Antioxidative caffeoylquinic acids and flavonoids from Hemerocallis fulva flowers

Tumor necrosis factor-α (TNF-α)-induced reactive oxygen species (ROS) production in HepG2 was used to screen hepatocyte protective compounds from the flowers of Hemerocallis fulva. Three new polyphenols, n-butyl 4-trans-O-caffeoylquinate (1), kaempferol 3-O-{α-L-rhamnopyranosyl(1→6)[α-L-rhamnopyranosyl(1→2)]}-β-D-galactopyranoside (2), and chrysoeriol 7-O-[β-D-glucuronopyranosyl(1→2)(2-O-trans-feruloyl)-β-D-glucuronopyranoside (3), together with four caffeoylquinic acid derivatives (4-7), eight known flavones (8-15), one naphthalene glycoside, stelladerol (16), one tryptophan derivative (17), adenosine (18), and guanosine (19) were isolated from the bioactive fractions of the aqueous ethanol extract of H. fulva flowers. The structures of isolated compounds were characterized by means of spectroscopic data. Compounds 1-3 were described as first isolated natural products. Among the above-mentioned compounds, the caffeoylquinic acid derivatives are the major components with potent free radical scavenging activity in HepG2 cells and are for the first time isolated from H. fulva flowers. A convenient ultraperformance liquid chromatography (UPLC) method was also developed to simultaneously separate and identify caffeoylquinic acids and flavonoids promptly.     

Identification of antioxidative flavonols and anthocyanins in Sicana odorifera fruit peel

Ten flavonols and three anthocyanins were identified in the fruit peel of melo?n de olor (Sicana odorifera), and their structures were established by spectrometric and spectroscopic (ESI-MS and NMR) techniques. One of the identified flavonols, quercetin 3-O-(6'-O-malonyl)-β-D-glucopyranoside 4'-O-β-D-glucopyranoside, has not been reported before in the plant kingdom. Although quercetin-3-O-α-L-rhamnopyranosyl-(1→6)-β-d-glucopyranoside-4'-O-β-D-glucopyranoside had been reported before in literature and structure elucidation was done by comparison of NMR data with published data, to the best of our knowledge complete 1D and 2D NMR data have not been not delineated so far. Moreover, the antioxidant activity of pure compounds was measured by ABTS assay. It was established that quercetin 3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside, quercetin-3-O-(6'-malonyl)-glucopyranoside, quercetin-3-O-β-D-glucopyranoside, and quercetin-3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside-4'-O-β-D-glucopyranoside contribute significantly to the antioxidant activity exhibited by the fruit peel methanolic extract.     

Identification of cyanidin 3-O-β-(6″-(3-hydroxy-3-methylglutaroyl)glucoside) and other anthocyanins from wild and cultivated blackberries

Anthocyanins from blackberries are natural dietary pigments. The aim of this study was to investigate the occurrence of anthocyanins in fruits of wild Norwegian blackberries and three blackberry ( Rubus fruticosus L.) cultivars and to report the complete identification of cyanidin 3-O-β-(6″-(3-hydroxy-3-methylglutaroyl)glucopyranoside), 5. This new pigment is most probably the same pigment that has previously been reported to occur in various blackberry samples as cyanidin 3-dioxalylglucoside. All of the examined blackberry samples contained in similar relative proportions the 3-glucoside (1), 3-rutinoside (2), 3-xyloside (3), and 3-O-β-(6″-malonylglucoside) (4) of cyanidin and 5. The absolute amounts of 1-5 in the wild Norwegian blackberries were 249, 18, 10, 24, and 22 mg of cyanidin 3-glucoside equivalents/100 g of fresh weight, respectively.     

Isolation and identification of flavonoids accumulated in proanthocyanidin-free barley

Flavonoids accumulated in proanthocyanidin-free near-isogenic lines iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi, developed by backcross breeding using a leading cultivar, Nishinohoshi, as a recurrent parent and a proanthocyanidin-free mutant as a nonrecurrent parent in Japan, were examined. A new flavanone, (2RS)-dihydrotricin 7-O-β-D-glucopyranoside (1), known flavanones (2RS)-dihydrotricin (2) and (2RS)-homoeriodictyol (3), and known flavones chrysoeriol 7-O-[α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside] (4), chrysoeriol 7-O-β-D-glucopyranoside (5), tricin (6), and chrysoeriol (7) were isolated from iso ant 17 of Nishinohoshi. The structures and stereochemistries of the isolated flavonoids (1-7) were elucidated on the basis of spectroscopic analyses. The concentrations of the isolated flavonoids (1-7) in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi were similar to each other, whereas the flavonoids 1-5 and 7 were not detected in Nishinohoshi, an old Japanese cultivar, Amaginijo, and North American cultivar Harrington. The concentration of tricin (6) in Nishinohoshi was a half those in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi. Except for iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi, the concentration of tricin (6) was highest in Nishinohoshi, followed by Amaginijo and Harrington. Thus, tricin (6), its precursor dihydrotricin (2), and its glucopyranoside, dihydrotricin 7-O-β-D-glucopyranoside (1), as well as chrysoeriol (7) and homoeriodictyol (3) were accumulated in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi probably by blocking at the step of flavanone 3-hydroxylase in the procyanidin biogenetic pathway, resulting in enhancement of the alternative biogenetic pathway.     

Triterpene saponins from the roots of Medicago hybrida

Fourteen triterpene saponins (1-14) have been isolated from the roots of Medicago hybrida and their structures elucidated by FAB-MS and NMR analysis. Two of them are new compounds and were identified as hederagenin 3-O-[alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranosyl]-28-O-beta-D-glucopyranoside (7) and oleanolic acid 3-O-[beta-D-galactopyranosyl(1-->2)-beta-D-glucuronopyranosyl]-28-O-[alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranoside] (14). Seven saponins being mono- and bidesmosides of hederagenin (1, 5, 6, 9), one bidesmoside of bayogenin (2), and two bidesmosides of 2beta,3beta-dihydroxyolean-12-en-23-al-28-oic acid (11) and oleanolic acid (13) are known compounds but not previously reported as saponin constituents of Medicago, whereas five other saponins, being mono- and bidesmosides of medicagenic acid (3, 4, 8, 10, 12), and one monodesmoside of hederagenin (8) have been previously isolated from other Medicago species. The presence of 2beta,3beta-dihydroxyolean-12-en-23-al-28-oic acid might represent an interesting intermediate in the biosynthesis of these substances.     

Structures of new triterpenoids and cytotoxicity activities of the isolated major compounds from the fruit of Momordica charantia L

Two new cucurbitane-type triterpene glycosides, charantagenins D (1) and E (2), and one new sterol, 7-oxo-stigmasta-5,25-diene-3-O-β-d-glucopyranoside (3), were isolated from the fruit of Momordica charantia L. together with another eight known compounds. Their structures were determined on the basis of spectral analysis. Cytotoxicity activities of the isolated major compounds were evaluated against lung cancer cell line A549, glioblastoma cell line U87, and hepatoma carcinoma cell line Hep3B by using a 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) in vitro assay. Results showed compounds 1 and 7 (goyaglycoside d) with an -OMe substituent group in the side chain exhibited significant cytotoxic activities against cancer cells. Impressively, the IC(50) values of the new compound 1 to A549, U87, and Hep3B were 1.07, 1.08, and 14.01 μmol/L, respectively, which were much lower than those of other tested compounds.     

Triterpene saponins from aerial parts of Medicago arabica L

Eight major triterpene saponins have been isolated from the aerial parts of Medicago arabica and their structures elucidated by FAB-MS and NMR analysis. Three of them are new compounds and are identified as 3-O-(alpha-L-arabinopyranoside) bayogenin, 3-O-(alpha-L-arabinopyranosyl), 28-O-(beta-D-glucopyranoside) bayogenin, and 3-O-[alpha-L-arabinopyranosyl(1-->2)-beta-D-glucuronopyranosyl], 28-O-beta-D-glucopyranoside 2-beta-hydroxyoleanolic acid. Two saponins, identified as 3-O-(alpha-L-arabinopyranoside) hederagenin and 3-O-(alpha-L-arabinopyranosyl), 28-O-(beta-D-glucopyranoside) hederagenin are known compounds but not previously reported as saponin constituents of Medicago species, while three other saponins, being mono- and bidesmosides of hederagenin, have been previously isolated from roots of M. sativa.     

Isolation and identification of sea buckthorn (Hippophae rhamnoides) phenolics with antioxidant activity and α-glucosidase inhibitory effect

This study was performed to evaluate the antioxidant and α-glucosidase inhibitory effects from the extract, fractions, and isolated compounds of sea buckthorn leaves. Six compounds, kaempferol-3-O-β-D-(6'-O-coumaryl) glycoside, 1-feruloyl-β-D-glucopyranoside, isorhamnetin-3-O-glucoside, quercetin 3-O-β-D-glucopyranoside, quercetin 3-O-β-D-glucopyranosyl-7-O-α-L-rhamnopyranoside, and isorhamnetin-3-O-rutinoside, were isolated from sea buckthorn leaf extracts. The butanol fraction (EC(50) = 1.81 μg/mL) along with quercetin 3-O-β-D-glucopyranoside (EC(50) = 1.86 μg/mL) had a higher DPPH radical-scavenging activity and showed stronger reducing power (OD(700) = 1.83 and 1.78, respectively). The butanol fraction (477 mg GAE/g) contained the highest amount of phenolic compounds and also the most powerful α-glucosidase inhibitory effect (86%) at 5 μg/mL. The results indicate that sea buckthorn leaf extracts could potentially be used for food additives and the development of useful natural compounds.     

Alfalfa (Medicago sativa L.) flavonoids. 2. Tricin and chrysoeriol glycosides from aerial parts.

Ten flavone glycosides have been isolated and identified in aerial parts of alfalfa. These included six tricin, one 3'-O-methyltricetin, and three chrysoeriol glycosides. Most of these compounds were acylated with ferulic, coumaric, or sinapic acids, and acylation occurred on the terminal glucuronic acid. Eight of these compounds, including 7-O-beta-D-glucuronopyranosyl-3'-O-methyltricetin, 7-O-beta-D-glucuronopyranosyl-4'-O-beta-D-glucuronopyranosidechrysoeriol, 7-O-[2'-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]chrysoeriol, 7-O-[2'-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]chrysoeriol, 7-O-[2'-O-sinapoyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, 7-O-[2'-O- feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, 7-O-[2'-O-p-coumaroyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, and 7-O-[2'-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, have not been reported previously in the plant kingdom. Two previously identified alfalfa flavones, 7-O-beta-D-glucuronopyranosidetricin and 7-O-[beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside]tricin, were also isolated.     

Hydroxycinnamoylmalic acids and their methyl esters from pear (Pyrus pyrifolia Nakai) fruit peel

Two novel caffeoylmalic acid methyl esters, 2-O-(trans-caffeoyl)malic acid 1-methyl ester (6) and 2-O-(trans-caffeoyl)malic acid 4-methyl ester (7), were isolated from pear (Pyrus pyrifolia Nakai cv. Chuhwangbae) fruit peels. In addition, 5 known hydroxycinnamoylmalic acids and their methyl esters were identified: 2-O-(trans-coumaroyl)malic acid (1), 2-O-(cis-coumaroyl)malic acid (2), 2-O-(cis-coumaroyl)malic acid 1-methyl ester (3), 2-O-(trans-coumaroyl)malic acid 1-methyl ester (4), and 2-O-(trans-caffeoyl)malic acid (phaselic acid, 5). The chemical structures of these compounds were determined by spectroscopic data from ESI MS and NMR. Of all the isolated compounds, five hydroxycinnamoylmalic acids and their methyl esters (2-4, 6, 7) were identified in the pear for the first time.     

Anthocyanins from new red leaf tea 'Sunrouge'

New red leaf tea cultivar 'Sunrouge' (Camellia taliensis × Camellia sinensis), for which an application for registration was made in 2009, is an anthocyanin-rich tea. The anthocyanin content of 'Sunrouge' was the highest among 4 tea cultivars, and was 8.4 times higher than that of 'Yabukita'. We purified and isolated 6 anthocyanins from 'Sunrouge' by chromatography, and identified them by LC/MS/MS and NMR analysis. As a result, the four anthocyanins were identified as delphinidin-3-O-β-D-(6-(E)-p-coumaroyl)galactopyranoside (2), delphinidin-3-O-β-D-(6-(E)-p-coumaroyl)glucopyranoside (3), cyanidin-3-O-β-D-(6-(E)-p-coumaroyl)galactopyranoside (4), and cyanidin-3-O-β-D-(6-(E)-p-coumaroyl)glucopyranoside (5), and the other two were estimated as delphinidin-(Z)-p-coumaroylgalactopyranoside (1), petunidin-(E)-p-coumaroylgalactopyranoside (6). Compound 3 was found in tea for the first time. In general, anthocyanins have various bioactivities, including relieving eyestrain and antioxidative effects, so it is expected that drinking 'Sunrouge' tea brings in similar bioactivities.     

Isolation and identification of compounds responsible for antioxidant capacity of Euryale ferox seeds

Euryale ferox seed is consumed medicinally or for food in China. The present study revealed it to contain significant antioxidant activity, which may be associated with its medical applications as a proteinuria inhibitor of diabetic nephropathy. This study resulted in the identification of 3 new sesquineolignans, named euryalins A-C (1-3), and 16 known compounds, which were all first isolated from this plant apart from 5,7,4-trihydroxy-flavanone. The antioxidant potential of the partial isolates was evaluated using the DPPH radical scavenging assay and mesangial cellular assay. Compounds 2, rel-(2α,3β)-7-O-methylcedrusin (4), syringylglycerol-8-O-4-(sinapyl alcohol) ether (5), and (+)-syringaresinol (7) were found to be most active on DPPH assay, whereas compounds 2, 4, 7, (1R,2R,5R,6S)-2-(3,4-dimethoxyphenyl)-6-(3,4-dihydroxyphenyl)-3,7-dioxabicyclo[3.3.0]octane, and buddlenol E could significantly inhibit high glucose-stimulated reactive oxygen species production in mesangial cells. The results suggested that E. ferox seed could be considered as an excellent source of natural antioxidants and is useful in the prevention of diabetic nephropathy.     

Alfalfa (Medicago sativa L.) flavonoids. 1. Apigenin and luteolin glycosides from aerial parts

Nine flavones and adenosine have been identified in aerial parts of alfalfa, and their structures were established by spectral (FABMS and NMR) techniques. Five of the identified compounds, including apigenin 7-O-[beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], apigenin 7-O-[2-O-p-coumaroyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], and luteolin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, have not been reported before in the plant kingdom. Additionally, five known compounds, including apigenin 7-O-beta-D-glucuronopyranoside, apigenin 4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[beta-D- glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], luteolin 7-O-beta-D-glucuronopyranoside, and adenosine, were identified.     

Potent in vivo antifungal activity against powdery mildews of pregnane glycosides from the roots of Cynanchum wilfordii

Two new pregnane glycosides, kidjoranine 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 4)-α-L-cymaropyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1→4)-α-L-diginopyranosyl-(1 → 4)-β-D-cymaropyranoside (5) and caudatin 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 4)-α-L-cymaropyranosyl-(1 → 4)-β-D-cymaropyranosyl-(1 → 4)-α-L-diginopyranosyl-(1 → 4)-β-D-cymaropyranoside (6), were isolated from the roots of Cynanchum wilfordii along with four known compounds (1-4). The antifungal activities of the six compounds against barley powdery mildew caused by Blumeria graminis f. sp. hordei were compared to the antifungal activity of polyoxin B. The caudatin glycosides (1, 4, and 6) showed stronger antifungal activities than polyoxin B, whereas kidjoranine glycosides (2, 3, and 5) had weaker activities than polyoxin B. A wettable powder-type formulation (C. wilfordii-WP20) of the ethyl acetate extract from C. wilfordii roots prohibited the development of barley powdery mildew much more effectively than the commercial fungicide polyoxin B-WP10. In addition, C. wilfordii-WP20 effectively controlled strawberry powdery mildew caused by Sphaerotheca humuli under greenhouse conditions. Thus, the crude extract containing the pregnane glycosides can be used as a botanical fungicide for the environmentally benign control of powdery mildews.     

Polymorphism for novel tetraglycosylated flavonols in an Eco-model crucifer, Barbarea vulgaris

Nineteen apparent flavonoids were determined by HPLC-DAD in foliage of a chemotype (G-type) of Barbarea vulgaris , and four were isolated. Two were novel tetraglycosylated flavonols with identical glycosylation patterns, kaempferol 3-O-(2,6-di-O-β-d-glucopyranosyl)-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (1) and quercetin 3-O-(2,6-di-O-β-d-glucopyranosyl)-β-d-glucopyranoside-7-O-α-l-rhamnopyranoside (2). The identification of d/l configuration was tentatively based on susceptibility to α-l-rhamnosidase and β-d-glucosidases. A characteristic feature of 1 and 2 was appreciable water solubility, an expected consequence of the extensive glycosylation. A less complex pair of flavonols comprised 3-O-β-d-glucopyranoside-7-O-α-l-rhamnopyranosides of kaempferol and quercetin. Two natural chemotypes of B. vulgaris differed in levels of 1 and 2, with the P-type deficient in 1 and 2 and the insect-resistant G-type rich in 1 (ca. 3-4 μmol/g dry wt) and with moderate levels of 2 (ca. 0.3-0.8 μmol/g dry wt). However, there was only modest seasonal variation in flavonols 1 and 2, in contrast to a strong seasonal variation in insect resistance.     

Maple syrup phytochemicals include lignans, coumarins, a stilbene, and other previously unreported antioxidant phenolic compounds

Twenty-three phenolic compounds were isolated from a butanol extract of Canadian maple syrup (MS-BuOH) using chromatographic methods. The compounds were identified from their nuclear magnetic resonance and mass spectral data as 7 lignans [lyoniresinol (1), secoisolariciresinol (2), dehydroconiferyl alcohol (3), 5'-methoxy-dehydroconiferyl alcohol (4), erythro-guaiacylglycerol-β-O-4'-coniferyl alcohol (5), erythro-guaiacylglycerol-β-O-4'-dihydroconiferyl alcohol (6), and [3-[4-[(6-deoxy-α-l-mannopyranosyl)oxy]-3-methoxyphenyl]methyl]-5-(3,4-dimethoxyphenyl)dihydro-3-hydroxy-4-(hydroxymethyl)-2(3H)-furanone (7)], 2 coumarins [scopoletin (8) and fraxetin (9)], a stilbene [(E)-3,3'-dimethoxy-4,4'-dihydroxystilbene (10)], and 13 phenolic derivatives [2-hydroxy-3',4'-dihydroxyacetophenone (11), 1-(2,3,4-trihydroxy-5-methylphenyl)ethanone (12), 2,4,5-trihydroxyacetophenone (13), catechaldehyde (14), vanillin (15), syringaldehyde (16), gallic acid (17), trimethyl gallic acid methyl ester (18), syringic acid (19), syringenin (20), (E)-coniferol (21), C-veratroylglycol (22), and catechol (23)]. The antioxidant activities of MS-BuOH (IC50>1000 μg/mL), pure compounds, vitamin C (IC50=58 μM), and a synthetic commercial antioxidant, butylated hydroxytoluene (IC50=2651 μM), were evaluated in the diphenylpicrylhydrazyl (DPPH) radical scavenging assay. Among the isolates, the phenolic derivatives and coumarins showed superior antioxidant activity (IC50<100 μM) compared to the lignans and stilbene (IC50>100 μM). Also, this is the first report of 16 of these 23 phenolics, that is, compounds 1, 2, 4-14, 18, 20, and 22, in maple syrup.     

Isolation and structural elucidation of some glycosides from the rhizomes of smaller galanga (Alpinia officinarum Hance)

Glycosidically bound compounds were isolated from the methanol extract of fresh rhizomes of smaller galanga (Alpinia officinarum Hance). Nine glycosides (1-9) were finally obtained by reversed-phase HPLC and their structures were elucidated by MS and NMR analyses. They were the three known glycosides, (1R,3S,4S)-trans-3-hydroxy-1,8-cineole beta-D-glucopyranoside (1), benzyl beta-D-glucopyranoside (3), and 1-O-beta-D-glucopyranosyl-4-allylbenzene (chavicol beta-D-glucopyranoside, 4); and the six novel glycosides, 3-methyl-but-2-en-1-yl beta-D-glucopyranoside (2), 1-hydroxy-2-O-beta-D-glucopyranosyl-4-allylbenzene (5), 1-O-beta-D-glucopyranosyl-2-hydroxy-4-allylbenzene (demethyleugenol beta-D-glucopyranoside, 6), 1-O-(6-O-alpha-L-rhamnopyranosyl-beta-D-glucopyranosyl)-2-hydroxy-4-allylbenzene (demethyleugenol beta-rutinoside, 7), 1-O-(6-O-alpha-L-rhamnopyranosyl-beta-D-glucopyranosyl)-4-allylbenzene (chavicol beta-rutinoside, 8), and 1,2-di-O-beta-D-glucopyranosyl-4-allylbenzene (9). Compounds 2-9 were detected for the first time as constituents of galanga rhizomes.     

Constituents and their sweetness of food additive enzymatically modified licorice extract

Enzymatically modified licorice extract (EMLE) is a natural sweetener, which is prepared with cyclodextrin glucanotransferase. It is used because of its unique properties such as higher solubility and better taste than those of licorice extract. In the present paper, the structures of six major constituents isolated from EMLE were determined, and their sweetness was studied. The isolated compounds were glycyrrhizin (1), 3-O-[beta-D-glucuronopyranosyl-(1-->2)-beta-D-glucuronopyranosyl]liquiritic acid (2), and their derivatives glucosylated at the C-4 position of the terminal glucuronopyranose with additional one (3 and 4, respectively) and two (5 and 6, respectively) glucose moieties. Compounds 1 and 2 are the major and minor sweet constituents in licorice extract, respectively. Compounds 3-6 are new compounds isolated for the first time. Compound 2 was sweeter than compound 1. Interestingly, compound 3, which is a monoglucosylated derivative of compound 1, was sweeter than compound 4. The sweetness of both compounds was lower than that of the parent compounds, while the lingering sweet aftertaste was markedly improved. Compounds 5 and 6, which have two additional glucose moieties, showed only slight sweetness.     

A-type proanthocyanidins from lychee seeds and their antioxidant and antiviral activities

Two new A-type trimeric proanthocyanidins with two doubly bonded interflavanoid linkages, litchitannin A1 [epicatechin-(2β→O→7,4β→6)-epicatechin-(2β→O→7,4β→8)-catechin] (1) and litchitannin A2 [epicatechin-(2β→O→7,4β→6)-epicatechin-(2β→O→7,4β→6)-epicatechin] (2), were isolated from lychee (Litchi chinensis Sonn. cv. Heiye) seeds together with aesculitannin A (3), epicatechin-(2β→O→7,4β→8)-epiafzelechin-(4α→8)-epicatechin (4), proanthocyanidin A1 (5), proanthocyanidin A2 (6), proanthocyanidin A6 (7), epicatechin-(7,8-bc)-4β-(4-hydroxyphenyl)-dihydro-2(3H)-pyranone (8), and epicatechin (9). Their structures were elucidated on the basis of spectroscopic and chemical evidence. It is the first time that compounds 1-4, 7, and 8 have been reported in this species. Compounds 1-9 showed more potent antioxidant activity than L-ascorbic acid with ferric reducing antioxidant power (FRAP) values of 3.71-24.18 mmol/g and IC50 values of 5.25-20.07 μM toward DPPH radicals. Moreover, litchitannin A2 (2) was found to exhibit in vitro antiviral activity against coxsackie virus B3 (CVB3) and compounds 3 and 6 displayed antiherpes simplex virus 1 (HSV-1) activity.     

Triterpenoid glycosides from the leaves of two cultivars of Medicago polymorpha L

The saponin composition of leaves from the Medicago polymorpha cultivars 'Santiago' and 'Anglona' belonging to the botanical varieties brevispina and vulgaris, respectively, was investigated by a combination of chromatographic, spectroscopic, and spectrometric techniques. Several compounds were detected and quantitated by HPLC analysis using the external standard method. Twelve triterpene saponins (1-12) were purified by reverse-phase chromatography and their structures elucidated by spectroscopic (1D and 2D NMR, ESI-MS/MS) and chemical methods. They were identified as glycosides of echinocystic acid, hederagenin, caulophyllogenin, bayogenin, and soyasapogenol B. Two of them (2, 10) were previously reported in M. polymorpha; five of them (4, 6, 7, 9, 12) were already identified in other Medicago species; and three of them (1, 8, 11) were found in other plant genera. The two saponins identified as 3-O-α-L-arabinopyranosyl-28-O-[β-D-glucopyranosyl(1→6)β-D-glucopyranoside] echinocystic acid (3) and 3-O-α-L-arabinopyranosyl-28-O-β-D-glucopyranoside echinocystic acid (5) are newly identified natural compounds. The presence of echinocystic acid is reported here for the first time in the genus Medicago. Saponins from the cultivar 'Anglona' were characterized by a higher amount of echinocystic acid glycosydes, whereas saponins from the cultivar 'Santiago' were characterized by a higher amount of hederagenin glycosydes.