan, China, six new oleanane-type triterpene glycosides named yunganosides A1, B1, C1, D1, E2 and F2 were isolated together with hypaphorine. The structures of these glycosides were established by spectroscopic and chemical means.     

Fluorescence correlation spectroscopy as a sensitive and useful tool for revealing potential overlaps between the epitopes of monoclonal antibodies on viral particles

Although the enzyme-linked immunosorbent assay (ELISA) is well established for quantitating epitopes on inactivated virions used as vaccines, it is less suited for detecting potential overlaps between the epitopes recognized by different antibodies raised against the virions. We used fluorescent correlation spectroscopy (FCS) to detect the potential overlaps between 3 monoclonal antibodies (mAbs 4B7-1H8-2E10, 1E3-3G4, 4H8-3A12-2D3) selected for their ability to specifically recognize poliovirus type 3. Competition of the Alexa488-labeled mAbs with non-labeled mAbs revealed that mAbs 4B7-1H8-2E10 and 4H8-3A12-2D3 compete strongly for their binding sites on the virions, suggesting an important overlap of their epitopes. This was confirmed by the cryo-electron microscopy (cryo EM) structure of the poliovirus type 3 complexed with the corresponding antigen-binding fragments (Fabs) of the mAbs, which revealed that Fabs 4B7-1H8-2E10 and 4H8-3A12-2D3 epitopes share common amino acids. In contrast, a less efficient competition between mAb 1E3-3G4 and mAb 4H8-3A12-2D3 was observed by FCS, and there was no competition between mAbs 1E3-3G4 and 4B7-1H8-2E10. The Fab 1E3-3G4 epitope was found by cryoEM to be close to but distinct from the epitopes of both Fabs 4H8-3A12-2D3 and 4B7-1H8-2E10. Therefore, the FCS data additionally suggest that mAbs 4H8-3A12-2D3 and 4B7-1H8-2E10 bind in a different orientation to their epitopes, so that only the former sterically clashes with the mAb 1E3-3G4 bound to its epitope. Our results demonstrate that FCS can be a highly sensitive and useful tool for assessing the potential overlap of mAbs on viral particles.