湖北贝母茎叶中的生物碱类成分研究

目的对湖北贝母Fritillaria hupehensis茎叶中生物碱类化学成分进行了研究。方法采用硅胶柱色谱分离化学成分,IR、MS、1H-NMR和13C-NMR以及与对照品对照等方法进行结构鉴定。结果从湖北贝母茎叶中分离并鉴定了8个生物碱类化学成分,分别是浙贝乙素(peiminine,Ⅰ)、湖贝甲素(hupehenine,Ⅱ)、湖贝新(hupehenisine,Ⅲ)、湖贝啶(hupehenidine,Ⅳ)、鄂贝新(ebeiensine,Ⅴ)、浙贝甲素(peimine,Ⅵ)、湖贝苷(hupehemonoside,Ⅶ)和湖贝甲素苷(hupeheninoside,Ⅷ)。结论化合物Ⅰ～Ⅷ均为首次从湖北贝母茎叶部位分离得到。     

HPLC-ELSD法测定皖贝止咳胶囊中贝母素甲和贝母素乙的含量

目的:建立皖贝止咳胶囊中贝母素甲和贝母素乙的含量测定方法。方法:采用迪玛C₁₈柱,乙腈-0.1%三乙胺溶液(70∶30)为流动相;ELSD参数:漂移管温度:93℃,载气流量:2.2mL·min^-1。结果:贝母素甲的回收率为97.35%,RSD=1.24%(n=5);贝母素乙的回收率为97.46%,RSD=1.27%(n=5)。结论:本法简便、快速、重复性好,可作为制剂的定量分析方法。     

HPLC-ELSD测定彭泽贝母中浙贝甲素和浙贝乙素

目的建立HPLC-ELSD测定彭泽贝母中浙贝甲素、浙贝乙素的分析方法。方法以C18柱为色谱柱,蒸发光闪射检测器,运用HPLC法分离及分析彭泽贝母中的浙贝甲素和浙贝乙素。结果建立了HPLC-ELSD测定彭泽贝母中浙贝甲素、浙贝乙素的分析方法:色谱柱:Hypers il ODS2(200 mm×4.6 mm,5μm),柱温30℃。流动相:乙腈-0.03%二乙胺水(65∶35),体积流量1.0 mL/m in。检测器参数:漂移管温度83.5℃,载气体积流量2.2 mL/m in,进样量10μL。结论运用HPLC-ELSD能够同时测定彭泽贝母中浙贝甲素、浙贝乙素的量。     

小蜡树香豆素类成分及其抗氧化活性

目的：对木樨科梣属植物小蜡树Fraxinux sieboldiana的化学成分进行研究并进行抗氧化活性筛选。方法：采用硅胶、大孔吸附树脂、Sephadex LH-20柱色谱和制备型高效液相色谱方法进行分离；应用NMR和MS等波谱方法鉴定化合物的结构；采用Fe²⁺-半胱氨酸诱导的大鼠肝微粒体脂质过氧化模型测定化合物对Fe²⁺-Cys诱导大鼠肝微粒体丙二醛(MDA)生成抑制活性。结果：从小蜡树乙醇提取物中分离得到8个香豆素类成分，分别鉴定为秦皮甲素(1)、秦皮乙素(2)、秦皮苷(3)、秦皮素(4)、6,7-di-O-β-D-glucopyranosylesculetin(5)，东莨菪素(6)，cleomiscosin D(7)和cleomiscosin B(8)。在10^-6 mol·L^-1浓度下，化合物4对Fe²⁺-Cys诱导大鼠肝微粒体丙二醛(MDA)生成抑制率为60％。讨论：化合物5，7，8为首次从该属植物中分离得到，其中化合物4在10^-6 mol·L^-1浓度能使脂质过氧化产物MDA的生成抑制50%以上，强于阳性对照药VE(抑制率35％)，具有显著的抗氧化作用。     

HPLC测定不同产地平贝母中贝母甲素的含量

 目的建立平贝母中贝母甲素含量的反相离子对HPLC测定方法。方法采用Kromasil ODS C₁₈(4.6 mm×250 mm,5μm)色谱柱,流动相为甲醇-水(69∶31),内含7.5 mmol·L^-1 SDS,pH=4.5±0.1;体积流量:0.5 mL·min^-1;柱温:27℃;检测波长为208nm,并与TLC对照测定了10种不同产地平贝母中贝母甲素的含量。结果贝母甲素在0.515～3.09μg与峰面积线性关系良好(r=0.999 7),平均加样回收率为98.54%,RSD为2.12%(n=5)。不同产地平贝母中贝母甲素含量有一定的差异,其中黑龙江省的铁力和辽宁省的新宾平贝母中贝母甲素含量较高。而其他吉林省的8个产地贝母甲素含量均较低。结论本方法灵敏度高,而且简便、准确、重现性好,可用于平贝母的内在质量控制。     

优异贝母生物碱的分离与鉴定

从优异贝母的鳞茎中分离得到6种生物碱,鉴定其中4种生物碱为湖贝乙素、湖贝嗪、湖贝甲素和湖贝甲素甙。     

HPLC-ELSD测定浙贝母中贝母素甲、贝母素乙的含量

 目的建立HPLC-ELSD测定浙贝母中贝母素甲、贝母素乙含量的方法,并对市售17批样品进行考察,制定含量限度。方法色谱柱:Agilent Hypersil BDS-C₁₈(4.0 mm×250 mm,5μm);流动相:乙腈-水-二乙胺(70:30:0.03),流速:0.8 mL·min^-1; ELSD参数:漂移管温度为85℃,载气流速为2.2 L·min^-1。结果贝母素甲、贝母素乙线性范围分别为47.02～1 003.46.92～1 001 mg·L^-1,平均回收率分别为102.7%,98.7%,RSD分别为2.1%,2.5%(n=6)。通过市售17批样品中贝母素甲、贝母素乙含量的测定,制定了不同规格浙贝母的含量限度。结论此法简便,快捷,结果可靠,可用于浙贝母的质量评价,为2005年版药典中浙贝母质量标准的修订提供了依据。     

HPLC-MS测定癃闭康泰片中贝母素甲、贝母素乙的含量

 目的建立癃闭康泰中贝母素甲、贝母素乙的高效液相色谱-质谱联用含量测定法。方法癃闭康泰片经碱化,用氯仿-甲醇(4∶1)提取生物碱有效部位,提取液浓缩,残渣用甲醇溶解后,进行高效液相色谱-质谱测定。色谱柱为Agilent Zorbax ex-tend C₁₈(2.1 mm×100 mm,5μm);流动相为乙腈和10 mmol·L^-1甲酸铵(pH 8.0),梯度洗脱(0～15 min:乙腈30%～55%;15～25min乙腈55%);流速0.2 mL·min^-1;柱温30℃。质谱条件为电喷雾电离源(ESI),以选择性正离子方式检测,贝母素甲和贝母素乙的选择性检测离子分别为m/z 432.4和m/z 430.4。结果贝母素甲和贝母素乙的的线性范围均为0.01～10 mg·L^-1,相关系数均大于0.999,检测限均为0.45μg·L^-1,方法回收率均大于95%,日内日间精密度(RSD)均小于5%。结论本方法专属性强,灵敏度高,线性关系良好,操作简便,适用于癃闭康泰中贝母素甲、贝母素乙的含量测定。     

紫花鄂北贝母中非生物碱成分的化学研究

紫花鄂北贝母Fritillariaebeiensisvar.pur-pureaG.D.YuetP.Li系百合科贝母属植物,原野生于鄂豫交界的桐柏山脉南端,已栽培成功。笔者曾从其总生物碱部分分离得到浙贝甲素(peimine)、浙贝乙素(peiminine)、鄂贝甲素(ebeinine)、鄂贝乙素(ebeinone)、鄂贝新(ebeiesine)和紫鄂贝碱(ziebeimine)等7种生物碱[1,2];在非生物碱部位,又报道了鄂贝缩醛甲(fritillebinideA)、鄂贝缩醛乙(fritillebinideB)、鄂贝醇甲(fritillebinolA)[3]、鄂贝新醇(fritillaziebinol)、ent-kauran-16β,17-diol和ent-kauran-3β,16β,17-diol[4]等化学成分。在对其…     

毛叶巴豆化学成分的研究

 目的研究大戟科(Euphorbiaceae)植物毛叶巴豆(Croton caudatus Geisel.var.tomentosus Hook.)茎中的化学成分。方法利用硅胶柱,凝胶柱色谱等常规分离技术分离纯化化合物,根据现代波谱学技术(MS,¹H-NMR,¹³C-NMR)进行结构鉴定。结果从毛叶巴豆茎的体积分数95%乙醇提取物中分离得到11个化合物,分别鉴定为:三十六烷酸乙酯(ethyl hexatriacontanoate,1),棕榈酸(palmic acid,2),硬脂酸(stearic acid,3),浙贝素(zheberiesinol,4),香草醛(vanillin,5),香草酸(vanillic acid,6),丁香酸(syringic acid,7),二十八烷酸(octacosanoic acid,8),琥珀酸(succinic acid,9),肌苷(inosine,10),异橙黄酮(isosinensetin,11)。结论所有化合物均为首次从该植物中分离得到,其中化合物4,7,9,10,11为首次从该属植物中分得。     

基于气相色谱离子迁移谱技术的川贝母差异性探索

目的:采用气相色谱离子迁移谱法(GC-IMS)对川贝母及其他贝母进行鉴别。方法:利用GC-IMS得到川贝母(包括松贝、青贝、炉贝)、平贝母、伊贝母的指纹图谱,计算挥发性物质含量;采用主成分分析(PCA)对不同贝母及不同川贝母所含挥发性物质进行比较。结果:松贝、炉贝和青贝样品中相似的挥发性物质较多,且这些挥发性成分在平贝母和伊贝母样品中含量很低或者不含有。通过主成分动态分析,选取所有的信号峰,5种样品区分明显,其中松贝、炉贝和青贝样品的聚类较为集中,平贝母和伊贝母的聚类较为分散。结论:采用GC-IMS能够有效区分不同的贝母样品,可为川贝母的快速真伪鉴别提供参考。     

Jatrophane diterpenoids from Euphorbia mongolica as modulators of the multidrug resistance of L5128 mouse lymphoma cells

The dried aerial parts of Euphorbia mongolica afforded three new acylated polyhydroxy diterpenoids based on the jatrophane framework. The structures were established by means of a combination of 1D and 2D NMR techniques and mass spectrometry as (2S,3S,4R,5R,7S,8R,13S,15R)-5alpha,7beta,8alpha-triacetoxy-3beta-benzoyloxy-15beta-hydroxyjatropha-6(17),11E-diene-9,14-dione (1), (2S,3S,4R,5R,7S,8S,9S13S,15R)-5alpha,7beta,8alpha,9alpha,15beta-pentaacetoxy-3beta-benzoyloxyjatropha-6(17),11E-dien-14-one (2), and (2S,3S,4R,5R,7S,8S,9S13S,15R)-3beta,7beta,8alpha,9alpha,15beta-pentaacetoxy-5alpha-benzoyloxyjatropha-6(17),11E-dien-14-one (3). When the isolates were assayed for multidrug resistance-reversing activity in a rhodamine 123 exclusion test using L5178 mouse lymphoma cells, all compounds demonstrated a concentration-dependent effect in inhibiting the efflux pump activity of these tumor cells in the range 11.2-112 microM.     

Cytotoxic withaphysalins from the leaves of Acnistus arborescens

Three withaphysalins, rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-1,18-dioxowitha-2,24-dienolide(withaphysalin M) (1), rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-18-ethoxy-1-oxowitha-2,24-dienolide (withaphysalin F ethyl ether, withaphysalin O) (2), and rel-(17S,20R,22R)-5 beta,6 beta:18,20-diepoxy-4 beta-hydroxy-1,18-dioxowitha-24-enolide (withaphysalin N) (3), were isolated from the leaves of Acnistus arborescens. The structures were deduced from 1D ((1)H NMR, (13)C NMR, DEPT-(13)C NMR) and 2D (COSY, HMQC, HMBC) NMR analysis and the relative stereochemical assignments based on 1D NOESY correlations and analysis of coupling constants. Compounds 1 and 2 displayed potent cytotoxic activity against a panel of human cancer cell lines.     

Bioactive steroids from the whole herb of Euphorbia chamaesyce

Three new ergostane-type steroids, 3beta-hydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (1); 3beta, 11alpha-dihydroxy-4alpha,14alpha-dimethyl-5alpha -ergosta-8, 24(28)-dien-7-one (2); and 3beta,7alpha-dihydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (3), were isolated, together with two known triterpenoids, wrightial and lup-20(30)-ene-3beta,29-diol from the whole herb of Euphorbia chamaesyce. Compound 3 showed a potent inhibitory effect on Epstein-Barr virus early antigen activation induced by the tumor promoter 12-O-tetradecanoylphorbol 13-acetate (TPA).     

Withanolides from Vassobia lorentzii

Eight new withanolides were isolated from the aerial parts of Vassobia lorentzii and characterized by spectroscopic methods and with the aid of molecular modeling. The compounds were identified as (17S,20R,22R)-5beta,6beta:18,20-diepoxy-18-hydro xy-1-oxowitha-2,5, 24-trienolide (1); (17S,20R,22R)-18,20-epoxy-4beta, 18-dihydroxy-1-oxowitha-2,5,24-trienolide (2); (17S,18R,20R, 22R)-4beta-hydroxy-18,20-epoxy-18-methoxy-1-oxowitha-2,5, 24-trienolide (3); (17S,18S,20R,22R)-4beta-hydroxy-18, 20-epoxy-18-methoxy-1-oxowitha-2,5,24-trienolide (4); (17S,20R, 22R)-4beta-hydroxy-18,20-epoxy-1,18-dioxowitha-2,5,24-tri enolide (5); (17S,18R,20R,22R)-18,20-epoxy-18-methoxy-1,4-dioxowitha++ +-2,5, 24-trienolide (6); (17S,18S,20R,22R)-18,20-epoxy-18-methoxy-1, 4-dioxowitha-2,5,24-trienolide (7); and (17S,20R,22R)-5beta, 6beta-epoxy-4beta,18,20-trihydroxy-1-oxowitha-2,24-die nolide (8). Compounds 1 and 2 were obtained as epimeric mixtures at C-18.     

Secondary metabolites from the roots of Astragalus zahlbruckneri

Four new phenolic glycosides, beta-apiofuranosyl-(1-->2)-beta-glucopyranosides (1-4), along with the cycloartane triterpenes 20(R),25-epoxy-3beta,6alpha,16beta,24alpha-tetrahydroxycycloartane (5) and 20(R),24(S)-epoxy-3beta,6alpha,25-trihydroxycycloartan-16-one (6) were isolated from roots of Astragalus zahlbruckneri. The structure elucidation of all compounds was based on their (1)H and (13)C NMR spectral data including 1D-TOCSY, DQF-COSY, HSQC, and HMBC experiments.     

Diterpenoids from the roots of Suregada glomerulata

Six new diterpenoids, 7beta,8alpha-dihydroxy-12-oxo- ent-abietan-16,14-olide ( 1), 3,4,18beta-cyclopropa-7beta,17-dihydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 2), 3alpha,7beta-dihydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 3), 3-oxo-8beta,14beta-epoxy- ent-abieta-11,13(15)-dien-16,12-olide ( 4), 17-hydroxy- ent-pimara-8(14),15-dien-3-one ( 5), and 3alpha,6beta-dihydroxy- ent-kaur-16-ene ( 6), and two known compounds, 7beta-hydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 7) and jolkinolide B, were isolated from roots of Suregada glomerulata. The structures of the new compounds were elucidated on the basis of 1D and 2D NMR and other spectroscopic studies. The structure of compound 1 was confirmed by X-ray crystallography. Cytotoxic activities were evaluated against five human tumor cell lines.     

Beesiosides A-F, six new cycloartane triterpene glycosides from Beesia calthaefolia.

Six new cycloartane triterpene glycosides (1-6), beesiosides A-F, were isolated from whole plants of Beesia calthaefolia, and their structures were elucidated on the basis of extensive NMR experiments and chemical methods. Beesiosides A-F were assigned as (20S,24R)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-beta-D-xylopyranoside (1), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,12beta,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (2), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,12alpha,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (3), (20S,24R)-16beta-acetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,12alpha,18,25-tetraol-3-O-beta-D-xylopyranoside (4), (20S,24R)-epoxy-9,19-cyclolanostane-3beta,15alpha,16beta,18,25-pentaol-3-O-beta-D-xylopyranoside (5), and (20S,24R)-16beta-acetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,12beta,25-triol-3-O-beta-D-xylopyranoside (6), respectively.     

Three new triterpenes from Nerium oleander and biological activity of the isolated compounds

New ursane-type triterpene 1, oleanane-type triterpene 2, and dammarane-type triterpene 15 were isolated from the leaves of Nerium oleander together with 12 known triterpenes, 3beta-hydroxy-12-ursen-28-oic acid (ursolic acid, 3), 3beta,27-dihydroxy-12-ursen-28-oic acid (4), 3beta,13beta-dihydroxyurs-11-en-28-oic acid (5), 3beta-hydroxyurs-12-en-28-aldehyde (6), 28-norurs-12-en-3beta-ol (7), urs-12-en-3beta-ol (8), urs-12-ene-3beta,28-diol (9), 3beta-hydroxy-12-oleanen-28-oic acid (oleanolic acid, 10), 3beta,27-dihydroxy-12-oleanen-28-oic acid (11), 3beta-hydroxy-20(29)-lupen-28-oic acid (betulinic acid, 12), 20(29)-lupene-3beta,28-diol (betulin, 13), and (20S,24R)-epoxydammarane-3beta,25-diol (14). On the basis of their spectroscopic data, the structures of the new compounds 1, 2, and 15 were established as 3beta,20alpha-dihydroxyurs-21-en-28-oic acid, 3beta,12alpha-dihydroxyoleanan-28,13beta-olide, and (20S,24S)-epoxydammarane-3beta,25-diol, respectively. The anti-inflammatory activity of the seven isolated compounds and methyl esters of ursolic acid and oleanoic acid in vitro was examined on the basis of inhibitory activity against the induction of the intercellular adhesion molecule-1 (ICAM-1). The anticancer activity of the 14 isolated compounds, including 1, 2, 15, and methyl esters of ursolic acid and oleanolic acid in vitro was examined on the basis of the cell growth inhibitory activities toward three kinds of human cell lines.     

Spiranoid withanolides from Jaborosa odonelliana

Six new spiranoid withanolides, (20R,22R,23S)-5alpha-chloro-6beta,12beta,17beta,22-tetrahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (2), (20R,22R,23S)-5beta,6beta-epoxy-12beta,17beta,22-trihydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (3), (20R,22R,23S)-5beta,6beta-epoxy-4beta,12beta,17beta,22-tetrahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (4), (20R,22R,23S)-5alpha,6beta,12beta,17beta,22-pentahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (5), (20R,22R,23S)-6beta,12beta,17beta,22-tetrahydroxy-5alpha-methoxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (6), and (20R,22R,23S)-6beta,12beta,17beta,22-tetrahydroxy-2alpha,5alpha-epidioxy-1-oxo-12,23-cycloergosta-3,24-dien-26,23-olide (7), were isolated from the leaves of Jaborosa odonelliana. Compounds 2-7 were characterized by a combination of spectroscopic methods (1D and 2D NMR, MS) and molecular modeling.