Terpenoids from the seed of chamaecyparis pisifera: the structures of six diterpenoids

Six new diterpenes, 12-hydroxy-20-nor-abieta-1(10),2,8,11,13-pentaene, pisiferanol (10S,12-dihydroxy-9(10 → 20)-abeo-abieta-8,11,13-triene), pisiferadinol (20S-hydroxypisiferanol), 12-deoxypisiferanol, 1β-hydroxyisopisiferin (1R,12-dihydroxy-9(10 → 2O)abeo-abieta-8,10(20),11,13-tetraene), and the dimethylamine salt of O-methylpisiferic acid were isolated from the seed of Chamaecyparis pisifera. The structures of these diterpenes were established by spectral and chemical methods. In addition, 15 mono-, four sesqui- and nine diterpenes were identified.     

Polyphenols isolated from antiradical extracts of Mallotus metcalfianus

Six flavonoids including two new flavones, luteolin 7-O-(4″-O-(E)-coumaroyl)-β-glucopyranoside), chrysoeriol-7-O-(4″-O-(E)-coumaroyl)-β-glucopyranoside) and a mixture of two pairs of diastereoisomeric flavonolignans, (±)-hydnocarpin 7-O-(4″-O-(E)-coumaroyl)-β-glucopyranoside)/(±)-hydnocarpin-D 7-O-(4″-O-(E)-coumaroyl)-β-glucopyranoside) with a 2:1 ratio were isolated from the whole plant of Mallotus metcalfianus Croizat, in addition to 10 known compounds. Their structures were evaluated on the basis of different spectroscopic methods, including extensive 1D and 2D NMR spectroscopy. Some extracts have moderate antimicrobial properties and interesting antiradical (DPPH) activity, as well as some compounds isolated from this species. Tannins were also identified in some active extracts.     

The extracellular polysaccharides of porphyridium cruentum and porphyridium aerugineum

The extracellular mucilages from Porphyridium cruentum and P. aerugineum contain D-xylose, D-glucose, D-and L-galactose, 3-O-methylxylose, 3- and 4-O-methyl-galactose, and D-glucoronic acid in the approximate molar proportions of 3:1:2.5:0.13:0.13:0.8 and 1.7:1:1.1:0.3:0.6:0.5, respectively. In addition, P cruentum mucilage contains 2-O-methylhexose (0.13) and 2-O-methylglucuronic acid (0.2), whereas P. aeruginum mucilage is devoid of these two sugars but contains 2,4-di-O-methylgalactose (0.5). Both polysaccharides contain ～10% of half-ester sulphate and appear to be linked to ～5% of protein. Attempted fractionation into homopolysaccharides was unsuccessful. Methylation, periodate oxidation, and partial hydrolysis studies revealed that the glucuronic acid is 1,3-linked and is attached solely to O–3 of D-galactose in both mucilages. The 2-O-methylglucuronic acid in P. cruentum is linked to O–4 of L-galactose. Xylose, glucose, and galactose are present in both mucilages as end groups, and 1,3- and 1,4-linked residues, with galactose and glucose also present as, 1,3,4-linked or sulphated residues. Molecular weight determinations on Sepharose 4B indicate a $\text{M}$_w of 4 x 10(su6) for P. cruentum mucilage and 5 x 10⁶ for that from P. aerugineum.     

Steroidal saponins of Asparagus curillus

Three spirostanol and two furostanol glycosides were isolated from a methanol extract of the roots of Asparagus curillus and characterized as 3-O-[α-l-arabinopyranosyl (1→4)- β-d-glucopyranosyl]-(25S)-5β-spirostan-3β-ol, 3-O-[{α-l-rhamnopyranosyl (1→2)} {α-l-arabinopyranosyl (1→4)}-β-d-glucopyranosyl]-(25S)-5β-spirostan- 3β-ol, 3-O-[{β-d-glucopyranosyl (1→2)} {α-l-arabinopyranosyl (1→4)}-β- d-glucopyranosyl]-(25S)-5β-spirostan-3β-ol, 3-O-[{β-d-glucopyranosyl (1→2)} {α-l-arabinopyranosyl (1→4)}-β-d-glucopyranosyl]-26-O-[β-d-glucopyranosyl]- 22α-methoxy-(25S)-5β-furostan-3β, 26-diol and 3-O-[{β-d-glucopyranosyl (1→2)} {α-l-arabinopyranosyl (1→4)}-β-d-glucopyranosyl]-26-O-[β-d-glucopyranosyl]- (25S)-5β-furostan-3β, 22α, 26-triol respectively.     

Steroidal saponins of Asparagus adscendens

From the methanol extract of the fruits of Asparagus adscendens sitosterol-β-d-glucoside, two spirostanol glycosides (asparanin A and B) and two furostanol glycosides (asparoside A and B) were isolated and characterized as 3-O-[β-d-glucopyranosyl (1→2)-β-d-glucopyranosyl]-(25S)-5β-spirostan-3β-ol, 3-O-{[β-d-glucopyranosyl(1→2)][α-l-rhamnopyranosyl(1→4)]-β-d-glucopyranosyl}-(25S)-5β-spirostan-3β-ol,3-O-{[β-d-glucopyranosyl(1→2)][α-l-rhamnopyranosyl(1→4)]-β-d-glucopyranosyl|} -26-O-(β- d-glucopyranosyl)-22α-methoxy-(25S)-5β-furostan-3β,26-diol and 3-O-{[β-d-glucopyranosyl(1→2)][α-l-rhamnopyranosyl(1→4)]-β-d-glucopyranosyl}-26-O-(β-d-glucopyranosyl)- 25S)-5β-furostan-3β,22α, 26-triol, respectively.     

Metabolomics-oriented isolation and structure elucidation of 37 compounds including two anthocyanins from Arabidopsis thaliana

In order to conduct metabolomic studies in a model plant for genome research, such as Arabidopsis thaliana (Arabidopsis), it is a prerequisite to obtain structural information for the isolated metabolites from the plant of interest. In this study, we isolated metabolites of Arabidopsis in a relatively non-targeted way, aiming at the construction of metabolite standards and chemotaxonomic comparison. Anthocyanins (5 and 7) called A8 and A10 were isolated and their structures were elucidated as cyanidin 3-O-[2-O-(β-d-xylopyranosyl)-6-O-(4-O-(β-d-glucopyranosyl)-E-p-coumaroyl)-β-d-glucopyranoside]-5-O-[6-O-(malonyl)-β-d-glucopyranoside] and cyanidin 3-O-[2-O-(2-O-(E-sinapoyl)-β-d-xylopyranosyl)-6-O-(4-O-(β-d-glucopyranosyl)-E-p-coumaroyl)-β-d-glucopyranoside]-5-O-[β-d-glucopyranoside] from analyses of 1D NMR, 2D NMR (¹H NMR, NOE, ¹³C NMR, HMBC and HMQC), HRFABMS, FT-ESI-MS and GC-TOF-MS data. In addition, 35 known compounds, including six anthocyanins, eight flavonols, one nucleoside, one indole glucosinolate, four phenylpropanoids and a derivative, together with three indoles, one carotenoid, one apocarotenoid, three galactolipids, two chlorophyll derivatives, one steroid, one hydrocarbon, and two dicarboxylic acids, were also isolated and identified from their spectroscopic data.     

Dihydrofurocoumarin glucosides from Angelica archangelica and Angelica silvestris

A water-soluble root extract of Angelica archangelica subsp. litoralis afforded, in addition to adenosine, coniferin and the two known dihydrofurocoumarin glycosides, apterin and 1′-O-β-d-glycopyranosyl-(S)-marmesin (marmesinin), two new dihydrofuranocoumarin glycosides, 1′-O-β-d-glucopyranosyl-(2S, 3R)-3-hydroxymarmesin, and 2′-β-d-glucopyranosyloxymarmesin. For the latter a 2S-configuration was demonstrated, the stereochemistry at position 1′ remaining undefined. Roots of A. silvestris similarly afforded 1′-O-β-d-glucopyranosyl-(2S, 3R)-3-hydroxymarmesin. By correlation with the aglycone 2S,3R)-3-hydroxymarmesin obtained in this work, the absolute configurations (2S,3R) were established for the known dihydrofurocoumarin diesters smirniorin and smirnioridin.     

Furostanol glycosides from Trigonella foenum-graecum seeds

Two new furostanol glycosides trigofoenosides A and D have been isolated from the Trigonella foenum-graecum seeds as their methyl ethers, A-1 and D-1. Their structures have been determined as (25S)-22-O-methyl-furost-5-ene-3β,26-diol, 3-O-α-L-rhamnopyranosyl (1 → 2)-β-D-glucopyranoside; 26-O-β-D-glucopyranoside (A-1) and (25S)-22-O-methyl-furost-5-ene-3β,26-diol, 3-O-α-L-rhamnopyranosyl (1 → 2)-[β-D-glucopyranosyl (1 → 3)]-β-D-glucopyranoside; 26-O-β-D-glucopyranoside (D-1).     

The structure of bael (Aegle marmelos) gum

Purified, bael-gum polysaccharide containsd-galactose (71%),l-arabinose (12.5%),l-rhamnose (6.5%), andd-galacturonic acid (7%). Hydrolysis of one mole of the fully methylated polysaccharide gave: (a) from the neutral part, 2,3,4-tri-O-methyl-l-rhamnose (2 moles), 2,3,5-tri-O-methyl-l-arabinose (4 moles), 2,3,4,6-tetra-O-methyl-d-galactose (8 moles), 3,4-di-O-methyl-l-rhamnose (2 moles), 2,5-di-O-methyl-l-arabinose (1 mole), 2,4,6-tri-O-methyl-d-galactose (10 moles), 2,3-di-O-methyl-l-arabinose (1 mole), 2,4-di-O-methyl-d-galactose (14 moles), and 2-O-methyl-d-galactose (2 moles); and (b) from the acidic part, 2,3,4-tri-O-methyl-d-galacturonic acid (1 mole), 2,4,6-tri-O-methyl-3-O-(2,3,4-tri-O-methyl-d-galactopyranosyluronic acid)-d-galactose (2.6 moles), and 2,4,6-tri-O-methyl-3-O-[2,4,6-tri-O-methyl-3-O-(2,3,4-tri-O-methyl-d-galactopyranosyluronic acid)-d-galactopyranosyl]-d-galactose (1 mole). Mild hydrolysis of the whole gum yielded oligosaccharides from which 3-O-β-d-galactopyranosyl-l-arabinose, 5-O-β-d-galactopyranosyl-l-arabinose, 3-O-β-d-galactopyranosyl-d-galactose, and 6-O-β-d-galactopyranosyl-d-galactose could be isolated and characterized. The results of methylation, periodate oxidation, Smith degradation, Barry degradation, and graded hydrolysis studies were employed for the elucidation of the structure of the whole gum.     

Iridoids from Gentiana loureirii

Iridoid glycosides, 2′,3′,6′-tri-O-acetyl-4′-O-trans-p-(O-β-d-glucopyranosyl)coumaroyl-7-ketologanin (1), 2′-O-caffeoylloganic acid (2), 2′-O-p-hydroxybenzoylloganic acid (3), 2′-O-trans-p-coumaroylloganic acid (4), and 2′-O-cis-p-coumaroylloganic acid (5), were isolated from whole plants of Gentiana loureirii along with six known iridoids, 7-ketologanin (6), loganin (7), loganic acid (8), sweroside, boonein, and isoboonein, and three other known compounds. Their structures were elucidated by spectroscopic means and chemical correlations. The isolated iridoids were evaluated for antibacterial and antioxidant activities, but were either inactive or very weakly active.     

Rhamnazin- und rhamnetin-3-O-trioside aus Rhamnus petiolaris

From the fruits of Rhamnus petiolaris two new flavonol-3-O-triosides were isolated and identified as rhamnazin-3-O-[α-l-rhamnopyranosyl (1 → 4)-α-l-rhamnopyranosyl (1 → 6)]-β-d-galactopyranoside and rhamnetin-3-O-α-l-rhamnopyranosyl (1 → 2)-α-l-rhamnopyranosyl (1 → 6)]-β-d-galactopyranoside, respectively.     

Sesquiterpene lactones from Smyrnium cordifolium

In addition to previously obtained furanosesquiterpenes, two new eudesmanolides and a new glechomanolide were isolated from the fruits of Smyrnium cordifolium, while the roots gave two new eudesmanolides. The new compounds from the fruits were 1β-acetoxy-eudesman-4(15), 7(11)-dien-8,12-olide, 1β-acetoxy-8β-hydroxy-eudesman-4(15),7(11)-dien-8,12-olide, 1β,10α;4α,5β-diepoxy-8-hydroxy-glechomanolide, those obtained from the roots were smyrnicordiolide and the corresponding 8β-hydroxy derivative belonging to a new type of oxepine derivative.     

Structures of 3,28-O-bisglycosidic triterpenoid saponins of Fatsia japonica

Four novel 3,28-O-bisglycosidic triterpenoid saponins were isolated from the mature fruits of F. japonica. They were characterized as the 28-O-α-l-rhamnopyranosyl-(1 → 4)-β-d-glucopyranosyl-(1 → 4)-β- d-glucopyranosides of 3-O-α-l-arabinopyranosyl echinocystic acid, 3-O-α-l-arabinopyranosyl hederagenin, 3-O-β-d-glucopyranosyl-(1 → 2)-α-l-arabinopyranosyl oleanolic acid and 3-O-β- d-glucopyranosyl-(1 → 2)-α-l-arabinopyranosyl hederagenin respectively.     

Steroidal saponins from the leaves of Beaucarnea recurvata

Thirteen steroidal saponins were isolated from the leaves of Beaucarnea recurvata Lem. Their structures were established using one- and two-dimensional NMR spectroscopy and mass spectrometry. Six of them were identified as: 26-O-β-d-glucopyranosyl (25S)-furosta-5,20(22)-diene 1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5,20(22)-diene 1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2)-4-O-acetyl-β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25R)-furosta-5,20(22)-diene-23-one-1β,3β,26-triol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5-ene-1β,3β,22α,26-tetrol 1-O-α-l-rhamnopyranosyl-(1 → 4)-6-O-acetyl-β-d-glucopyranoside, 26-O-β-d-glucopyranosyl (25S)-furosta-5-ene-1β,3β,22α,26-tetrol 1-O-α-l-rhamnopyranosyl-(1 → 2) β-d-fucopyranoside, and 24-O-β-d-glucopyranosyl (25R)-spirost-5-ene-1β,3β,24-triol 1-O-α-l-rhamnopyranosyl-(1 → 2)-4-O-acetyl-β-d-fucopyranoside. The chemotaxonomic classification of B. recurvata in the family Ruscaceae was discussed.     

Co-pigmentation and flavonoid glycosyltransferases in blue Veronica persica flowers

Glycosylation is one of the key modification steps for plants to produce a broad spectrum of flavonoids with various structures and colors. A survey of flavonoids in the blue flowers of Veronica persica Poiret (Lamiales, Scrophulariaceae), which is native of Eurasia and now widespread worldwide, led to the identification of highly glycosylated flavonoids, namely delphinidin 3-O-(2-O-(6-O-p-coumaroyl-glucosyl)-6-O-p-coumaroyl-glucoside)-5-O-glucoside (1) and apigenin 7-O-(2-O-glucuronosyl)-glucuronide (2), as two of its main flavonoids. Interestingly, the latter flavone glucuronide (2) caused a bathochromic shift on the anthocyanin (1) toward a blue hue in a dose-dependent manner, showing an intermolecular co-pigment effect. In order to understand the molecular basis for the biosynthesis of this glucuronide, we isolated a cDNA encoding a UDP-dependent glycosyltransferase (UGT88D8), based on the structural similarity to flavonoid 7-O-glucuronosyltransferases (F7GAT) from Lamiales plants. Enzyme assays showed that the recombinant UGT88D8 protein catalyzes the 7-O-glucuronosylation of apigenin and its related flavonoids with preference to UDP-glucuronic acid as a sugar donor. Furthermore, we identified and functionally characterized a cDNA encoding another UGT, UGT94F1, as the anthocyanin 3-O-glucoside-2″-O-glucosyltransferase (A3Glc2″GlcT), according to the structural similarity to sugar-sugar glycosyltransferases classified to the cluster IV of flavonoid UGTs. Preferential expression of UGT88D8 and UGT94F1 genes in the petals supports the idea that these UGTs play an important role in the biosynthesis of key flavonoids responsible for the development of the blue color of V. persica flowers.     

Three flavonoid glycosides containing acetylated allose from stachys recta

By means of ¹³C and ¹H NMR spectroscopy three flavone glycosides, obtained from Stachys recta, were identified as 7-O-(2″-O-6″′-O-acetyl-β-D-allopyranosyl-β-D-glucopyranosides) of 4′-O-methylisoscutellarein, isoscutellarein and 3′-hydroxy-4′-O-methylisoscutellarein. The latter two compounds are isolated for the first time. Only mannose and glucose have been reported previously as sugar components of flavonoids of the genus Stachys.     

Obtusilobinin and obtusilobin,two new triterpene saponins from Anemone obtusiloba

Obtusilobinin and obtusilobin, two new saponins, have been isolated from the ethanolic extract of Anemone obtusiloba (Ranunculaceae). The structural elucidation of obtusilobinin and obtusilobin have showed them to be olean-12-ene-28-oic-3-O-(α-l-arabinofuranosyl 1→2) (α-l-rhamnopyranosyl 1→4)-β-d-glucopyranoside and olean-12-ene-28-oic-3-O-α-l-rhamnopyranosyl 2→1-O-α-l-arabinofuranoside, respectively.     

Identification of N, O-diacetyl-, N-acetyl- and N-glycolylneuraminyl-(2 → 3)-lactose in rat urine

The structure of three neuraminyl-oligosaccharides isolated from rat urine-have been studied by chromatographic and mass spectrometric analyses of different hydrolysis and methylation products. The structures of the oligosaccharides were identifies as O-α-N-acetyl(O-acetyl)neuraminyl-(2 → 3)-O-β-galactopyranosyl-(1 → 4)-glucopyranose, O-α-N-acetylneuraminyl-(2 → 3)-O-β-galactopyranosyl-(1 → 4)-glucopyranose and O-α-N-glycolylneuraminyl-(2 → 3)-O-β-galactopyranosyl-(1 → 4)-glucopyranose.     

Triterpenoid saponins from Fatsia japonica

Five triterpenoid saponins isolated from the flowers, the mature fruits and the leaves of Fatsia japonica were identified as 3-O-[β-d-glucopyranosyl(1→4)-β-d-glucopyranosyl]-hederagenin (1), 3-O-[β-d-glucopyranosyl-(1→4)-α-l-arabinopyranosyl]-oleanolic acid (2), 3-O-[α-l-arabinopyranosyl]-hederagenin (3), 3-O-[β-d-glucopyranosyl]-hederagenin (4) and 3-O-[β-d-glucopyranosyl(1→4)-α-l-arabinopyranosyl]-hederagenin (5). The saponins 1 and 2 are new, naturally occurring, triterpenoid saponins. The distribution of the five saponins in three parts of the plant was investigated. Saponins 2, 3 and 5 were present in the flowers, saponins 1, 3, 4 and 5 were in the mature fruits and saponins 2, 3, 4 and 5 were in the leaves.     

Enzymatically derived aldouronic acids from Cryptomeria japonica arabinoglucuronoxylan

An arabinoglucuronoxylan was extracted from the holocellulose of sugi (Cryptomeria japonica) wood with 10% KOH and subjected to hydrolysis by partially purified xylanase fraction from a commercial cellulase preparation “Meicelase”. Neutral sugars liberated were analyzed by size exclusion chromatography showing the presence of xylooligosaccharides up to xylohexaose. Aldouronic acids liberated were purified by preparative anion exchange chromatography. Their structures were identified by monosaccharide analysis, comparison of their volume distribution coefficients (Dvs) with those of the authentic samples in anion exchange chromatography and ¹H and ¹³C NMR spectroscopy, resulting in the characterization of eight aldouronic acids including acids consisting of two 4-O-Me-α-D-GlcAp residues and 3-5 D-Xyl residues.

1.

Fr. 1-S1: (aldohexaouronic acid, MeGlcA³Xyl₅), O-β-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)-(1 → 2)]-O-β-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

2.

Fr. 1-S2: (aldopentaouronic acid, MeGlcA³Xyl₄), O-β-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)-(1 → 2)]-O-β-D-Xylp-(1 → 4)-O-β-Xylp-(1 → 4)-D-Xyl

3.

Fr. 2-S1: (aldotetraouronic acid, MeGlcA³Xyl₃), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

4.

Fr. 3-S1: (aldotetraouronic acid, GlcA³Xyl₃), O-(α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-Xylp-(1 → 4)-D-Xyl,

5.

Fr. 4-S1: (aldotriouronic acid, GlcA²Xyl₂), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-D-Xyl

6.

Fr. 4-S2: (MeGlc⁴MeGlcA³Xyl₅), O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

7.

Fr. 6-S1: (MeGlcA⁴MeGlcA³Xyl₄), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-[(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

8.

Fr. 7-S1: (MeGlcA³MeGlc²Xyl₃), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-[(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-D-Xyl

Fr. 4-S2 was a new acidic oligosaccharide. The distribution pattern of these vicinal uronic acid units along the D-xylan chain was discussed.