Biologically active labdane-type diterpene glycosides from the root-stalks of Gleichenia japonica.

A glycoside showing a strong growth inhibition of lettuce was isolated from the root-stalks of Gleichenia japonica and its structure was established to be the 3-O-alpha-rhamnopyranosyl-(1----2)-beta-glucopyranoside of 13-O-alpha-rhamnopyranosyl-(+)-3 beta-hydroxymanool. In addition, two related glycosides were also isolated and they were characterized as the 3-O-beta-fucopyranosyl-(1----3)-alpha-rhamnopyranosyl-(1----2)-beta- glucopyranoside of 13-O-alpha-rhamnopyranosyl-(+)-3 beta-hydroxymanool and the 13-O-rhamnopyranoside of the same diterpene alcohol. The diterpene alcohol accelerated the growth of lettuce.     

Phenylethanoids, iridoids and a spirostanol saponin from Veronica turrilliana

From the aerial parts of Veronica turrilliana two phenylethanoid glycosides, turrilliosides A and B and a steroidal saponin, turrillianoside were isolated and their structures elucidated as beta-(3,4-dihydroxyphenyl)ethyl-4-O-E-caffeoyl-O-[beta-glucopyranosyl-(1-->4)-alpha-rhamnopyranosyl-(1-->6)]-beta-glucopyranoside, beta-(3,4-dihydroxyphenyl)ethyl-4-O-E-caffeoyl-[6-O-E-feruloyl-beta-glucopyranosyl-(1-->4)-alpha-rhamnopyranosyl-(1-->6)]-beta-glucopyranoside and (23S,25S)-12beta,23-dihydroxyspirost-5-en-3beta-yl O-alpha-rhamnopyranosyl-(1-->4)-beta-glucopyranoside, respectively. Furthermore, eight known glucosides are reported namely, catalpol, catalposide, verproside, amphicoside, isovanilloylcatalpol, aucubin, arbutin, and 6-O-E-caffeoylarbutin, the latter two for the first time in the genus Veronica. The two phenylethanoid glycosides were found to be potent DPPH radical scavengers. All of the tested compounds were inactive against the representative species of fungi and bacteria.     

Monoterpene and pregnane glucosides from Solenostemma argel

From the aerial parts of Solenostemma argel, two monoterpene glucosides have been isolated and identified as 6,7-dihydroxy-dihydrolinalool 3-O-beta-glucopyranoside and 6,7-dihydroxy-dihydrolinalool 7-O-beta-glucopyranoside. A pregnane glucoside was also isolated and assigned as pregn-5-ene-3,14-beta-dihydroxy-7,20-dione 3-O-beta-glucopyranoside together with the known compounds benzyl alcohol O-beta-apiofuranosyl-(1-->6)-beta-glucopyranoside, 2-phenylethyl O-alpha-arabinopyranosyl-(1-->6)-beta-glucopyranoside, astragalin and kaempferol-3-O-alpha-rhamnopyranosyl-(1-->2)-beta-glucopyranoside.     

Glycosides from Phlomis lunariifolia

An aliphatic alcohol glycoside, lunaroside 1-octen-3-yl [O-beta-apiofuranosyl-(1-->6)-O-[beta-glucopyranosyl-(1-->2)]-beta-glucopyranoside, a phenylethanoid glycoside, lunariifolioside 2-(3,4-dihydroxyphenyl)ethylO-beta-apiofuranosyl-(1-->6)-O-[O-beta-apiofuranosyl-(1-->4)-alpha-rhamnopyranosyl-(1-->3)]-4-O-(E)-caffeoyl-beta-glucopyranoside and a flavone glycoside, luteolin 7-O-[4-O-acetyl-alpha-rhamnopyranosyl-(1-->2)]-beta-glucuronopyranoside, were isolated from the aerial parts of Phlomis lunariifolia, in addition to 15 known glycosides. Their structures were elucidated on the basis of extensive 1D and 2D NMR spectroscopic interpretation and chemical degradation.     

Acylated flavonoids and phenol glycosides from Veronica thymoides subsp. pseudocinerea

A new acylated flavone glucoside, 3'-hydroxyscutellarein 7-O-(6'-O-protocatechuoyl)-beta-glucopyranoside (1), and a new phenol glucoside, 3,5-dihydroxyphenethyl alcohol 3-O-beta-glucopyranoside (6) were isolated from Veronica thymoides subsp. pseudocinerea together with seven known flavone, phenol and lignan glycosides; 3'-hydroxyscutellarein 7-O-(6'-O-trans-feruloyl)-beta-glucopyranoside (2), 3'-hydroxy, 6-O-methylscutellarein 7-O-beta-glucopyranoside (3), luteolin 7-O-beta-glucopyranoside (4), isoscutellarein 7-O-(6'-O-acetyl)-beta-allopyranosyl (1' --> 2')-beta-glucopyranoside (5), 3,4-dihydroxyphenethyl alcohol 8-O-beta-glucopyranoside (7), benzyl alcohol 7-O-beta-xylopyranosyl (1" --> 2')-beta-glucopyranoside (8), and (+)-syringaresinol 4'-O-beta-glucopyranoside (9). Compounds 2, 3 and 7-9 were reported for the first time in the genus Veronica. The structures of the isolates were determined by means of spectroscopic (UV, IR, 1D and 2D NMR, HR ESI-MS) methods. Isolated compounds (1-7) exhibited potent radical scavenging activity against the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical.     

Further saponins from Taverniera aegyptiaca

From the saponin fraction of the total methanolic extract of the dried root and stem barks of Taverniera aegyptiaca Boiss, six new triterpenoidal saponins of oleanane type were isolated and identified as 28-methyl serratagenate-3-beta-O-beta-xylopyranosyl (1-->2)-beta-glucopyranoside (2), 28-methyl serratagenate 3-beta-O-alpha-rhamnopyranosyl (1-->2)-beta-glucopyranoside (3), 3beta-O-alpha-rhamnopyranosyl (1-->2) beta-glucopyranosyl-olean-11,13(18)-dien-1beta, 3beta, 22beta-triol (4), 3beta-O-beta-glucopyranosyl (1-->2)-beta-glucuronopyranosylolean-11,13(18)-dien-1beta,3beta,22beta-triol (5), 3beta-O-beta-xylopyranosyl(1-->2)-beta-glucuronopyranosylolean-11,13(18)-dien-1beta,3beta,22beta-triol (6), 3beta-O-alpha-rhamnopyranosyl (1-->2)-beta-glucuronopyranosylolean-11,13(18)-dien-1beta, 3beta, 22beta-triol (7) together with the known oleanolic acid 3-beta-O-beta-glucoside (1). The identification of the isolated compounds was done on the basis of chemical and spectral evidences.     

Triterpene saponins from Silphium radula

Nine triterpene saponins (1-9) were isolated from leaves and stems of Silphium radula Nutt. (Asteraceae). Their structures were determined by extensive 1D ((13)C, (1)H, DEPT, TOCSY) and 2D NMR (NOESY, HSQC, HMBC) and ESI-MS studies. The compounds were identified as 3beta,6beta,16beta-trihydroxyolean-12-en-23-al-3-O-beta-glucopyranosyl-16-O-beta-glucopyranoside (1), urs-12-ene-3beta,6beta,16beta-triol-3-O-beta-galactopyranosyl-(1-->2)-beta-glucopyranoside (2), 3beta,6beta,16beta-trihydroxyolean-12-en-23-oic acid-3-O-beta-glucopyranosyl-16-O-beta-glucopyranoside (3), urs-12-ene-3beta,6beta,16beta,21beta-tetraol-3-O-beta-glucopyranoside (4), olean-12-ene-3beta,6beta,16beta,21beta-tetraol-3-O-beta-glucopyranoside (5), olean-12-ene-3beta,6beta,16beta,21beta,23-pentaol-3-O-beta-glucopyranosyl-16-O-beta-glucopyranoside (6), olean-12-ene-3beta,6beta,16beta-triol-3-O-beta-glucopyranosyl-16-O-alpha-arabinopyranosyl-(1-->2)-beta-glucopyranoside (7), olean-12-ene-3beta,6beta,16beta,23-tetraol-3-O-beta-glucopyranosyl-16-O-alpha-arabinopyranosyl-(1-->2)-beta-glucopyranoside (8), 3beta,6beta,16beta,21beta-tetrahydroxyolean-12-en-23-al-3-O-beta-glucopyranoside (9). The presence of a 6beta-hydroxyl function was not common in the oleanene or ursene class and the aglycones of these compounds were not found previously in the literature. Moreover, the cytotoxic activities of the isolated compounds were tested against human breast cancer cell line MDA-MB-231. Results showed that compound 2 decreased cell proliferation in a statistically significant manner at 25 microg/ml.     

Iridoid and megastigmane glycosides from Phlomis aurea

From the leaves of Phlomis aurea, two new iridoids of unique structures named 3-epiphlomurin (1) and phlomurin (2), a new megastigmane glucoside phlomuroside (3) and a new benzyl alcohol glycoside having the structure benzyl alcohol-O-beta-xylopyranosyl-(1-->2)-beta-glucopyranoside (4) have been isolated together with four known iridoids auroside, lamiide, 8-epiloganin and ipolamiide, two known phenolic glycosides acteoside (verbascoside) and syringin, one known phenylethanoid glycoside 2-phenylethyl-O-beta-xylopyranosyl-(1-->2)-beta-glucopyranoside, one known lignan liriodendrin and three known flavonoids chrysoeriol-7-O-beta-glucopyranoside, acacetin-7-O-beta-glucopyranoside and luteolin-7-O-beta-glucopyranoside. The structures of the isolated compounds were verified by means of mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectral analyses.     

中国植物区系的性质和各成分间的关系

根据植物区系平衡理论,以“中国种子植物区系研究”项目的结果材料分析中国植物区系的性质和各成分间的关系。从全国整体来看,中国植物区系是亚热带性质,热带成分和温带成分分别占50.2%和49.8%,即基本平衡。而各地区间有显著差异,文中做了具体比较分析及揭示其变化规律,大致是热带成分在热带地区占75%～85%,亚热带地区占40%～60%,温带地区占15%～25%,寒温,高寒和中亚荒漠地区占5%～10%,自南向北向西方向递减,温带成分与之相反,而且北方温带成分变化曲线与热带成分呈反射状,表明二者是以相反方向同等发展的。文中又据中国种子属15个分布型或地理成分所归科的相似性系数矩阵来研究各成分间的关系,结果是相似性系数为12～58强,分为10级（10～60）,排列出各成分间相似性程度及其变化梯度,其中以东亚和中国特有成分间关系最密切,温带亚洲和热带亚洲间关系最疏远,同时显出3个关系很密及最密区域,即旧大陆热带,古地中海和东亚,这三区域里可能是中国植物区系的发源地。     

蓍草化学成分研究

研究蓍草Achillea alpine L.全草的化学成分。采用大孔树脂、ODS、Sephadex LH-20凝胶柱色谱和pre-HPLC等方法分离与纯化,运用NMR、MS等波谱技术鉴定化合物结构。从蓍草95%乙醇提取物中分离得到16个化合物,分别是(2 E,4 E)-N-(2-methylbutyl)deca-2,4-dienamide(1)、墙草碱(2)、(E,E,Z)-2,4,8-decatrienoicacid isobutylamide-8,9-dehydropellitorine(3)、N-2′-methylbutyl-(E,E)-2,4-decadienam(4)、methyl-(E,E)-2,4,9-oxooctadeca-10,12-dienoate(5)、(S)-14-(E,E)-10,12-methyl 14-hydroxy-9-oxo-octadeca-10,12-dienoate(6)、(E,E)-2,4-undecadiene-8,10-diynamide-N-(2-methylpropyl)(7)、(E,E)-2,4-decadienoic acid p-hydroxyphenethylamide(8)、sinapyl alcohol diisovalerate(9)、(S)-13-hydroxyoctadeca-(Z,E)-9,11-dienoic acid(10)、(E,E)-2,4-decadienamide acid p-methoxyphenethylamide(11)、erythro-N-isobutyl-4,5-dihydroxy-2-(E)-decenamide(12)、3-O-阿魏酰-奎宁酸(13)、肉桂酸(14)、绿原酸(15)、3-O-咖啡酰-5-O-阿魏酰奎宁酸(16)。化合物1是一个新的酰胺类化合物;化合物4~6、9、10、12、13、16为首次从该属植物中分离得到;化合物8、11为首次从蓍草中分离得到。化合物1~11在四种不同的胃癌细胞株上进行细胞毒活性筛选,结果显示化合物2、5与9在50μM时对MGC-803细胞株具有较弱抑制活性,其抑制率依次为38.7%、34.7%、31.5%。     

Two new sulfated furostanol saponins from Tribulus terrestris

The known furostanol saponins methylprotodioscin and protodioscin and two new sulfated saponins, sodium salt of 26-O-beta-glucopyranosyl-22alpha-methoxy-(25R)-furost-5-ene-3beta,26-diol-3-O-alpha-rhamnopyranosyl-(1-->2)-beta-4-O-sulfo-glucopyranoside (methylprototribestin) and sodium salt of 26-O-beta-glucopyranosyl-22alpha-hydroxy-(25R)-furost-5-ene-3beta,26-diol-3-O-alpha-rhamnopyranosyl-(1-->2)-beta-4-O-sulfo-glucopyranoside (prototribestin) have been isolated from the aerial parts of Tribulus terrestris L. growing in Bulgaria. The structures of the new compounds were elucidated on the basis of 1D and 2D (DQF-COSY, TOCSY, HSQC-TOCSY, HSQC, HMBC, ROESY) NMR data, ESI mass spectra and chemical transformation.     

Characterisation of new oligoglycosidic compounds in two Chinese medicinal herbs

A series of caffeic acid derivatives (3,5-dicaffeoyl-quinic acid, 3,4-dicaffeoyl-quinic acid, and 4,5-dicaffeoyl-quinic acid), and the new compound beta,3,4-trihydroxyphenethyl-O-[beta-apiofuranosyl-(1-->4)-alpha- rhamnopyranosyl-(1-->3)]-(4-O-caffeoyl)-beta-glucopyranoside (wedelosin), as well as three known flavonoid glycosides (quercetin 3-O-beta-glucoside, kaempferol 3-O-beta-apiosyl-(1-2)-beta-glucoside, and astragalin or kaempferol 3-O-beta-glucoside) were isolated from the Chinese medicinal herb Wedelia chinensis. Wedelosin showed an inhibitory activity on both the classical and the alternative activation pathway of the complement system. Another Chinese medicinal herb, Kyllinga brevifolia, yielded two known flavonoid glycosides [kaempferol 3-O-beta-apiosyl-(1-2)-beta-glucoside and isorhamnetin 3-O-beta-apiosyl-(1-2)-beta-glucoside], and a new quercetin triglycoside [quercetin 3-O-beta-apiofuranosyl-(1-->2)-beta-glucopyranoside 7-O-alpha-rhamnopyranoside]. The latter compound showed a moderate anti-viral activity.     

Iridoid and aromatic glycosides from Scrophularia ningpoensis Hemsl. and their inhibition of [Ca2+](i) increase induced by KCl

Bioassay-guided fractionation of EtOH extract of the roots of Scrophularia ningpoensis Hemsl. resulted in the isolation of three new iridoid glycosides, i.e., 6'-O-caffeoylharpagide (1), 6'-O-feruloylharpagide (2), and 6'-O-beta-glucopyranosylharpagoside (3), and five new aromatic glycosides, i.e., 2-(3-hydroxy-4-methoxyphenyl)ethyl O-alpha-arabinopyranosyl-(1-->6)-O-alpha-rhamnopyranosyl-(1-->3)-O-beta-glucopyranoside (4), phenyl O-beta-xylopyranosyl-(1-->6)-O-beta-glucopyranoside (5), 3-methylphenyl O-beta-xylopyranosyl-(1-->6)-O-beta-glucopyranoside (6), 6-O-cinnamoyl beta-fructofuranosyl-(2-->1)-O-alpha-glucopyranosyl-(6-->1)-O-alpha-glucopyranoside (7), and 6-O-feruloyl beta-fructofuranosyl-(2-->1)-O-alpha-glucopyranosyl-(6-->1)-O-alpha-glucopyranoside (8), together with four known compounds, i.e., 6'-O-alpha-D-galactopyranosyl harpagoside (9), 6'-O-(p-coumaroyl) harpagide (10), harpagoside (11), and angoroside C (12). Activity of the isolated compounds on [Ca2+](i) increase induced by KCl was evaluated on rat cardiac myocytes using confocal laser scanning microscopy. Iridoid glycosides 1, 10, and 11, and aromatic glycosides 5 and 6 significantly inhibited the increase of [Ca2+](i) induced by KCl at 100 microM.     

Monoterpene glucosides from Origanum syriacum.

From the aerial parts of Origanum syriacum, three new monoterpene glucosides thymoquinol 2,5-O-beta-diglucopyranoside (3), carvacrol 2-O-beta-glucopyranosyl-(1-->2)-beta-glucopyranoside (4) and p-menth-1-ene-3,4-diol 4-O-beta-glucopyranoside (5) together with two known monoterpene glucosides thymoquinol 2-O-beta-glucopyranoside (1), thymoquinol 5-O-beta-glucopyranoside (2) have been isolated. The structures of the isolated compounds were verified by means of MS and NMR spectral analyses.     

Physocalycoside,a new phenylethanoid glycoside from Phlomis physocalyx Hub.-Mor

A new phenylethanoid tetraglycoside, physocalycoside (2), was isolated from the aerial parts of Phlomis physocalyx. Its structure was identified as 3-hydroxy-4-methoxy-beta-phenylethoxy-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)]-4-O-feruloyl-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside, on the basis of spectroscopic evidence. In addition, one known iridoid glucoside, lamiide (1) and five known phenylethanoid glycosides, wiedemannioside C (3), verbascoside (= acteoside) (4), leucosceptoside A (5), martynoside (6), and forsythoside B (7) were also characterized. Compounds 2-7 demonstrated radical scavenging properties towards the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical.     

Covalent anthocyanin-flavone dimer from leaves of Oxalis triangularis

The anthocyanin-flavone C-glycoside, (malvidin 3-O-(6(II)-O-alpha-rhamnopyranosyl(AIV)-beta-glucopyranoside(AII))-5-O-beta-glucopyranoside(AIII)) (apigenin 6-C-(2(II)-O-beta-glucopyranosyl(FIII)-beta-glucopyranoside(FII))) malonate(AV) (A(IV)-4-->A(V)-1, F(III)-6-->A(V)-3) (1), has been isolated from leaves of Oxalis triangularis A. St.-Hil. In the 1D (1)H NMR spectrum of 1 dissolved in CD(3)OD-CF(3)CO(2)D (95:5), MTFA, recorded 45 min after sample preparation, this covalently linked dimer occurred mainly as flavylium cation (38%) and two equilibrium forms assigned to be quinonoidal bases (54%), whereas only minor amounts of the hemiacetal forms were present. After five days storage at 300 K, the hemiacetals (39%) and flavylium cation (38%) constituted the main forms of 1. More simple anthocyanins are normally considered to be on the flavylium cation form in acidified deuterated methanol. The cross-peaks observed in NOESY NMR spectra of 1 indicated the presence of vertical 'pi-pi' stacking between the B-ring of the flavone unit and the A-ring of each of the two forms assigned to be quinonoidal bases. It was not possible to discriminate between inter- or intramolecular association mechanisms. The equilibria between the various forms of 1 were studied by two-dimensional NOESY and ROESY NMR spectroscopy. 2D HSQC-TOCSY NMR spectroscopy was among the methods used for characterization of the various forms.     

Chemistry and antioxidative factors in rosemary and sage

Rosemary and sage are common spices used in food. In our recent search of cancer chemopreventive agents from spices, the alcohol extracts of rosemary and sage showed strong antumorigenic activities. Rosemary and sage extracts contain active antioxidative factors such as phenolic diterpenes, flavonoids and phenolic acids. Here we discuss chromatographic methods used to separate and purify compounds from these spices and MS and NMR spectrometry to identify the isolated compounds. Several new compounds isolated from sage were determined to be 6-O-caffeoyl-beta-D-fructofuranosyl-(2-->1)-beta-glucopyranoside, 1-O-caffeoyl-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, 1-O-p-hydroxybenzoyl-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, 1-O-(3-methyl-2,3,4-trihydroxybutyl)-6-O-feruloyl-beta-D-glucopyranoside, 4-hydroxyacetophenone 4-O-[5-O-(3,5-dimethoxy-4-hydroxybenzoyl)-beta-D-apiofrunosyl]-(1-->2)-beta-D-glucopyranoside and 1-O-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-6-O-trans-caffeoyl-beta-D-glucopyranoside.     

Iridoid and phenolic glycosides from Morinda coreia

From the leaves and branches of Morinda coreia, six compounds [yopaaosides A-C, 10-O-acetylmonotropein, 6-O-acetylscandoside and 3,4,5-trimethoxyphenyl 1-O-beta-apiofuranosyl (1"-->6')-beta-glucopyranoside] have been isolated together with five known compounds. Structural elucidations were based on analyses of physical and spectroscopic data.     

Acylated flavone glycosides from Veronica

A survey of the flavonoid glycosides of selected taxa in the genus Veronica yielded two new acylated 5,6,7,3',4'-pentahydroxyflavone (6-hydroxyluteolin) glycosides and two unusual allose-containing acylated 5,7,8,4'-tetrahydroxyflavone (isoscutellarein) glycosides. The new compounds were isolated from V. liwanensis and V. longifolia and identified using NMR spectroscopy as 6-hydroxyluteolin 4'-methyl ether 7-O-alpha-rhamnopyranosyl(1"'-->2")[6"-O-acetyl-beta-glucopyranoside] and 6-hydroxyluteolin 7-O-(6"-O-(E)-caffeoyl)-beta-glucopyranoside, respectively. Isoscutellarein 7-O-(6"'-O-acetyl)-beta-allopyranosyl(1"'-->2")-beta-glucopyranoside was obtained from both V. intercedens and V. orientalis and its 4'-methyl ether from V. orientalis only. Complete 1H and 13C NMR spectral assignments are presented for both isoscutellarein glycosides. Two iridoid glucosides new to the genus Veronica (melittoside and globularifolin) were also isolated from V. intercedens.     

Further constituents from Caralluma negevensis

Two new megastigmane glycosides (1 and 2) and two new flavone glycosides (3 and 4) were isolated from the methanol extract of the whole plant of Caralluma negevensis Zohary (Asclepiadaceae). The structures of the isolated compounds were characterized as (9R)-2beta,9-dihydroxymegastigma-4,7-dien-3-one-9-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (1), 2beta,9-dihydroxymegastigma-4-en-3-one 9-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (2), luteolin 3'-O-beta-D-glucopyranoside-4'-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (3), and luteolin 3',4'-di-O-beta-D-glucopyranoside (4). The structures of the isolated compounds were established on the basis of spectral evidence and chemical transformation.