Malonylated flavonol glycosides from the petals of Clitoria ternatea

Three flavonol glycosides, kaempferol 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside, quercetin 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside, and myricetin 3-O-(2",6"-di-O-alpha-rhamnosyl)-beta-glucoside were isolated from the petals of Clitoria ternatea cv. Double Blue, together with eleven known flavonol glycosides. Their structures were identified using UV, MS, and NMR spectroscopy. They were characterized as kaempferol and quercetin 3-(2(G)- rhamnosylrutinoside)s, kaempferol, quercetin, and myricetin 3-neohesperidosides, 3-rutinosides, and 3-glucosides in the same tissue. In addition, the presence of myricetin 3-O-(2"-O-alpha-rhamnosyl-6"-O-malonyl)-beta-glucoside was inferred from LC/MS/MS data for crude petal extracts. The flavonol compounds identified in the petals of C. ternatea differed from those reported in previous studies.     

Acylated anthocyanins from the blue-violet flowers of Anemone coronaria

Five polyacylated anthocyanins were isolated from blue-violet flowers of Anemone coronaria 'St. Brigid'. They were identified as delphinidin 3-O-[2-O-(2-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(malonyl)-beta-D-galactopyranoside]-7-O-[6-O-(trans-caffeoyl)-beta-D-glucopyranoside]-3'-O-[beta-D-glucuronopyranoside], and its demalonylated form, delphinidin 3-O-[2-O-(2-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(2-O-tartaryl)malonyl)-beta-D-galactopyranoside]-7-O-[6-O-(trans-caffeoyl)-beta-D-glucopyranoside]-3'-O-[beta-D-glucuronopyranoside], and its cyanidin analog as well as delphinidin 3-O-[2-O-(2-O-(trans-caffeoyl)-beta-D-glucopyranosyl)-6-O-(2-O-(tartaryl)malonyl)-beta-D-galactopyranoside]-7-O-[6-O-(trans-caffeoyl)-beta-D-glucopyranoside].     

Coumarin glucosides from Cruciata taurica

Two new coumarin glycosides (1 and 2) along with two known coumarin glucosides, daphnin (3) and daphnetin glucoside (4) were isolated from the aerial parts of Cruciata taurica. The structures of the new compounds were elucidated by spectral methods and chemical means as 7-O-(6' -acetoxy-beta-D-glucopyranosyl)-8-hydroxycoumarin (1) and 7-O-[6 '-O-(3',4'-dihydroxycinnamoyl)-beta-D-glucopyranosyl]-8-hydroxycoumarin (2). The phylogenetic significance of coumarins in C. taurica was discussed.     

Characterization of novel glycolipids from the giant cockroach (Blaberus colosseus)

A novel class of glycolipids, assigned the trivial name blaberosides, was isolated from whole head tissues of the giant cockroach (Blaberus colosseus). The class consists of two closely related families, blaberoside I and blaberoside II, each containing species differing by 26 atomic mass units. The structure of these gentiobiose-based glycoglycerolipids was elucidated by chromatographic behavior, nuclear magnetic resonance spectroscopy, mass spectrometry, and analysis of chemical degradation products and derivatives. Species in the blaberoside I family have been identified as 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D-glucopyranosyl)-bet a-D- glucopyranosyl]-3-(hexadecyloxy)-1-(3-hydroxy-11-eicosenoyl)-1,2-p ropanediol (blaberoside Ia) and 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D-glucopyranosyl)-bet a- D-glucopyranosyl]-3-(6-octadeceloxy)-1-(3-hydroxy-11-eicosenoyl )-1,2- propanediol (blaberoside Ib). Two smaller homologs of the blaberoside II family were discerned to be 2-O-[6'-O-(6"-O-3-hydroxy-11- eicosenoyl-beta-D-glucopyranosyl)-beta-D-glucopyranosyl]-3-(hex ade cyloxy)- 1,2-propanediol (blaberoside IIa), and 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D- glucopyranosyl)-beta-D-glucopyranosyl]-3-(4-octadeceloxy)-1,2-prop anediol (blaberoside IIb). These compounds are unique because they are animal origin glyceroglycolipids with a highly flexible gentiobiose backbone, and a beta-linkage of the carbohydrate to the glycerol ether at the 2 position rather than the usual 1 position.     

Neolignan glycosides from Symplocos caudata

A phytochemical investigation of the roots of Symplocos caudata Wall (Symplocaceae) resulted in isolation and characterization of four optical isomers of a neolignan glycoside (1-4), a lignan lactone glycoside (5), a phenylpropanoid glycoside (6), as well as two known compounds (7, 8). Their structures were elucidated as (7S,8S)-threo-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (1), (7R,8R)-threo-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (2), (7R,8S)-erythro-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (3), (7S,8R)-erythro-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (4), 8R,8'R-matairesinol-4-O-beta-d-xylopyranosyl-(1-->2)-O-beta-d-glucopyranoside (5), 1-O-[beta-d-xylopyranosyl-(1-->6)-O-beta-d-glucopyranosyl]-2,6-dimethoxy-4-propenyl-phenol (6), matairesinoside (7), and (R)-1-O-(beta-d-glucopyranosyl)-2-[2-methoxy-4-(omega-hydroxypropyl)-phenoxyl]-propan-3-ol (8) on the basis of spectroscopic data (1D and 2D NMR, MS and CD) and chemical evidence.     

New flavonoid glycosides from Aconitum naviculare (Brühl) Stapf, a medicinal herb from the trans-Himalayan region of Nepal

Three new flavonoid glycosides, 3-O-[beta-D-glucopyranosyl-(1-->3)-(4-O-trans-p-coumaroyl)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl]-7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]kaempferol, 3-O-[beta-D-glucopyranosyl-(1-->3)-(4-O-trans-p-coumaroyl)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl]-7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]quercetin and 7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]quercetin were isolated from the aqueous extract of the aerial parts of Aconitum naviculare. Their structures were elucidated by spectral analysis (HRAPI-TOF MS, 1H, 13C NMR, HMQC, HMBC, DFQ-COSY, ROESY and TOCSY).     

Triterpenoid saponins from Oreopanax guatemalensis

Seven oleanane-type saponins were isolated from the leaves and stems of Oreopanax guatemalensis, together with ten known saponins of lupane and oleanane types. The new saponins were respectively characterized as 3-O-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha- L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-beta-D-glucopyranosyl 3beta-hydroxy olean-11,13(18)-dien-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta- D-glucopyranosyl]ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl]3beta-hydroxy olean-11,13(18)-dien-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]3beta, 23 dihydroxy olean-18-en-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-6-O-acetyl glucopyranosyl-(1-->6)-beta-D-glucopyranosyl]ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl] hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[beta-D-xylopyranosyl-(1-->2 )-]beta-D-glucopyranosyl]ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[beta-D-glucopyranosyl-(1-->2)-]beta-D-glucopyranosyl] ester and 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl] hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[alpha-L-arabinofuranosyl-(1-->2)]-beta-D-glucopyranosyl] ester. The structures were determined by spectral analyses. The NMR assignments were made by means of HOHAHA, 1H-1H COSY, HMQC, HMBC spectra and NOE difference studies.     

7-Polyacylated delphinidin 3,7-diglucosides from the blue flowers of Leschenaultia cv. Violet Lena

The triacyl anthocyanins, Leschenaultia blue anthocyanins 1 and 2 (LBAs 1 and 2) were isolated from the blue flowers of Leschenaultia R. Br. cv. Violet Lena (Goodeniaceae), in which LBA 1 was present as a dominant pigment. The structure of LBA 1 was elucidated to be delphinidin 3-O-[6-O-(malonyl)-beta-D-glucopyranoside]-7-O-[6-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranoside] by application of chemical and spectroscopic methods. Since LAB 2 was isolated in small amount, its structure was tentatively assigned as either delphinidin 3-(malonylglucoside)-7-[(glucosyl-p-coumaroyl)-(glucosylcaffeoyl)-glucoside] or delphinidin 3-(malonyl-glucoside)-7-[(glucosyl-caffeoyl)(glucosyl-p-coumaroyl)-glucoside]. This is the first report of the occurrence of 7-polyacylated anthocyanins in the family of Goodeniaceae, although others have been found in the families of the Ranunculaceae, Campanulaceae, and Compositae. Moreover, delphinidin 3-glycoside-7-di-(glucosylcaffeoyl)-glucoside has been reported only in the flowers of Platycodon grandiflorum (Campanulaceae). From a chemotaxonomical viewpoint, the Goodeniaceae may be closely related to the Campanulaceae.     

Two triacylated and tetraglucosylated anthocyanins from Ipomoea asarifolia flowers

Two triacylated and tetraglucosylated anthocyanins derived from cyanidin were isolated from the flowers of Ipomoea asarifolia and their structures elucidated using chemical, GC, MS and NMR methods (1H and 13C, TOCSY-1D, DQF-COSY, DIFFNOE and HMBC). These complex pigments were found to consist of cyanidin 3-O-[2-O-(6-O-E-caffeoyl-beta-D-glucopyranosyl)]-[6-O-[4-O-(6-O-E-3,5-dihydroxycinnamoyl-beta-D-glucopyranosyl)-E-caffeoyl]-beta-D-glucopyranosyl]-5-O-beta-D-glucopyranoside and cyanidin 3-O-[2-O-(6-O-E-p-coumaroyl-beta-D-glucopyranosyl)]-[6-O-[4-O-(6-O-E-p-coumaroyl-beta-D-glucopyranosyl)-E-caffeoyl]-beta-D-glucopyranosyl]-5-O-beta-D-glucopyranoside.     

Triacylated cyanidin 3-(3X-glucosylsambubioside)-5-glucosides from the flowers of Malcolmia maritima

Three acylated cyanidin 3-(3(X)-glucosylsambubioside)-5-glucosides (1-3) and one non-acylated cyanidin 3-(3(X)-glucosylsambubioside)-5-glucoside (4) were isolated from the purple-violet or violet flowers and purple stems of Malcolmia maritima (L.) R. Br (the Cruciferae), and their structures were determined by chemical and spectroscopic methods. In the flowers of this plant, pigment 1 was determined to be cyanidin 3-O-[2-O-(2-O-(trans-sinapoyl)-3-O-(beta-D-glucopyranosyl)-beta-D-xylopyranosyl)-6-O-(trans-p-coumaroyl)-beta-D-glucopyranoside]-5-O-[6-O-(malonyl)-(beta-D-glucopyranoside) as a major pigment, and a minor pigment 2 was determined to be the cis-p-coumaroyl isomer of pigment 1. In the stems, pigment 3 was determined to be cyanidin 3-O-[2-O-(2-O-(trans-sinapoyl)-3-O-(beta-D-glucopyranosyl)-beta-D-xylopyranosyl)-6-O-(trans-p-coumaroyl)-beta-d-glucopyranoside]-5-O-(beta-D-glucopyranoside) as a major anthocyanin, and also a non-acylated anthocyanin, cyanidin 3-O-[2-O-(3-O-(beta-D-glucopyranosyl)-beta-D-xylopyranosyl)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside) was determined to be a minor pigment (pigment 4). In this study, it was established that the acylation-enzymes of malonic acid has important roles for the acylation of 5-glucose residues of these anthocyanins in the flower-tissues of M. maritima; however, the similar enzymatic reactions seemed to be inhibited or lacking in the stem-tissues.     

Saponins and acylated saponins from Dizygotheca kerchoveana

Four new triterpenoid saponins were isolated from the leaves and stem of branches of Dizygotheca kerchoveana along with seven known ones. The new saponins were respectively characterized as 3-O-[beta-D-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid, 3-O-[beta-D-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-[beta-D-3-O-trans-p-coumaroyl-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester and 3-O-[beta-d-3-O-cis-p-coumaroyl-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester. Their structures were elucidated by 1D and 2D NMR experiments, FAB-MS as well as chemical means.     

A rationale for the shift in colour towards blue in transgenic carnation flowers expressing the flavonoid 3',5'-hydroxylase gene

Recently marketed genetically modified violet carnations cv. Moondust and Moonshadow (Dianthus caryophyllus) produce a delphinidin type anthocyanin that native carnations cannot produce and this was achieved by heterologous flavonoid 3',5'-hydroxylase gene expression. Since wild type carnations lack a flavonoid 3',5'-hydroxylase gene, they cannot produce delphinidin, and instead accumulate pelargonidin or cyanidin type anthocyanins, such as pelargonidin or cyanidin 3,5-diglucoside-6"-O-4, 6"'-O-1-cyclic-malyl diester. On the other hand, the anthocyanins in the transgenic flowers were revealed to be delphinidin 3,5-diglucoside-6"-O-4, 6"'-O-1-cyclic-malyl diester (main pigment), delphinidin 3,5-diglucoside-6"-malyl ester, and delphinidin 3,5-diglucoside-6",6"'- dimalyl ester. These are delphinidin derivatives analogous to the natural carnation anthocyanins. This observation indicates that carnation anthocyanin biosynthetic enzymes are versatile enough to modify delphinidin. Additionally, the petals contained flavonol and flavone glycosides. Three of them were identified by spectroscopic methods to be kaempferol 3-(6"'-rhamnosyl-2"'-glucosyl-glucoside), kaempferol 3-(6"'-rhamnosyl-2"'-(6-malyl-glucosyl)-glucoside), and apigenin 6-C-glucosyl-7-O-glucoside-6"'-malyl ester. Among these flavonoids, the apigenin derivative exhibited the strongest co-pigment effect. When two equivalents of the apigenin derivative were added to 1 mM of the main pigment (delphinidin 3,5-diglucoside-6"-O-4,6"'-O-1-cyclic-malyl diester) dissolved in pH 5.0 buffer solution, the lambda(max) shifted to a wavelength 28 nm longer. The vacuolar pH of the Moonshadow flower was estimated to be around 5.5 by measuring the pH of petal. We conclude that the following reasons account for the bluish hue of the transgenic carnation flowers: (1). accumulation of the delphinidin type anthocyanins as a result of flavonoid 3',5'-hydroxylase gene expression, (2). the presence of the flavone derivative strong co-pigment, and (3). an estimated relatively high vacuolar pH of 5.5.     

Triterpenoid saponins from Schefflera arboricola

Nine triterpenoid saponins were isolated from the leaves and stems of Schefflera arboricola. The saponins were characterised, on the basis of chemical and spectral evidence, as 3-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucuronopyranosyl] oleanolic acid, 3-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucuronopyranosyl] echinocystic acid, 3-O-[beta-D-apiofuranosyl-(1-->4)-beta-D-glucuronopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-ramnopyranosyl-(1-->4)-[alpha-L-arabinopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid, 3-O-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-arabinopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl-(1-->4)-[beta-D-galactopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid, 3-O-alpha-L-rhamnopyranosyl-(1-->4)-[beta-D-galactopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-beta-D-apiofuranosyl-(1-->4)-[alpha-L-arabinopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid and 3-O-beta-D-apiofuranosyl-(1-->4)-[alpha-L-arabinopyranosyl-(1-->2)-] beta-D-glucuronopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl ester.     

Acylated flavonol glycosides as probing stimulants of a bean aphid,Megoura crassicauda,from Vicia angustifolia

A bean aphid, Megoura crassicauda, which feeds selectively on the plant genus Vicia (Fabaceae), was found to be stimulated to probe an extract solution of the host plant, narrowleaf vetch, Vicia angustifolia L., depositing characteristic stylet sheaths on a parafilm membrane. Two acylated flavonol glycosides were isolated as the specific probing stimulants from the extracts and characterized as quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-glucopyranoside and quercetin 3-O-alpha-L-arabinopyranosyl-(1-->6)-[2"-O-(E)-p-coumaroyl]-beta-D-galactopyranoside. A mixture of these compounds in the same equivalency strongly induced the probing response from M. crassicauda, suggesting their kairomonal roles during host recognition.     

7-O-Methylated anthocyanidin glycosides from Catharanthus roseus

Anthocyanins were isolated from orange-red flowers of Catharanthus roseus cv 'Equator Deep Apricot', and identified as rosinidin 3-O-[6-O-(alpha-rhamnopyranosyl)-beta-galactopyranoside] (1), and also 7-O-methylcyanidin 3-O-[6-O-(alpha-rhamnopyranosyl)-beta-galactopyranoside] (2) by chemical and spectroscopic methods. Pigment 1 was found to be a major anthocyanin in the flowers of this cultivar. By contrast, the distribution of rosinidin glycosides is very limited in plants, and reported only in the flowers of Primula. Pigment 2 was found in smaller concentrations, but its aglycone, 7-O-methylcyanidin, has been reported only once before, from the fruit of mango.     

Further saponins from Meryta lanceolata

Five new oleanane-type saponins along with 11 known ones were isolated from the leaves and stems of Meryta lanceolata. The new saponins were characterised by spectroscopic analysis including FAMS, 1 and 2D NMR experiments and the results of hydrolysis as 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] hederagenin 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl] ester, 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl]ester, 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-6-O-acetyl glucopyranosyl-(1-->6)-beta-d-glucopyranosyl]ester, 3-O-[beta-d-glucopyranosyl-(1-->3)-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl] ester and 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] hederagenin, respectively.     

Acylated anthocyanins from the violet-blue flowers of Orychophragonus violaceus

Three acylated cyanidin 3-sambubioside-5-glucosides (1-3) were isolated from the violet-blue flowers of Orychophragonus violaceus, and their structures were determined by chemical and spectroscopic methods. Two of those acylated anthocyanins (1 and 3) were cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-acyl)-beta-D-glucopyranoside]-5-O-(6-O-malonyl-beta-D-glucopyranoside)s, in which the acyl groups were p-coumaric acid for 1, and sinapic acid for 3, respectively. The last anthocyanin 2 was cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-feruloyl)-beta-D-glucopyranoside]-5-O-beta-D-glucopyranoside. In these flowers, the anthocyanins 2 and 3 were present as dominant pigments, and 1 was obtained in rather small amounts.     

Glucuronide triterpene saponins from Bersama engleriana

Five 3-O-glucuronide triterpene saponins (1-5) were isolated from the stem bark of Bersama engleriana Gurke along with two known saponins, polyscias saponin C and aralia saponin 15, and one major C-glycoside xanthone, mangiferin. The structures of the saponins were established mainly by means of spectroscopic methods (one- and two-dimensional NMR spectroscopy as well as FAB-, HRESI-mass spectrometry) as 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-betulinic acid (1), 3-O-[beta-D-glucopyranosyl-(1-->2)-[beta-D-galactopyranosyl-(1-->3)]-beta-D-glucuronopyranosyl]-oleanolic acid (2), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-xylopyranosyl-(1-->6)-beta-d-glucopyranosyl]-oleanolic acid (3), 3-O-[beta-D-galactopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl]-oleanolic acid (4), and 3-O-[beta-d-glucopyranosyl-(1-->3)-beta-D-galactopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-d-xylopyranosyl-(1-->6)-beta-D-glucopyranosyl]-oleanolic acid (5).     

Acylated anthocyanins from red radish (Raphanus sativus L.)

Twelve acylated anthocyanins were isolated from the red radish (Raphanus sativus L.) and their structures were determined by spectroscopic analyses. Six of these were identified as pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-beta-D-glucopyranosyl]-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-caffeoyl-2-O-(6-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-p-coumaroyl-2-O-(6-(E)-caffeoyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-(6-(E)-caffeoyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), pelargonidin 3-O-[6-O-(E)-p-coumaroyl-2-O-(6-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside), and pelargonidin 3-O-[6-O-(E)-feruloyl-2-O-(2-(E)-feruloyl-beta-D-glucopyranosyl)-(1-->2)-beta-D-glucopyranoside]-5-O-(beta-D-glucopyranoside).     

Acetylated glucuronide triterpene bidesmosidic saponins from Symplocos glomerata

Nine new bidesmosidic 3-O-glucuronide oleanane triterpenoid saponins were isolated from the stem bark of Symplocos glomerata King along with two known saponins, salsoloside C and copteroside E, and two major lignans, (-)-pinoresinol and (-)-pinoresinol-4'-O-beta-D-glucopyranoside. The structures of the new saponins were established using one- and two-dimensional NMR spectroscopy and mass spectrometry as, 3-O-[beta-D-xylopyranosyl(1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[beta-D-xylopyranosyl(1-->4)-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[beta-D-xylopyranosyl (1-->4)-[2,3-O-diacetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[alpha-L-arabinopyranosyl(1-->4)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[alpha-L-arabinopyranosyl (1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-xylopyranosyl (1-->2)]-[beta-D-xylopyranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-glucopyranosyl (1-->2)]-[beta-D-xylopyranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-glucopyranosyl (1-->2)]-[alpha-L-arabinofuranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, and 3beta-O-[beta-D-xylopyranosyl(1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-morolic acid. The EtOH and EtOAc extracts of the stem bark showed no cytotoxic activity. At a concentration of 370 microg/ml, the saponin mixture showed haemolytic activity and caused 50% haemolysis of a 10% suspension of sheep erythrocytes.