Bufadienolides from Urginea hesperia

For the first time the composition of the bufadienolide complex in URGINEA HESPERIA Webb & Berth. has been investigated. From an extract of lyophilized plants, thirteen bufadienolides were isolated. By means of FAB-MS, (1)H-NMR, and (13)C-NMR studies the compounds were structurally elucidated as scillarenin, scilliphaeosidin, scillarenin-3- O-alpha- L-rhamnoside, scilliphaeosidin-3- O-alpha- L-rhamnoside, gamabufotalin-3- O-alpha- L-rhamnoside, 11alpha-hydroxyscilliglaucosidin-3- O-alpha- L-rhamnoside, scillarenin-3- O-alpha- L-2',3'-diacetylrhamnosido-4'-beta- D-glucoside, scillarenin-3- O-alpha- L-rhamnosido-4'-beta- D-glucosido-3'-beta- D-glucoside, scillarenin-3- O-alpha- L-rhamnosido-4'-beta- D-glucosido-4'-beta- D-glucoside, scillarenin-3- O-alpha- L-2',3'-diacetylrhamnosido-4'-beta- D-glucosido-3'-beta- D-glucoside, scillarenin-3- O-alpha- L-2',3'-diacetylrhamnosido-4'-beta- D-glucosido-4'-beta- D-glucoside, scilliphaeosidin-3- O-alpha- L-rhamnosido-4'-beta- D-glucosido-3'-beta- D-glucoside, and scilliphaeosidin-3- O-alpha- L-rhamnosido-4'-beta- D-glucosido-4'-beta- D-glucoside.     

A new triterpene ester, an anthraquinone and other constituents of the fern Lygodium flexuosum

LYGODIUM FLEXUOSUM, a fern reported to exhibit antifertility activity, has been found to contain a new compound characterized as O- P-coumaryl-dryocrassol, besides dryocrassol itself, tectoquinone, kaempferol, kaempferol-3-beta- D-glucoside, beta-sitosterol, and stigmasterol.     

About the Bufadienolide Complex of "Red" Squill

Red coloured bulbs of plants of the URGINEA MARITIMA aggregate from the northern and southern Mediterranean area were shown to exhibit different bufadienolide compositions. Therefore, the bufadienolide complex of "red squill" samples from Tunesia and from Sardegna was investigated. Twelve bufadienolides were isolated from bulbs of tetraploid squill from Tunesia, sixteen from tetraploid samples from Sardegna. The Compounds were identified by means of FAB-MS, (1)H-NMR, and (13)C-NMR studies or comparison with authentic substances. Both of the samples contained scilliroside ( 14), scillarenin 3- O-beta- D-glucoside ( 2), proscillaridin A (1), scilliphaeosidin 3- O-beta- D-glucoside ( 5), scilliglaucoside ( 17), scilliphaeoside ( 4), and 12- EPI-scilliphaeoside ( 7); the bulbs from Tunesia contained additionally glucoscilliphaeoside ( 6) and the four new bufadienolides 12- EPI-glucoscilliphaeoside ( 10), 12beta-hydroxyscilliglaucosidin 3- O-beta- D-glucoside ( 21), 12- EPI-scilliphaeosidin 3- O-beta- D-glucoside ( 8), and 12- EPI-scilliphaeosidin 3- O-alpha- L-rhamnosido-alpha- L-rhamnoside ( 9). In the bulbs from Sardegna scülaren A ( 3), gamabufotalin 3- O-alpha- L-rhamnoside ( 20), scilliglaucoside ( 17), scillirubrosidin 3- O-alpha- L-rhamnoside ( 11), scillirubroside ( 12), 12beta-hydroxyscilliroside ( 15), 5alpha-4,5-dihydroscillirosidin 3- O-alpha- L-thevetosido-beta- D-glucoside ( 19), and deacetyl-scilliroside ( 8) besides the new Compounds 10-carb-oxy-5beta,14beta-dihydroxybufa-3,20,22-trienolide 5- O-beta- D-glucoside ( 18) and scilliglaucogenin ( 16) were found in addition. Not only quantitative but even qualitative differences in the bufadienolide pattern between the samples of the northern and the southern Mediterranean area were proved. By now it is not clear whether the investigated samples belong to different chemodemes of URGINEA NUMIDICA or are two different species of the URGINEA MARITIMA aggregate.     

New Chalcones from Bidens pilosa

Okanin 4'- O-beta- D-(2',4',6'-triacetyl)-glucoside, okanin 4'- O-beta- D-(6'- TRANS-P-coumaroyl)-glucoside, both new natural compounds, and okanin 3'- O-beta- D-glucoside have been isolated from the leaves of BIDENS PILOSA L. Their structures have been elucidated by means of UV, FD-MS, (1)H-NMR, and (13)C-NMR spectroscopy. NMR spectral data for okanin 4'- O-beta- D-glucoside (marein) are given.     

Highly Methylated 6-Hydroxyflavones and Other Flavonoids from Thymus piperella

From the aerial parts of THYMUS PIPERELLA, the free flavone aglycones 5,6-dihydroxy-7,8,4'-trimethoxyflavone ( 1), 5,6-dihydroxy-7,8,3',4'-tetramethoxyflavone ( 2), 5,6-dihydroxy-7,3',4'-trimethoxyflavone ( 3), ladanein ( 4) (5,6-dihydroxy-7,4'-dimethoxy-flavone), 5-hydroxy-7,4'-dimethoxyflavone ( 5) and apigenin ( 6), the flavanones naringenin ( 7) and eriodictyol ( 8), and the flavone glycosides vicenin-2 ( 9), apigenin-7- O-beta- D-glucoside (10) and luteolin-7- O-beta- D-glucoside ( 11), have been isolated and identified. This is the first time that 5,6-dihydroxy-7,8,4'-trimethoxyflavone has been found as a natural product.     

Inhaltsstoffe tropischer Arzneipflanzen, 67. Mitt.: 24-Acetylaminofevicordin D-glucosid,ein artefizieller Inhaltsstoff von Fevillea cordifolia? — Zur Reaktivität der Fevicordine

Constituents of Tropical Medicinal Plants, LXVII: 24-Acetylaminofevicordin D-glucoside, an Artificial Constituent of Fevillea cordifolia? — On the Reactivity of the Fevicordines 24-Acetylaminofevicordin D-glucoside ( 1 ) was isolated as a minor component from the seeds of Fevillea cordifolia (Cucurbitaceae) and its structure was determined by spectroscopic methods. Experiments showed that the enone-system in the side chain of fevicordin A-glucoside ( 2 ) which represents the main constituent of the seeds, undergoes a Michael addition with nucleophiles, and ammonia reacts very easily under simultaneous migration of the acetyl group from C-25 to the nitrogen. Therefore, 1 probably has to be regarded as an artifact.     

New cytotoxic flavonoids from Thelypteris torresiana

During our search for anti-tumor agents from pteridophytes, three new flavonoids, protoapigenone (1), 5',6'-dihydro-6'-methoxyprotoapigenone (2), and protoapigenin (3), along with four known compounds, protoapigenin 4'- O-beta- D-glucoside (4), apigenin 4'- O-beta- D-glucoside (5), kaempferol 3- O-alpha- L-rhamnopyranoside (6), kaempferol 3,7-di- O-alpha- L-rhamnopyranoside (7), were isolated from Thelypteris torresiana using bioactivity-guided fractionation methods . The structures of the new isolates were elucidated by 1D- and 2D-NMR spectral analysis. Among the 7 compounds, protoapigenone (1) exhibited significant anti-tumor activities toward Hep G2, Hep 3B, MCF-7, A549, and MDA-MB-231 with IC50 values of 1.60, 0.23, 0.78, 3.88 and 0.27 microg/mL, respectively.     

双波长薄层扫描法测定黄芪茎叶中黄酮甙的含量

本实验采用日本岛津CS-930双波长薄层扫描仪对膜荚黄芪(Astragalus membranaceus)茎叶中的黄酮类成分,鼠李柠檬素3-葡萄糖甙的含量进行了测定。测定结果为茎中含量占0.122%,叶中含量占0.506%.     

Polygoacetophenoside, A New Acetophenone Glucoside from Polygonum multiflorum1

Polygoacetophenoside ( 3), a new acetophenone glucoside, was isolated from POLYGONUM MULTIFLORUM (Polygonaceae), together with quercetin 3- O-galactoside ( 1) and arabinoside ( 2). The structure of the new glucoside was deduced to be 2,3,4,6-tetrahy-droxyacetophenone 3- O-beta- D-glucoside ( 3) by its chemical and spectral data.     

Flavan-3-ols and flavonoids from Potentilla anserina

Roots/rhizomes and aerial parts of Potentilla anserina L. (Rosaceae) contain two flavan-3-ols: (+)-catechin and (+)-gallocatechin. The flavonol glycosides and glucuronides isolated from the herb were kaempferol 3- O-beta- D-glucoside, kaempferol 3- O-beta- D-(6'- O-( E)- P-coumaroyl)glucopyranoside, quercetin 3- O-beta- D-glucoside, quercetin 3- O-beta- D-xyloside, quercetin 3- O-alpha- L-rhamnoside, quercetin 3- O-beta- D-sambubioside, quercetin 3- O-beta- D-glucuronide, isorhamnetin 3- O-beta- D-glucuronide, myricetin 3- O-alpha- L-rhamnoside, and myricetin 3- O-beta- D-glucuronide. Herbacetin 8-methyl ether-3- O-beta- D-sophoroside (8-methoxykaempferol 3-sophoroside) was identified in the flowers. The 6'-methyl ester of quercetin 3- O-beta- D-galacturonide, which may be an artifact, was isolated from the herb. The total flavonoid content calculated as quercetin-3- O-beta- D-glucuronide was 1% in the lyophilized herb used in this study and 0.5% in a commercial drug, meeting DAC standards.     

Antimicrobial constituents from goldenseal (the Rhizomes of Hydrastis canadensis) against selected oral pathogens

Two new C-methyl flavonoids, 6,8-di- C-methylluteolin 7-methyl ether (1) and 6- C-methylluteolin 7-methyl ether (2), were isolated from a commercially available sample of the roots of Hydrastis canadensis, along with seven known compounds, berberine (3), beta-hydrastine (4), canadine (5), canadaline (6), isocorypalmine (7), canadinic acid (8), and beta-sitosterol 3- O-beta- D-glucoside (9). The structures of the new compounds 1 and 2 were elucidated on the basis of their spectral data including 1D and 2D NMR techniques. Of these isolates, berberine (3) and, to a lesser extent, 1 and 2, showed antimicrobial activity when evaluated against the oral pathogens Streptococcus mutans and Fusobacterium nucleatum. Berberine (3) exhibited an additive antimicrobial effect when tested against S. mutans in combination with 1.     

Auriculatin 4'-O-Glucoside: A New Prenylated Isoflavone Glycoside from Erythrina eriotricha1

In addition to known compounds, sigmoidin C and 8-(3,3-dimethylallyl)-erythrinin C, also called senegalensin, a new isoflavone glycoside designated auriculatin 4'- O-glucoside was isolated from the chloroform extract of the stem bark of ERYTHRINA ERIOTRICHA. Its structure was elucidated as 7,6-(2',2'-dimethyl-2 H-pyrano)-2',5-dihydroxy-8-(3,3-dimethylallyl)-isoflavone 4'- O-beta- D-glucoside on the basis of spectroscopic methods and chemical evidence.     

Preparation of 3-amino-3-deoxy derivatives of trehalose and sucrose and their activities

The 3-keto derivatives of trehalose and sucrose respectively were prepared by a one-step enzymatic route using D-glucoside 3-dehydrogenase from Flavobacterium saccharophilum. Reductive amination of 3-ketotrehalose with ammonium acetate and sodium cyanoborohydride gave three compounds, 3-amino-3-deoxy-alpha-D-allopyranosyl alpha-D-glucopyranoside, 3-amino-3-deoxy-alpha-D-glucopyranosyl alpha-D-glucopyranoside (3-trehalosamine) and 3-amino-3-deoxy-alpha-D-mannopyranosyl alpha-D-glucopyranoside. From the reductive amination of 3-ketosucrose, 3-amino-3-deoxy-alpha-D-allopyranosyl beta-D-fructofuranoside and 3-amino-3-deoxy-alpha-D-glucopyranosyl beta-D-fructofuranoside were obtained. The antibiotic and glycohydrolase inhibitory activities of these 3-amino-3-deoxy derivatives were determined.     

Bufadienolides from Urginea maritima sensu strictu

Fourteen bufadienolides were isolated from bulbs of hexaploid URGINEA MARITIMA (L.) Baker SENSU STRICTU. The compounds were identified by means of FAB-MS, (1)-NMR and (13)C-NMR studies or comparison with authentic substances. Besides the already known proscillaridin A, scillaren A, glucoscillaren A, scilliphaeoside, glucoscilliphaeoside, 12- EPI-scilliphaeoside, gamabufotalin-3- O-alpha- L-rhamnoside, 16beta- O-acetyl-gamabufotalin-3- O-alpha- L-rhamnoside, scilliglaucoside, and scillicyanoside, four new bufadienolides were isolated: 5alpha-4,5-dihydroproscillaridin A, 5alpha-4,5-dihydroglucoscillaren A, gamabufotalin-3- O-alpha- L-rhamnosido-beta- D-glucoside, and 19-oxo-5alpha-4,5-dihydro-proscillaridin A.     

HPLC法测定安神补脑液中2,3,5,4′-四羟基二苯乙烯-2-O-β-D葡萄糖苷的含量

目的：建立安神补脑液中2,3,5,4′-四羟基二苯乙烯-2-O-β-D葡萄糖苷的含量测定方法.方法：采用HPLC法,Agilent EcLipse XDB-C18柱（250 mm×215;4.6 mm,5 μm）,乙腈-水（19：81）为流动相,流速为1.0 ml·min^-1,荧光检测器,检测波长为λex=360 nm,λem=417 nm.结果：2,3,5,4′-四羟基二苯乙烯-2-O-β-D葡萄糖苷在5.34～213.60 μg·min^-1范围内线性关系良好,平均回收率为100.7%,RSD为1.8%（n=9）.结论：2,3,5,4′-四羟基二苯乙烯-2-O-β-D葡萄糖苷在5.34～213.60 μg·min^-1范围内线性关系良好,平均回收率为100.7%,RSD为1.8%（n=9）.     

Identification of isoflavones in the roots of Pueraria lobata

The isoflavones of the roots of Pueraria lobata (Willd.) Ohwi (Puerariae Radix) were investigated by high-performance liquid chromatography (HPLC) coupled to photodiode array (PDA) and to mass spectroscopy (MS) using atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI) in combination with collision-activated decomposition (CAD) (HPLC-APCI-CAD-MS or ESI-CAD-MS) for identification of glycosides and HPLC-APCI-CAD-MS for identification of aglycones. The major glycosides are derived from daidzein ( 9) and most are 8- C-glycosides. 3'-Hydroxypuerarin-4'- O-deoxyhexoside ( 2B) and 3'-methoxy-6'- O- D-xylosylpuerarin ( 6) were identified as new constituents. MS data were obtained for puerarin-4'- O- D-glucoside ( 1), 3'-hydroxypuerarin ( 2A), puerarin ( 3), 3'-methoxypuerarin ( 4), 6'- O- D-xylosylpuerarin ( 5), daidzin ( 7) and 3'-methoxydaidzin ( 8), which were previously characterized by NMR analysis. Isoflavones identified in Puerariae Radix comprise 3'-methoxydaidzein ( 10), genistein ( 12), daidzein-7- O-methyl ether ( 13A), 3'-methoxydaidzein-7- O-methyl ether or 3'-methoxyformononetin ( 13B) and biochanin A ( 15), while previous characterization of daidzein ( 9) and formononetin ( 14) was substantiated by MS data. The structure of compound 11 could not be established by MS techniques. The estrogenic activity was mainly located in the aglycone fraction.     

山楂叶中芳香族化合物的分离和鉴定

目的研究阐明山楂(Crataegus pinnatifida Bge.)叶的化学成分。方法运用硅胶柱色谱、Sephadex LH-20柱色谱、ODS柱色谱、制备HPLC等分离手段进行化学成分的分离纯化,根据理化性质和波谱数据鉴定其结构。结果从山楂叶体积分数为80%乙醇提取物中分离得到13个芳香族化合物,分别鉴定为3-乙氧基-4-羟基苯甲酸(1)、3,4-二甲氧基苯丙醛(2)、对乙氧基苯甲酸(3)、对甲基苯甲酸(4)、对羟基苯甲酸(5)、3-甲氧基-4-甲基苯甲酸(6)、对甲氧基苯丙酸(7)、对甲氧基苯丙醛(8)、反式对乙氧基桂皮酸(9)、1-(3,4,5-三甲氧基苯基)乙烷-1’S,2’-二醇(10)、3-甲氧基对羟基苯甲醛(11)、对羟基苯甲醛(12)、6-羟基苯甲酸苄酯-2-O-β-D-葡萄糖苷(13)。结论化合物1、2为新天然产物,3～13为首次从山楂属植物中分离得到。     

骨碎补中的苯丙素类成分及其对UMR 106细胞增殖作用的影响

目的研究骨碎补(Drynaria fortunei)中的苯丙素类成分,并讨论它们对大鼠类成骨细胞UMR 106增殖的影响。方法采用硅胶、Sephadex LH-20、ODS柱色谱分离骨碎补根茎的活性成分,应用理化方法及1D-NMR、2D-NMR方法确定化学结构,并检测对UMR 106细胞增殖的影响。结果从骨碎补体积分数为60%乙醇提取物中的大孔吸附树脂柱色谱的体积分数为30%乙醇洗脱部分,分离得到7个苯丙素类化合物和2个苯甲酸类化合物,分别鉴定为:(E)-4-O-β-D-吡喃葡萄糖基反式咖啡酸(1)、(E)-p-松针酸β-D-吡喃葡萄糖苷(2)、阿魏酸β-D-吡喃葡萄糖苷(3)、反式咖啡酸(4)、p-香豆酸4-O-β-D-吡喃葡萄糖苷(5)、二氢异阿魏酸(6)、二氢咖啡酸(7)、香草酸4-O-β-D-吡喃葡萄糖苷(8)、原儿茶酸(9)。并检测了化合物1~9对UMR 106细胞增殖的影响。结论化合物1首次从该种植物中分离得到,化合物2~8首次从该属植物中分离得到。化合物1~4显示了对UMR 106细胞的促增殖作用,而其他化合物则没有显示活性。