Further degradation product of hyperforin from Hypericum perforatum (St John's Wort)

Repeated examination of the aerial parts of Hypericum perforatum yielded a new degradation product of hyperforin (1) namely deoxyfurohyperforin A (2), together with the previously identified furohyperforin (3), furoadhyperforin (4), furohyperforin A (5a and 5b), pyrano[7,28-b]hyperforin (6) and 3-methyl-4,6-di(3-methyl-2-butenyl)-2-(2-methyl-1-oxopropyl)-3-(4-methyl-3-pentenyl)-cyclohexanone (7). The antimicrobial activity of the compounds 3, 5a and 5b, 6 and 7 was tested against Staphylococcus aureus, Candida albicans, Bacillus subtilis and Escherichia coli.     

Cytotoxic triterpene saponins from the leaves of Aralia elata

Phytochemical investigation of the leaves of Aralia elata has led to the isolation of four new compounds, 3-O-β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl oleanolic acid (1), 3-O-[β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl (1→3)]-[β-D-glucopyranosyl (1→2)]-β-d-glucopyranosyl hederagenin 28-O-β-D-glucopyranoside (2), 3-O-{[β-D-glucopyranosyl (1→2)]-[β-d-glucopyranosyl (1→3)-β-d-glucopyranosyl (1→3)]-β-D-glucopyranosyl} oleanolic acid 28-O-β-D-glucopyranosyl ester (3) and 3-O-[β-D-glucopyranosyl (1→2)]-[β-D-glucopyranosyl (1→3)]-β-d-glucopyranosyl caulophyllogenin (4) and two known compounds, 3-O-[β-D-glucopyranosyl (1→3)-α-l-arabinopyranosyl]-echinocystic acid (5) and 3-O-α-L-arabinopyranosyl echinocystic acid (6). The structural determination was accomplished with spectroscopic analysis, in particular (13)C-NMR, 2D-NMR and HR-ESI-MS techniques. Compounds 1-6 were tested for their inhibition of the growth of HL60, A549 and DU145 cancer cells. Compound 1 showed significant cytotoxic activity against HL60 and A549 cancer cells with IC(50) values of 6.99μM and 7.93μM respectively. In addition, compounds 5 and 6 showed significant cytotoxic activity against HL60 cancer cells with IC(50) values of 5.75μM and 7.51μM, respectively.     

Cytotoxic ceramides and glycerides from the roots of Livistona chinensis

A 70% ethanol extract of the roots of Livistona chinensis has been investigated, led to the isolation of 13 compounds, including a new ceramide, (2S,3S,4R,9Z)-2-[(2R)-2-hydroxytricosanoylamino]-9-octadecene-1,3,4-triol (2), a new glycosyl ceramide, 1-O-β-d-glucopyranosyl-(2S,3S,4R,9Z)-2-[(2R)-2-hydroxydocosanoylamino]-9-octadecene-1,3,4-triol (3), three new monoacylglycerols, 1-(34-hydroxytetratriacontanoyl)-sn-glycerol (9), 1-[nonadeca-(9Z,12Z)-dienoyl]-sn-glycerol (10), and 1-[12-hydroxypentatriaconta-(13E,15Z)-dienoyl]-sn-glycerol (11), a new diacylglycerol, 1-(heptadeca-6Z,9Z-dienoyl)-3-(octadeca-6Z,9Z,12Z-trienoyl)-sn-glycerol (12), as well as a new diacylglycerol aminoglycoside, 1-octadecanoyl-2-nonadecanoyl-3-O-(6-amino-6-deoxy)-β-d-glucopyranosyl-sn-glycerol (13). The structures of new compounds were elucidated, based on spectroscopic, zymologic and chemical methods. Among the compounds tested, compounds 3, 4 and 13 showed significantly antiproliferative effects against the human tumor cell lines (K562, HL-60, HepG2, and CNE-1) with the IC₅₀ of 10–65 μM. To our knowledge, this is first report of the occurrence of ceramides and acylglycerols in the genus Livistona.     

In vivo antidepressant activity of sesquiterpenes from the roots of Valeriana fauriei Briq

Antidepressant activity-guided fractionation of the MeOH extract of Valeriana fauriei Briq. roots resulted in the isolation of two new germacrane-type sesquiterpenes (1-2) in addition to seven known ones (3-9). Their structures were elucidated as 1β,10α-dihydroxyl-8α-acetoxyl-10β,11,11-trimethyl-4-formyl-bicyclogermacren-E-4(5)-ene (1), 1β-hydroxyl-8α-acetoxyl-11,11-dimethyl-4-formyl-bicyclogermacren-E-4(5),10(14)-diene (2), bicyclo[8,1,0]5β-hydroxyl-7β-1acetoxyl-5α,11,11'-trimethyl -E-1(10)-ene-4α,15-olide (3), 8α-acetoxyl-3α,4α,10-trihydroxyl-guaia-1(2)-ene-12,6α-olide (4), 2-Ethylhexyl-4-hydroxybenzoate (5), 11αH-gemacra-1(10)E,4Z-diene-3-one-12,6α-olide (6), β-Sitoterol (7), isovaleric acid (8), isoborneol acetate (9), using a combination of UV, IR, mass spectroscopy, 1D and 2D NMR spectroscopy. The antidepressant activity of compounds 1-4 was investigated by the FST on mice. Among them, compounds 3 and 4 showed the significant antidepressant activity (*, P<0.01).     

Iridoid, phenylethanoid and flavonoid glycosides from Sideritis trojana

From the MeOH extract of Sideritis trojana, a new iridoid glycoside, 10-O-(E)-feruloylmelittoside (1) was obtained in addition to four known iridoid glycosides [melittoside (2), 10-O-(E)-p-coumaroylmelittoside (3), stachysosides E (4) and G (5)]. Moreover, five phenylethanoid glycosides [verbascoside (6), isoacteoside (7), lamalboside (8), leonoside A (9), isolavandulifolioside (10), three flavone glycosides (isoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (11), 4'-O-methyisoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (12), 3'-hydroxy-4'-O-methyisoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (13) and a benzylalcohol derivative (di-O-methylcrenatin) were obtained and identified. The structures were elucidated on the basis of NMR and HRMS data. All compounds were tested for their antioxidant activity by in vitro TEAC assay and some of them exhibited moderate activity (0.97-1.44 mM) when compared with the reference compound (quercetin 1.86 mM). Glycosides 6-13, the most active compounds in the TEAC assay, were also tested by flow cytometry to evaluate their ability to affect the levels of reactive oxygen species (ROS) in human prostate cancer cells (PC3).     

Two new nortriterpenoid saponins from Salicornia bigelovii Torr. and their cytotoxic activity

Investigation of characteristic constituents of Salicornia bigelovii Torr. led to isolation of two new 30-nortriterpenoid glycosides, Bigelovii A (1), Bigelovii B (2), together with two known 30-nortriterpenoid glycosides 3-4 and three known oleanane-type triterpenoid glycosides 5-7. The structures of new compounds were elucidated by extensive 1D and 2D NMR, and MS spectroscopic analysis, and chemical evidences. All compounds were isolated for the first time from Chenopodiaceae. Thus compounds 1-4 were evaluated for their cytotoxicity and compouds 1, 3 showed moderate activity against four cell lines, HL-60 (promyelocytic leukemia), MCF-7 (breast carcinoma), HepG2 (liver carcinoma) and A549 (lung carcinoma), with IC(50) values of 6.18, 78.08, 13.64 and >100μM for 1; 31.87, >100, ~100, >100μM for 3, respectively.     

Glycocerebroside bearing a novel long-chain base from Sagina japonica (Caryophyllaceae)

A new glycocerebroside (1), along with one reported one (2), was isolated from the ethanol extract of Sagina japonica (Caryophyllaceae) and was fully characterized. The structures of two compounds were identified as (2S, 3S, 4R, 8E)-1-(β-D-glucopyranosyl-3, 4-dihydroxy-2-[(R)-2′- hydroxypalmitoyl]amino-8-heptadecaene (1) and (2S, 3R, 8E)-1-(β-D-glucopyranosyl-3-hydroxy-2-[(R)-2′-hydroxypalmitoyl]amino-8-octadecaene (2) by using spectroscopic methods (¹H, ¹³C, and 2D NMR, MS) and chemical degradation.     

New sesquiterpenoids from the dried flower buds of Tussilago farfara and their inhibition on NO production in LPS-induced RAW264.7 cells

Three new sesquiterpenoids, 1α-(3″-ethyl-cis-crotonoyloxy)-8-angeloyloxy-3β,4β-epoxy-bisabola-7(14),10-diene (1), 7β-angeloyloxy-14-hydroxy-notonipetranone (2) and 1α-hydroxy-7β-(4-methylsenecioyloxy)-oplopa-3(14)Z,8(10)-dien-2-one (3) were isolated from ethanolic extract of the dried flower buds of Tussilago farfara L., along with nine known sesquiterpenoids (4-12). All of these compounds were evaluated for their effect on the inhibition of nitric oxide (NO) production induced by lipopolysaccharide in macrophage cell line RAW 264.7 and exhibited inhibitory activity on NO production in a dose-dependent manner. 7β-(4-Methylsenecioyloxy)-oplopa-3(14)E,8(10)-dien-2-one (8) was proved to be the best among these tested sesquiterpenoids with an IC(50) value of 10.80 μM.     

Chemical constituents from endophytic fungus Fusarium oxysporum

A new oxysporidinone analogue (1) and a new 3-hydroxyl-2-piperidinone derivative (2), along with the known compounds (−)-4,6′-anhydrooxysporidinone (3), (+)-fusarinolic acid (4), gibepyrone D (5), beauvercin (6),cerevisterol (7), fusaruside (8), and (2S,2′R,3R,3′E,4E,8E)-1-O-D-glucopyranosyl-2-N-(2′-hydroxy-3′-octadecenoyl)-3-hydroxy-9-methyl-4,8-sphingadienine (9) were isolated from Fusarium oxysporum. Compounds 1-9 were evaluated for cytotoxicity using the MTT method against cancer cell lines, PC-3, PANC-1, and A549. Beauvericin showed cytotoxicity against PC-3, PANC-1, and A549 with IC₅₀ value of 49.5 ± 3.8, 47.2 ± 2.9, and 10.4 ± 1.6 μM, respectively. Beauvericin also exhibited anti-bacterial activity towards methicillin-resistant Staphylococcus aureus (MIC = 3.125 μg/mL) and Bacillus subtilis (MIC = 3.125 μg/mL).     

Flavonoids and stilbenoids from Derris eriocarpa

One new resveratrol analogue, 1-(3′,4′,5′-trimethoxyphenyl)-2-methoxy-2-(4″-methoxyphenyl)-ethane-1-ol (1), and two new prenylisoflavones, 4′-hydroxy-5,7-dimethoxy-6-(3-methyl-2-butenyl)-isoflavone (2), and derrubon 5-methyl ether (3), together with 17 known compounds including one new natural product, 5,7-dihydroxy-3-[4′-O-(3-methyl-2-butenyl)-phenyl]-isoflavone (4), were isolated from the stems of ethnomedicinal plant Derris eriocarpa How. (Leguminosae). Their structures were elucidated based on chemical evidence and spectroscopic techniques including two-dimensional NMR methods. All compounds are reported from this species for the first time. Antimicrobial activities of the new compounds were evaluated. Compound 2 exhibited good inhibitory activities against Candida guilliermondii, C. albicans and Microsporium gypseum with the minimal inhibitory concentration (MIC) values of 12.5 μg/ml.     

Alkaloids from Lycoris aurea and their cytotoxicities against the head and neck squamous cell carcinoma

Phytochemical investigation of the 80% EtOH extract of the bulbs of Lycoris aurea led to the isolation of six new alkaloids, 2-demethyl-isocorydione (1), 8-demethyl-dehydrocrebanine (2), 1-hydroxy-anhydrolycorin-7-one (3), (+)-1,2-dihydroxy-anhydrolycorine N-oxide (4), 5,6-dihydro-5-methyl-2-hydroxyphenanthridine (5), and (+)-8-hydroxy-homolycorine-α-N-oxide (6), and together with two known compounds, isocorydione (7) and anhydrolycorin-7-one (8). Structural elucidation of all the compounds was performed by spectral methods such as 1D and 2D (¹H–¹H COSY, HMQC, and HMBC) NMR spectroscopy, in addition to high resolution mass spectrometry. All the alkaloids were in vitro evaluated for their cytotoxic activities against seven tumor cell lines of the head and neck squamous cell carcinoma and anti-inflammatory activities. Compounds 1, 2, 6, and 7 exhibited significant cytotoxicities against all the tested cell lines. Moreover, alkaloids 1, 2, and 7 possessed selective inhibition of Cox-2 (> 85%).     

Three new antibacterial active diarylheptanoids from Alpinia officinarum

Three new diarylheptanoids, together with ten known ones, were isolated from the ethanol extract from the rhizomes of Alpinia officinarum Hance. The structural identification of these compounds was mainly achieved by spectroscopic methods. The new compounds were elucidated as 7-(4″, 5″-dihydroxy-3″-methoxyphenyl)-1-phenyl -4-heptene-3-one (1), 1, 7-diphenyl-5-heptene-3-one (2) and 4-phenethyl-1, 7-diphenyl -1-heptene-3, 5-dione (3), respectively. All of the compounds showed antibacterial activity against Helicobactor pylori. Especially, the three new compounds showed strong antibacterial activity against Hp-Sydney strain 1 with the MIC values of 9–12 μg/mL, and against Hp-F44 with the MIC values of 25–30 μg/mL.     

Cerebroside and ceramide from the pollen of Brassica napus L.

The new cerebroside 1-O-(β-d-glucopyranosyl)-(2 S, 3 S, 4R, 8E)-2-[(2′R)-2′-hydroxytetracosenoilamino]-8-octadecene-1,3,4-triol (1) and ceramide (2 S, 3 S, 4R, 8E)-2-[(2′R)-2′-hydroxytetracosenoilamino]-8-octadecene-1,3,4-triol (2) were isolated from the ethyl acetate extract of the pollen of Brassica napus L. The structures of 1 and 2 were elucidated on the basis of chemical and spectroscopic method. Two new compounds were evaluated for activity in vitro assays for the cytotoxic activities against human tongue squamous carcinoma cell line (Tca8113).     

A new cerebroside from Polygala japonica

The isolation of a new cerebroside, 1-O-beta-d-glucopyranosyl-(2S,3S,4R,11E)-2-[(2'R)-2'-hydroxypalmitoylamino]-11-octadecene-1,3,4-triol (polygalacerebroside) (1), from the aerial part of Polygala japonica is reported.     

Steroidal saponins from Fritillaria pallidiflora Schrenk

Five new steroidal saponins, Pallidifloside D (1), Pallidifloside E (2), Pallidifloside G (5), Pallidifloside H (6) and Pallidifloside I (7), together with seven other steroidal saponins (3, 4, 8-12) were isolated from the dry bulbs of Fritillaria pallidiflora Schrenk. Their structures were established by spectroscopic techniques (IR, MS, 1D and 2D NMR) and chemical means. The isolated steroidal saponins were evaluated for cyotoxic activity against human C6 brain gliomas and Hela cervix cancer cell lines using MTT assays. Compounds 1, 10, 11, 12 showed cytotoxicity against C6 and Hela cell lines with IC(50) values in the range of 5.1-75.8μM.     

Phenolic glycosides from Dodecadenia grandiflora and their glucose-6-phosphatase inhibitory activity

Phytochemical investigation of Dodecadenia grandiflora leaves led to the isolation and identification of three phenolic glycosides, designated 1-[(4′-O-(E)-p-coumaroyl)-β-d-glucopyranosyl]-oxy-2-phenol (1), 1-[(6′-O-(E)-p-coumaroyl)-β-d-glucopyranosyl]-oxy-2-phenol (2) and 1-[O-β-d-glucopyranosyl(1→2)-β-d-glucopyranosyl]-oxy-2-phenol (3), along with nine known compounds. Compounds 1, 2, 5 and 9 exhibited significant glucose-6-phosphatase inhibitory activity (63.7, 66.9, 82.9 and 85.4%) with IC₅₀ values of 88.5, 81.0, 51 and 50 μM respectively. On the basis of biological results, a structure–activity relationship has been discussed.     

Potent and selective butyrylcholinesterase inhibitors from Ficus foveolata

Four stilbenes (1-4), one inseparable mixture of two alkyl diferulates (5a, 5b), one alkyl ferulate (6) and four flavonoids (7-10) were isolated from Ficus foveolata Wall. Except for quercetin (10), the other ten constituents were isolated from F. foveolata for the first time. In addition, one of the two components in mixture 5 is a new compound identified as (1E,22E)-1,22-docosanediol diferulate (5a). All nine isolated compounds, plus the mixture of 5a and 5b known as 5, exhibited a low or no activity against acetylcholinesterase. However, and interestingly, the stilbenes 1-4 showed a high inhibition towards butyrylcholinesterase. Gnetol (4) had the lowest IC(50) value of 1.3μM towards butyrylcholinesterase and showed a reversible and competitive inhibition in the kinetic study.     

An unusual taxodione derivative from hairy roots of Salvia austriaca

From a root culture of Salvia austriaca, transformed with Agrobacterium rhizogenes, a new diterpenoid was isolated and its chemical structure was determined as 7-(2-oxohexyl)-11-hydroxy-6, 12-dioxo-7,9(11),13- abietatriene [= 7-(2-oxohexyl)-taxodione] on the basis of spectroscopic methods, especially 1D and 2D NMR, and by comparison with structurally related compounds. This compound represents a hitherto unknown 2-oxohexyl diterpenoid derivative. Cytotoxic studies revealed that the new compound exhibited high cytotoxic activity against three cancer cell lines with IC(50) values ranging from 0.63 to 0.72μM. Its cytotoxic effectiveness against the cancer cells was ten fold higher than that of taxodione.     

Anti-inflammatory homoisoflavonoids from the tuberous roots of Ophiopogon japonicus

Two new homoisoflavonoids, named ophiopogonone E (1) and ophiopogonanone H (2), together with thirteen known ones (3-15) were isolated from the tuberous roots of Ophiopogon japonicus. Their structures were elucidated by spectroscopic and chemical analyses. Compounds 7 and 15 were isolated from the genus for the first time. In addition, compounds 2-15 were evaluated for their effects on the inhibition of NO production induced by lipopolysaccharide in the murine microglial cell line BV-2. Compounds 2, 4, 6, 7, 10, 11 showed potent inhibitory effects on NO production with IC(50) values of 20.1, 17.0, 7.8, 5.1, 19.2 and 14.4 μM respectively.     

Five novel naphthylisoquinoline alkaloids with growth inhibitory activities against human leukemia cells HL-60, K562 and U937 from stems and leaves of Ancistrocladus tectorius

Two new 7,6′-coupled naphthylisoquinolines, namely ancistrotectorines A (1) and B (2), two new 5,3′-coupled naphthylisoquinolines, namely ancistrotectorines C (3) and D (4), and one new 7,8-coupled naphthylisoquinoline, namely ancistrotectorine E (5), together with 9 known naphthylisoquinoline alkaloids, hamatine (6), ancistrobertsonine B (7), ancistrocladinine (8), hamatinine (9), ancistrotanzanine A (10), ancistrotanzanine B (11), ancistrotectoriline B (12), 7-epi-ancistrobrevine D (13), and ancistrotectorine (14), were isolated from the 70% EtOH extract of Ancistrocladus tectorius. Their structures were elucidated based on the extensive analysis of spectroscopic data (1D, 2D NMR and MS). Compound 5 exhibited inhibitory activities against HL-60, K562 and U937 cell lines with IC₅₀ values of 1.70, 4.18 and 2.56 μM respectively.