Triterpene Glycosides from <Emphasis Type="Italic">Cussonia paniculata</Emphasis>. II. Acetylated Glycosides from Leaves

Structures of 13 new acetylated triterpene glycosides from leaves of Cussonia paniculata (Araliaceae) were established as 28-O-(2-O-acetyl- and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β -D-glucopyranosides of 23-hydroxybetulinic acid (1a and 1b) and hederagenin (2a and 2b), 3-O-α-L-arabinopyranosyl-28-O-(2-O-acetyl- and 3-O-acetyl-a-L-rhamnopyranosyl)-(1→ 4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glycopyranosides of oleanic (3a and 3b) and ursolic (3c and 3d) acids, 3-O-α-L-arabinopyranosyl-28-O-(4-O-acetyl-, 2-O-acetyl-, and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→ 6)-O-β-D-glucopyranosides of hederagenin (4, d5a and 5b), and 3-O-β-D-glucopyranosyl-(1→2)-O-α-L-arabinopyranosyl-28-O-(2-O-acetyl- and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D- glucopyranosides of oleanic acid (6a and 6b). The structures of the compounds were established using chemical methods and NMR spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 351–356, July–August, 2005.     

Triterpene glycosides ofHedera helix I. The structures of glycosides L-1, L-2a,L-2b,L-3, L-4a,L-4b,L-6a,L-6b,L-6c,L-7a,and L7-b from the leaves of common ivy

The leaves of common ivy have yielded 11 triterpene glycosides: the 3-O-α-L-pyranosides of oleanolic acid (1), of echinocystic acid (2), and of hederagenin; the 3-O-[O-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside]s of oleanolic acid (4), of echinocystic acid (5), and of hederagenin (6); the O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin 3-O-α-L-pyranoside (7); the O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin 3-O-[O-α-L-pyranosyl-(1→2)-α-L-arabinopyranoside] (9); and the O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl esters of oleanolic acid, echinocystic acid, and hederagenin 3-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside]s (8), (10), and (11), respectively. This is the first time that compounds (1), (2), (5), (7), (9), and (10) have been found in this plant. Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 742–746, November–December, 1994.     

超高效液相色谱-二极管阵列检测-串联质谱法测定茶叶中15种黄酮醇糖苷类化合物

采用ACQUITY UPLC HSS T3色谱柱,以含0.1%(v/v)甲酸的乙腈-水为流动相,梯度洗脱,建立了超高效液相色谱-二极管阵列检测-串联质谱(UPLC-PDA-MS/MS)联用技术测定茶叶中黄酮醇糖苷类化合物的方法。结合色谱保留时间、紫外光谱、一级和二级质谱参数等信息,在绿茶和红茶中共识别了15种黄酮醇糖苷类化合物,包括3种杨梅素糖苷、6种槲皮素糖苷和6种山柰素糖苷类化合物。定量分析中采用串联四极杆质谱检测,以槲皮素-3-葡萄糖-鼠李糖二糖糖苷(Q-GRh)为标准品,其他黄酮醇糖苷进行相对定量。结果表明,绿茶和红茶中黄酮醇糖苷类化合物的含量和分布差异显著,绿茶中的黄酮醇糖苷总量是红茶的1.7倍,绿茶中的黄酮醇糖苷主要以杨梅素-3-半乳糖糖苷(M-Ga)、杨梅素-3-葡萄糖糖苷(M-G)、槲皮素-3-葡萄糖-鼠李糖-葡萄糖三糖糖苷(Q-GaRhG)、槲皮素-3-半乳糖-鼠李糖-葡萄糖三糖糖苷(Q-GRhG)、山柰素-3-半乳糖-鼠李糖-葡萄糖三糖糖苷(K-GaRhG)和山柰素-3-葡萄糖-鼠李糖-葡萄糖三糖糖苷(K-GRhG)为主,而红茶中主要以Q-GRh、槲皮素-3-葡萄糖糖苷(Q-G)、山柰素-3-葡萄糖-鼠李糖二糖糖苷(K-GRh)和山柰素-3-半乳糖糖苷(K-Ga)为主。本方法简单快速,准确性好,可用于茶叶中黄酮醇糖苷类化合物的分析。     

Triterpene glycosides ofTragacantha and their genins. Cyclostipulosides A and B fromTragacantha stipulosa

Two new triterpene glycosides of the cycloartane series, which have been called cyclostipulosides A and B, have been isolated in the individual form from the roots ofTragacantha stipulosa Boviss. Their structures have been established by physicochemical methods. Cyclostipuloside A is 24R-cycloartane-3β,6α,16β,24,25-pentaol 16-O-β-D-glucopyranoside 3-O-β-D-xylopyranoside, and cyclostipuloside B is 24R-cycloartane-3β,6α,16β,24,25-pentaol 6-O-α-L-arabinopyranoside 16-O-β-D-glucopyranoside 3-O-β-D-xylopyranoside. By the acid hydrolysis of cyclostipulosides A and B we have obtained the new glycoside 24R-cycloartane-3β,6α,16β,24,25-pentaol 16-O-β-D-glucopyranoside. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (371) 120 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 670–674, September–October, 1998.     

Triterpene glycosides ofHedera taurica. XI. Structures of taurosides St-G1, St-H1, and St-H2 from the stems of Crimean ivy

The previously known glycosides 3-O-α-L-arabinopyranosyl-28-O-[α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl]hederagenin and 3-O-[α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranosyl]-28-O-[α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl]hederagenin and the new triterpene glycoside tauroside St-H₁ — 3-O-β-D-glucopyransyl-28-O-[α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl]hederagenin — have been isolated from the stems ofHedera taurica Carr. M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 571–579, July–August, 1993.     

Flavonoids ofCaragana alaica

A new isoflavonglycoside is isolated from the terrestrial part ofCaragana alaica A. Pojark in addition to the known flavonoids 3-O-α-L-rhamnopyrano- and 3-O-β-D-glucopyranosides of isorhamnetin, quercetin, and vistin. The structure 3′-hydroxy-6.4′-dimethoxy-7-O-β-D-glucopyranosylisoflavone is established on the basis of chemical and spectral data. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 734–737, November–December, 1999.     

High-performance liquid chromatographic separation of unusual amino acid enantiomers derivatized with (1S,2S)-1,3-diacetoxy-1-(4-nitrophenyl)-2-propyl-isothiocyanate

Summary A new chiral derivatizing agent (CDA), (1S,2S)-1,3-diacetoxy-1-(4-nitrophenyl)-2-propylisothiocyanate, (S,S)-DANI, was applied to the separation of the enantiomers of unusual amino acids containing two chiral centers. Different β-methyl-α-amino acids (β-MePhe, β-MeTyr and β-MeTrp) and β-amino acids with cycloalkane skeletons (2-aminocyclopentanecarboxylic acid and 2-aminocyclohexanecarboxylic acid) were derivatized and the thiourea derivatives produced were separated by reversed-phase high-performance liquid chromatography. The applicability of this new CDA in the separation of unusual amino acids is demonstrated. The four stereoisomers of the investigated amino acids (except β-MePhe) could be separated in one chromatographic run. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Triterpene glycosides ofHedera canariensis II. Determination of the structures of glycosides L-E2 and L-H3 from the leaves of Algerian ivy

The structures of two new triterpene glycosides, L-E₂ and L-H₃ from the leaves of Algerian ivyHedera canariensis Willd. (fam. Araliaceae), have been established on the basis of chemical and spectral characteristics: they are 30-norhederagenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside and the 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-gentiobiosyl ester of 30-norhederagenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside, respectively. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 772–776, November–December, 1998.     

Triterpene glycosides fromHedera canariensis VI. Structure of L-G1 and L-G1b glycosides from leaves of canary ivy

Two new minor triterpene glycosides L-G₁, and L-G_2b, the 3-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-gentiobiosyl and 3-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-(6-O-acetyl-β-D-glucopyranosyl)-(1→6)-O-β-D glucopyranosyl esters of 30-norhederagenin, respectively, are isolated from the leaves of canary ivy (Hedera canariensis Willd.). The structures of the glycosides are found by chemical methods and¹H and¹³C NMR spectroscopy. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 623–626, September–October, 1999.     

Chemical Components of <Emphasis Type="Italic">Leptopus chinensis</Emphasis>

Six substances were isolated from the branches and leaves of the Chinese herb Leptopus Chinensis (Bunge) Pojark. by column chromatography for the first time. Their structures were elucidated as 3α-hydroxyfriedelan-2-one, saccharose, triacontanol, friedelane-2α,3β-diols, β-sitosterol-3-O-β-D-glucoside, and β -sitosterol on the basis of x-ray, chemical, and spectroscopic methods. __________ Published in Kimiya Prirodnikh Soedinenii, No. 5, pp. 462–464, September–October, 2005.     

Analysis of antioxidant flavonoids from asteraceae and moraceae plants by capillary electrophoresis

Summary Antioxidant flavonoids from the plantsSolidago gigantea Ait.,Taraxacum officinale Wiggers and Webers (Asteraceae) andMorus nigra L. (Moraceae) have been analysed by capillary electrophoresis (CE).Solidago gigantea was investigated because of its diuretic, spasmolytic, antiphlogistic, and wound-healing effect,Taraxacum officinale because it has been shown to have good diuretic and choleretic activity, andMorus nigra because it is also widely regarded as a diuretic and antidiabetic agent. Aqueous and methanolic extracts of these plants have antioxidant properties. Because their flavonoid composition might be important in their free-radical-scavenging activity, a capillary electrophoretic method was developed for characterization of the flavonoids present. We identified quercetin-3-O-β-rutinoside (rutin), quercetin-3-O-β-d-glucoside (isoquercitrin), and chlorogenic acid as the most abundant compounds inSolidago gigantea andMorus nigra, and apigenin-7-O-β-glucoside, luteolin-7-O-β-glucoside, and chlorogenic acid inTaraxacum officinale. We also discovered that quercetin-3-O-α-rhamnoside (quercitrin) and quercetin-3-O-β-galactoside (hyperoside) were absent from our sample ofSolidago gigantea and quercitrin fromMorus nigra. Quantitative analysis of these extracts was performed by high-performance liquid chromatography (HPLC). Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

New lactoyl glycoside quercetin from <Emphasis Type="Italic">Melia azedarach</Emphasis> leaves

In the course of phytochemical investigations of Melia azedarach leaves, a novel cinnamoyl glycoside, cinnamoyl-1-α-L-rhamnoside (1), and a novel acylated quercetin triglycoside, quercetin-3-O-[rhamnosyl 1→6(4″-lactoyl glucoside)]-4′-O-glucoside (2), have been isolated and characterized on the basis of spectroscopic methods, together with the six known flavonoid compounds kaempferol-3-O-rutinoside, 3-O-rhamnoside, quercetin-3-O-rutinoside, 3-O-rhamnoside, and the aglycones quercetin and kaempferol. All isolated compounds have been evaluated for their structures by chromatographic methods, chemical degradation, and UV and NMR spectroscopy. The antioxidant activity of the extract was studied as well. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 12–14, January–February, 2008.     

大孔树脂-高速逆流色谱分离纯化薇甘菊中的黄酮类化合物

该文建立了大孔树脂-高速逆流色谱分离薇甘菊中黄酮类物质的方法。分离条件为:采用大孔树脂AB-8,洗脱液为50%（v/v）乙醇水溶液,高速逆流色谱溶剂体系为正丁醇-乙酸-水（4：1：5,v/v）。从薇甘菊中分离到4种黄酮类物质:槲皮素-3-O-芸香糖苷（纯度90.2%）、山奈酚-3-O-芸香糖苷（纯度98.55%）、木犀草苷（纯度98.33%）和紫云英苷（纯度99.23%）。建立的大孔树脂-高速逆流色谱方法简单、高效,可扩展应用于从其他植物中分离黄酮类物质。     

New Oligomeric Proanthocyanidins from Bark of <Emphasis Type="Italic">Platanus orientalis</Emphasis>

Two oligomeric proanthocyanidinglycosides were isolated from bark of Platanus orientalis. Their structures and relative configurations were established as 7-O-β-D-Glcp-(−)-epicatechingallate-(4β-8)-(−)-epicatechin-(4β-8)-(−)-epicatechin-(4β-8)-5-O-β-D-Glcp-epicatechingallate (Pl-1) and 7-O-β-D-Glc→6-O-β-D-Glcp-(−)-epigallocatechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(+)-catechingallate-(4β-8)-(−)-epigallocatechingallate-(4α-8)-(−)-epicatechin-(4β-8)-[5-O-β-D-Glcp-→6-O-β-D-Glc→6-galloyl(−)-epigallocatechingallate (Pl-7). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 325–330, July–August, 2005.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D,E, and F

In addition to the know steroid sapogenin (25S)-ruscogenin (I), three new glycosides have been isolated from the leaves ofNolina microcarpa S. Wats. (family Dracaenacea), and the following structures are suggested for them: (25S)-spirost-5-ene-1β,3β-diol 1-O-β-D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1β,3β,22α,26-tetraol 1-O-β-D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1β, 3β, 22α, 26-tetraol 1-O-β-D-fucopyranoside 26-O-β-D-glucopyranoside (nolinofuroside C, V). M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 672–678, September–October, 1991.     

Furostane-Type Steroidal Saponin from <Emphasis Type="Italic">Digitalis ciliata</Emphasis>

A new furostane-type steroidal glycoside and derivative of tigogenin (1) was isolated from aqueous wastes from production of the cardiac drug acetyldigitoxin from leaves of Digitalis ciliata Trautv. (Scrophulariaceae) and characterized. The structure of the glycoside was established using physical constants, chemical transformations, and spectral data as 3-O-β-D-glucopyranosyl-(1→3) [β-D-fucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-β-D-galactopyranosyl-(25R)-5α-furostan-3β,22α,26-triol-26-O-β-D-glucopyranoside.     

Triterpene glycosides ofHedera canariensis III. Determination of the structures of glycosides L-F1, L-F2, and L-I2 from the leaves of Algerian ivy

The leaves of Algerian ivyHedera canariensis Willd. (Araliaceae) have yielded two new triterpene glycosides — caulophyllogenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside (L-F₂) and its 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-gentiobiosyl ester (L-I₂) - and also the previously known hederagenin 3-O-α-L-rhamnopyranosyl-(1→2)-O-β-D-glucopyranoside (L-F₁). The structures of the glycosides were established on the basis of chemical transformations and¹H and¹³C NMR spectroscopy. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 777–781, November–December, 1998.     

Synthesis and anti-HIV activity of triterpene 3-<Emphasis Type="Italic">O</Emphasis>-galactopyranosides,analogs of glycyrrhizic acid

A new method for synthesizing triterpene 3-O-galactosides, analogs of glycyrrhizic acid (GA) based on 18βglycyrrhetic acid (GLA) methyl esters and 18,19-dehydro-GLA, using 2,3,4,6-tetra-O-acetyl-a-Dgalactopyranosyl bromide as the glycosyl donor, I–Br promoter, and 4-? molecular sieves was developed. The method could produce primarily 3-O-α-D- or β-D-galactopyranosides depending on the reaction conditions. The 3-O-α-D-galactopyranoside of GLA exhibited an index of selectivity (IS) 2.9 times greater than that of GA for inhibition of accumulation of virus-specific protein p24 of HIV-1. β-D-Galactopyranoside of GLA was more cytotoxic for MT-4 cells and exhibited weak anti-HIV-1 activity.     

Separation of patuletin-3-O-glucoside, astragalin, quercetin, kaempferol and isorhamnetin from Flaveria bidentis (L.) Kuntze by elution-pump-out high-performance counter-current chromatography

Flaveria bidentis (L.) Kuntze is an annual alien weed of Flaveria Juss. (Asteraceae) in China. Bioactive compounds, mainly flavonol glycosides and flavones from F. bidentis (L.) Kuntze, have been studied in order to utilize this invasive weed, Analytical high-performance counter-current chromatography (HPCCC) was successfully used to separate patuletin-3-O-glucoside, a mixture of hyperoside (quercetin-3-O-galactoside) and 6-methoxykaempferol-3-O-galactoside, astragalin, quercetin, kaempferol and isorhamnetin using two runs with different solvent system. Ethyl acetate-methanol-water (10:1:10, v/v) was selected by analytical HPCCC as the optimum phase system for the separation of patuletin-3-O-glucoside, a mixture of hyperoside and 6-methoxykaempferol-3-O-galactoside, and astragalin. A Dichloromethane-methanol-water (5:3:2, v/v) was used for the separation of quercetin, kaempferol and isorhamnetin. The separation was then scaled up: the crude extract (ca 1.5 g) was separated by preparative HPCCC, yielding 12 mg of patuletin-3-O-glucoside at a purity of 98.3%, yielding 9 mg of a mixture of hyperoside and 6-methoxykaempferol-3-O-galactoside constituting over 98% of the fraction, and 16 mg of astragalin (kaempferol-3-O-glucoside) at a purity of over 99%. The pump-out peaks are isorhanetin (98% purity), kaemferol (93% purity) and quercitin (99% purity). The chemical structure of patuletin-3-O-glucoside and astragalin were confirmed by MS and 1H, 13C NMR.     

全二维液相色谱串联质谱用于银杏叶提取物成分分析的研究

建立了全二维液相色谱串联质谱分离分析模式,将质脂体色谱柱和ODS反相色谱柱作为二维分析色谱柱,二者通过一个连有两个0.5 mL定量环的八通阀耦联。质脂体色谱柱上的馏分在反相色谱柱上分离后,直接进入紫外-检测器,然后经分流器分流后进入大气压电离质谱。将该体系用于银杏叶提取物的组成研究,共检测到至少41个组分,结合紫外-可见光谱和质谱信息,其中13个组分初步鉴定为银杏内酯B、银杏内酯C、白果内酯、槲皮素芸香糖苷、槲皮素、槲皮素-3-O-β-D-葡萄糖基(1-2)-α-L-鼠李糖苷、槲皮素-3-O-β-D-葡萄糖苷、异鼠李素、山柰酚-3-O-β-D-芸香糖基(1-2)-α-L-鼠李糖苷、异鼠李素-3-O-β-D-芸香糖苷、山柰酚-3-O-β-D-葡萄糖苷、山柰酚和山柰酚-3-O-β-D-芸香糖苷。