Sesquiterpenes from Curcuma zedoaria rhizomes and their cytotoxicity against human gastric cancer AGS cells

Curcuma zedoaria rhizome (Zingiberaceae) is a well-known traditional medicinal plant used in Ayurvedic and traditional Chinese medicine to treat various cancers. This study aimed to identify the cytotoxic components from C. zedoaria rhizomes that act against gastric cancer, which is the third leading cause of death from cancer worldwide because the MeOH extract of C. zedoaria rhizome was found to show a cytotoxic effect against gastric cancer AGS cells. Repeated column chromatography and semi-preparative HPLC purification were used to separate the components from the C. zedoaria MeOH extract. Two new sesquiterpenes, curcumenol-9,10-epoxide (1) and curcuzedoalide B (2), and 12 known related sesquiterpenes (3–14) were isolated from the C. zedoaria MeOH extract. The structures of new compounds were determined by 1D and 2D NMR spectroscopic experiments and HR-ESIMS, and quantum chemical ECD calculations. The cytotoxic effects of the isolated compounds were measured in human gastric cancer AGS cells using an MTT cell viability assay. Compounds 9, 10, and 12 exhibited cytotoxic effects against gastric cancer AGS cells, with IC₅₀ values in the range of 212–392 μM. These findings provide further experimental scientific evidence to support the traditional use of C. zedoaria rhizomes for the treatment of cancer. Curcumenol (9), 4,8-dioxo-6β-methoxy-7α,11-epoxycarabrane (10), and zedoarofuran (12) were identified as the main cytotoxic components in C. zedoaria rhizomes.     

New derivatives from the aerial parts of Boerhaavia diffusa L. (Nyctaginaceae)

Boerhaavia diffusa L. is used in the traditional medicine of several Asian countries. The isolation and identification of five new compounds, together with 11 known compounds, from the ethyl acetate extract of the aerial part of B. diffusa grown Vietnam is reported. The structure of the new compounds was established by 1D and 2D NMR spectroscopy, and high resolution ESI-MS analysis. New compounds are two rotenoids: 9,11-dihydroxy-6,10-dimethoxy[1]benzopyrano[3,4-b][1]benzopyran-12(6H)-one (boeravinone P, 3) and 3-[2-(β-d-glucopyranosyloxy)-3-hydroxyphenyl]-5-hydroxy-2-hydroxymethyl-7-methoxy-6-methyl-4H-1-benzopyran-4-one (boeravinone Q, 9), an atropisomeric mixture of two rotenoid glycosides (3′,5-dihydroxy-2-hydroxymethyl-7-methoxy-6-methylisoflavone 2′-O-β-d-glucopyranoside, 11), a sesquiterpene lactone (4,10-dihydroxy-8-methoxyguai-7(11)-en-8,12-olide, 5) and a new phenylpropanoid glycoside (boerhaavic acid, 15).     

Cucurbitane-type triterpenoids from the aerial parts of Momordica charantia L.

Six new cucurbitane-type triterpenoids (1–6), together with two known analogues (7 and 8) were isolated from the aerial parts of Momordica charantia L. The structures of new compounds were identified as cucurbita-6,24-dien-3β,23-diol-19,5β-olide (1), (19R)-5β,19-epoxy-19-methoxycucurbita-6,24-dien-3β,23-diol (2), (19S)-5β,19-epoxy-19-methoxycucurbita-6,24-dien-3β,23-diol (3), (19R)-5β,19-epoxy-19-isopropoxycucurbita-6,24-dien-3β,23-diol (4), 3β,23-dihydroxy-5-methoxycucurbita-6,24-dien-19-al (5) and (19R)-7β,19-epoxy-19-methoxycucurbita-5,24-dien-3β,23-diol (6), by extensive MS, 1D and 2D NMR spectroscopic technologies. This is the first report of the isolation of tetracyclic triterpenoids possessing a 7β,19-epoxy system, viz., 6, from M. charantia L.     

Reduced perylenequinone derivatives from an endophytic Alternaria sp. isolated from Pinus ponderosa

The consecutive solvent extraction of endophytic Alternaria sp. (DC401) isolated from Pinus ponderosa followed by chromatographic techniques led to the isolation of five perylenequinone compounds and one dihydronaphthaquinone derivative, which include three new perylenequinones (1–3). The compounds were identified as 6-methoxy-3,6a,7,10-tetrahydroxy-4,9-dioxo-4,5,6,6a,6b,7,8,9-octahydroperylene (1), 3,6a,9,10-tetrahydroxy-7,8-epoxy-4-oxo-4,5,6,6a,6b,7,8,9-octahydroperylene (2), 6-methoxy-3,6a,9,10-tetrahydroxy-7,8-epoxy-4-oxo-4,5,6,6a,6b,7,8,9-octahydroperylene (3), 3,6a,7,10-tetrahydroxy-4,9-dioxo-4,5,6,6a,6b,7,8,9-octahydroperylene (altertoxin I) (4), 3,6a,7,10-tetrahydroxy-4,9-dioxo-4,6a,6b,7,8,9-hexahydroperylene (dehydroaltertoxin I) (5), and 7-chloroscytalone (6). Structure of compounds 1–6 was determined on the basis of detailed spectroscopic analysis, as well as by comparison with literature reports. The antileismanial, antimicrobial, antimalarial and in vitro cytotoxic activities of compounds 1–6 were evaluated.     

(2S)-Prenylflavanones and taraxerane triterpenoids from Mallotus mollissimus

Three prenylflavanones, (2S)-5,7-dihydroxy-4′-methoxy-8-(3″,3″-dimethylallyl)flavanone (3), (2S)-5,4′-dihydroxy-7-methoxy-6-(3″,3″-dimethylallyl)flavanone (6), 8-prenylnaringenin (11), and a new epimeric pair (2″S/2″R)-(2S)-5,7-dihydroxy-4′-methoxy-6-(2″-hydroxy-3″-methylbut-3″-enyl)flavanones (4a/4b) were isolated together with taraxerone, taraxerol, epitaraxerol, β-sitosterol, oleanolic acid, 1-O-docosanoyl glycerol, apigenin, and apigenin 7-O-β-D-glucopyranoside from the MeOH extract of the leaves of Mallotus mollissimus. The structures of the isolated compounds were determined on the basis of 1D/2D NMR and HR-MS spectroscopic data; the 2S configuration of the prenylflavanones 3, 4, and 6 was deduced from CD spectroscopic data. The presence of three taraxerane triterpenoids reinforces the inclusion of M. mollissimus (syn. Croton mollissimus) in Mallotus genus. Among species of Mallotus the occurrence of the (2S)-prenylflavanones 3, 4, and 6 is confined to M. mollissimus.     

Tyrosinase inhibitory activity of three new glycosides from Breynia fruticosa

Two new flavanone glycoside derivatives and one new sulfur-containing spiroacetal glycoside, (2R, 3R)-3-acetyl-7-methoxy-(−)-epicatechin 5-O-(6-isobutanoyl)-β-d-glucopyranoside (1), (2R, 3R)-3-acetyl-7-methoxy-(−)-epicatechin 5-O-[6-(2-methylbutanoyl)]-β-d-glucopyranoside (2) and 4-[(carboxymethyl)thio]-5′-hydroxy-phyllaemblic acid O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside ester (3), along with twelve known flavonoids and one known sulfur-containing spiroacetal glycoside, were isolated from Breynia fruticosa. Their structures were elucidated by the use of extensive spectroscopic methods (UV, IR, HR-ESI-MS, 1D and 2D NMR, and CD). The in vitro inhibition of tyrosinase activity by all of these compounds was also evaluated, and we concluded that the flavanol-containing 5-O- and 7-O-sugar moieties possessed more potent effects than the other compounds examined herein.     

Microbial transformation of acetyl-11-keto-β-boswellic acid and their inhibitory activity on LPS-induced NO production

The capabilities of 20 strains of fungi to transform acetyl-11-keto-β-boswellic (AKBA) were screened. And biotransformation of AKBA by Cunninghamella blakesleana AS 3.970 afforded five metabolites (1–5), while two metabolites (6, 7) were isolated from biotransformation of Cunninghamella elegans AS 3.1207. The chemical structures of these metabolites were identified by spectral methods including 2D NMR and their structures were elucidated as 7β-hydroxy-3-acety-11-keto-β-boswellic acid (1), 21β-dihydroxy-3-acety-11-keto-β-boswellic acid (2), 7β,22α-dihydroxy-3-acety-11-keto-β-boswellic acid (3), 7β,16α-dihydroxy-3-acety-11-keto-β-boswellic acid (4), 7β,15α-dihydroxy-3-acety-11-keto-β-boswellic acid (5); 7β,15α,21β-trihydroxy-3-acety-11-keto-β-boswellic acid (6) and 15α,21β-dihydroxy-3-acety-11-keto-β-boswellic acid (7). All these products are previously unknown. Their primary structure–activity relationships (SAR) of inhibition activity on LPS-induced NO production in RAW 264.7 macrophage cells were evaluated.     

Two new lignans with their biological activities in Portulaca oleracea L.

Two new lignans, identified as 6,7-dihydroxy-4-(4′’-hydroxy-3′’-methoxyphenyl)-2-naphthoic acid, named Oleralignan C (1), and 4-(3,4-dihydroxyphenyl)-6-hydroxy-7-methoxy-2-naphthoic acid, named Oleralignan D (2), were obtained from Portulaca oleracea L. The structures were determined by spectroscopic methods, including UHPLC-ESI-QTOFMS, ¹D and ²D NMR. Both Oleralignan C (1) and Oleralignan D (2) inhibited the inflammatory factors, IL-1β and TNF-α in RAW 264.7 cells induced by lipopolysaccharide (LPS). Both compounds also could clear 1,1-diphenyl-2-picryl-hydrazyl (DPPH) radicals indicating their antioxidant potential.     

Phytochemical investigation of Eremostachys moluccelloides Bunge (Lamiaceae)

Phytochemical investigation of the aerial parts of Eremostachys moluccelloides Bunge led to the identification of a new diterpene, 2β,14-dihydroxy −11-formyl- 12-carboxy-13-des-isopropyl-13-hydroxymethyl-abieta-8,11,13- triene- 16(17)- lactone (1), along with the known compounds 12, 18-dicarboxy-14-hydroxy-13-des -isopropyl-13-hydroxymethyl- abieta-8,11,13-triene-16(17)-lactone (2), 5-hydroxy-3′,4′,7-trimethoxyflavone (3), 5-hydroxy-4’,7-dimethoxyflavone (4), luteolin-7-O-β-glucoside (5), verbascoside (6), luteolin 7-O-(6″-O-β-D-apiofuranosyl) -β-D-glucopyranoside (7), chlorogenic acid (8), echinacoside (9), apigenin-7-O-β-D-glucoside (10), p-coumaric acid (11), vanillic acid (12), apigenin-7-O-(6″-E-p-coumaroyl)-β-D-glucopyranoside (13), apigenin-7-O-(3″,6″-E-p-dicoumaroyl)-β-glucoside (14), lamalbide (15), 6β-hydroxy-7-epi-loganin (16), phloyoside II (17) The structures were elucidated on the basis of 1D and 2D NMR spectroscopy, UV, MS and by comparison with compounds previously reported in the literature. Compounds 1–4, 8, 9, 11, 12, 14 have not been reported previously from any species within the genus Eremostachys. Compounds 1–14, 17 were obtained from this species for the first time. The chemotaxonomic significance of the isolated compounds is discussed.     

Sappanin-type homoisoflavonoids from Sansevieria trifasciata Prain

Two new sappanin-type homoisoflavonoids, (3R)-7-hydroxy-8-methoxy-3′,4′-methylenedioxyhomoisoflavanone (trifasciatine A) 1 and (3R)-3,7-dihydroxy-8-methoxy-3′,4′-methylenedioxyhomoisoflavanone (trifasciatine B) 2 were isolated as minor components from the EtOAc soluble fraction of the methanol extract of Sansevieria trifasciata collected in Cameroon together with the known 1-(stearoyl)-glycerol 3 and spirosta-5,25(27)-dien-1β,3β-diol-1-O-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranoside 4. Their structures were elucidated mainly by extensive spectroscopic analysis (1D and 2D NMR) and HRESIMS. Compounds 1 and 2 were screened for their antiproliferative activity on HeLa cells and no significant effect was observed when compare to 5-FU (fluorouracil) used as positive control.     

Four new lanostane-type triterpenoids from Inonotus obliquus

Four new lanostane-type triterpenoids, inonotsuoxodiol B (1), inonotsuoxodiol C (2), epoxyinonotsudiol (3), and methoxyinonotsutriol (4), were isolated from the sclerotia of Inonotus obliquus. Their structures were determined to be 3β,22R-dihydroxylanosta-9(11),24-dien-7-one (1), 3β,22R-dihydroxylanosta-7,24-dien-11-one (2), 9α,11α-epoxy-lanosta-7,24-diene-3β,22R-diol (3), and 7β-methoxylanosta-8,24-diene-3β,11α,22R-triol (4) on the basis of NMR spectroscopy, including 1D and 2D (¹H–¹H-COSY, NOESY, HMQC, HMBC) NMR spectra, and EIMS.     

A new nortriterpenoid from the fruiting bodies of Ganoderma tropicum

Ganoderma tropicum has been widely used by the local folks for coronary heart disease treatment, liver protection, and sleep aid. In order to discover natural active components and tap the medical potential of G. tropicum, the chemical investigation of its fruiting bodies was carried out. This study led to the isolation of a new nortriterpenoid named 26-nor-11,23-dioxo-5α-lanost-8-en-3β,7β,15α,25-tetrol (1) and a known nortriterpenoid lucidone D (2). The structure of the new nortriterpenoid was elucidated by spectroscopic techniques including UV, IR, MS, 1D and 2D NMR spectroscopy.     

Two new guaiane sesquiterpenes from Datura metel L. with anti-inflammatory activity

Chemical investigation of an acidic methanol extract of the whole plants of Datura metel resulted in the isolation of two new guainane sesquiterpenes, 1β,5α,7β-guaiane-4β,10α,11-triol (1) and 1α,5α,7α-11-guaiene-2α,3β,4α,10α,13-pentaol (2), along with eight known compounds: pterodontriol B (3), disciferitriol (4), scopolamine (5), kaempferol 3-O-β-d-glucosyl(1 → 2)-β-d-galactoside 7-O-β-d-glucoside (6), kaempferol 3-O-β-glucopyranosyl(1 → 2)-β-glucopyranoside-7-O-α-rhamnopyranoside (7), pinoresinol 4′′-O-β-d-glucopyranoside (8), (7R,8S,7′S,8′R)-4,9,4′,7′-tetrahydroxy-3,3′-dimethoxy-7,9′-epoxy-lignan-4-O-β-d-glucopyranoside (9), and (7S,8R,7′S,8′S)-4,9,4′,7′-tetrahydroxy-3,3′-dimethoxy-7,9′-epoxylignan-4-O-β-d-glucopyranoside (10). Their structures were elucidated by extensive spectroscopic methods, including 1D and 2D NMR and MS spectra. Compounds 2-4 and 6-10 were shown to have modest anti-inflammatory effects through inhibition of NO production in LPS-stimulated BV cells.     

Phenylethanoid glycosides from the leaves of Magnolia hodgsonii

Three new phenylethanoid glycosides, 2-(3-hydroxy-4-methoxyphenyl)ethyl 1-O-β-d-allopyranoside (hodgsonialloside A, 1), 2-(3-hydroxy-4-methoxyphenyl)ethyl 1-O-β-d-glucopyranosyl-(1 → 4)-β-d-allopyranoside (hodgsonialloside B, 2) and 2-(3-methoxy-4-hydroxyphenyl)ethyl 1-O-β-d-allopyranoside (hodgsonialloside C, 3) were isolated from the leaves of Magnolia hodgsonii in addition to six known compounds, tyrosol 4-O-β-d-xylopyranosyl-(1 → 6)-β-d-glucopyranoside (4), kaempferol 3-O-neohesperidoside (5), kaempferol 3-O-rutinoside (6), kaempferol 3-O-α-l-rhamnopyranosyl-(1 → 2)-[α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside (7), (+)-syringaresinol O-β-d-glucopyranoside (8), and oblongionoside C (9). The structure elucidation of these compounds was based on analyses of physical and spectroscopic data including 1D and 2D NMR experiments.     

Biotransformation of capsaicin by Penicillium janthinellum AS 3.510

Biocatalysis of capsaicin (1) was performed by Penicillium janthinellum AS 3.510. Nine metabolites including four new compounds were afforded, and their structures were elucidated as (8S)-trans-8-hydroxy-8-hydroxymethyl-N-vanillyl-6-nonenamide (2), 6-hydroxy-8-methyl-N-vanillyl-7-nonenamide (3), trans-8-methoxy-8-methyl-N-vanillyl-6-nonenamide (4), 6-methoxy-8-methyl-N-vanillyl-7-nonenamide (5), dihydrocapsaicin (6), ω-1-hydroxydihydrocapsaicin (7), ω-1-hydroxycapsaicin (8), ω-hydroxycapsaicin (9), N-(4-hydroxy-3-methoxybenzyl)-5-[3-(propan-2-yl)oxiran-2-yl]pentanamide (10) by 1D and 2D NMR and HRESIMS spectra. The biotransformation processes include hydroxylation, methylation, reduction, and epoxylation.     

New purine alkaloids from the Red Sea marine tunicate Symplegma rubra

Investigation of the Red Sea marine tunicate Symplegma rubra Monniot, 1972 gave three new purine alkaloids namely 6-methoxy-7,9-dimethyl-8-oxoguanine (1), 6-methoxy-9-methyl-8-oxoguanine (2), and 2-methoxy-7-methyl-8-oxoadenine (4) together with seven known compounds: 6-methoxy-7-methyl-8-oxoguanine (3), 9-methyl-8-oxoadenine (5), 7-methyl-8-oxoadenine (6), 8-oxoadenine (7), 3-methylxanthine (8), inosine (9), and homarine (pyridinium-2-carboxylic acid-1-methyl) (10). Compound 6 was reported here for the first time from a natural source. The structure determination of the compounds was accomplished by extensive interpretation of their spectroscopic data including 1D (¹H and ¹³C) and 2D (¹H–¹H COSY, HSQC, and HMBC) NMR and high-resolution mass spectral data. The isolated compounds were evaluated for their protein kinase inhibitory activity against different kinases (CDK5, CK1, DyrK1A, and GSK3) at 10 μg/mL. The compounds showed moderate activity against these kinases.     

Furanocoumarins from Dorsteniafoetida

The linear furanocoumarins 5-(2,3-epoxy-3-methyl-butoxy)-chalepensin, 5-methoxy-3-(3-methyl-2,3-dihydroxybutyl)-psoralen-diacetate (7), 5-methoxy-3-[3-(β-d-glucopyranosyloxy)-2-acetyloxy-3-methyl-butyl]-psoralen and 5-(3-methyl-2,3-dihydroxybutyloxy)-3-[3-(β-d-glucopyranosyloxy)-2-hydroxy-3-methyl-butyl]-psoralen, and the coumarin derivative 7-hydroxy-5-methoxy-6-carboxymethyl-3-[3-(β-d-glucopyranosyloxy)-2-hydroxy-3-methyl-butyl]-coumarin were isolated from the leaves of Dorstenia foetida (Moraceae) along with the known compounds psoralen, bergapten, isopimpinellin, phellopterin, 5-methoxychalepensin and turbinatocoumarin. Further furanocoumarins were characterized by ESI-MS/MS investigations. The nonpolar extracts of D. foetida exhibit antifungal, antibacterial and cytotoxic activity, however, no anthelminthic activity.     

Renoprotective chemical constituents from an edible mushroom,Pleurotus cornucopiae in cisplatin-induced nephrotoxicity

Pleurotus cornucopiae (Pleurotaceae) is an edible and medicinal mushroom widely distributed in Korea, China, and Japan. The MeOH extract of the fruiting bodies of P. cornucopiae showed renoprotective effects against cisplatin-induced kidney cell damage. Chemical investigation of the MeOH extract led to the isolation and identification of 12 compounds including noransine (1), uridine (2), uracil (3), (3β, 5α, 6β, 22E, 24S) -ergosta-7, 22-diene-3, 5, 6, 9-tetrol (4), (22E,24S)-ergosta-7,22-diene-3β,5α,6β-triol (5), (22E,24R)-ergosta-8(14),22-diene-3β,5α,6β,7α-tetrol (6), cerebroside B (7), (2R) -N- [(1S, 2R, 3E, 7E) -1- [(β-d-glucopyranosyloxy) methyl] -2-hydroxy-8-methyl-3, 7-heptadecadien-1-yl] -2-hydroxy-heptadecanamide (8), cerebroside D (9), nicotinamide (10), 1,2-bis(hydroxymethyl)-4,5-dimethoxybenzene (11), and benzoic acid (12). Among them, compounds 1 and 11 were isolated as naturally occurring products for the first time, though they were reported as synthetic products in previous papers. All of the compounds (except 8 and 11) abrogated cisplatin-induced LLC-PK1 cell damage in a dose-dependent manner. Of special note, compounds 2, 5, 6, and 12 ameliorated cisplatin-induced nephrotoxicity to 80% of the control value at 10 μM. The protective effects of compounds 2, 5, 6, and 12 were mediated via the deactivation of JNK-caspase 3 apoptotic cascade. This study is the first to demonstrate that the chemical constituents of P. cornucopiae display renoprotective effects against anticancer drug-induced damage in kidney cells.     

Two new cyclohexylethanol derivatives from the whole plants of Incarvillea delavayi and their inhibition on LPS-induced NO release in BV-2 cells

Delavatones A (4β, 7α-dihydroxy-7β-(13-methylpent-11-one-12-ene)-octahydrobenzofuran, 1) and B (4β, 7α-dihydroxy-7β-(propan-9-one)-octahydrobenzofuran, 2), two structurally unique cyclohexylethanol derivatives with a substituted alkyl chain, were isolated from the 90% ethanol extract of the whole plants of Incarvillea delavayi. The structures of delavatones A and B were characterized by the interpretation of 1D and 2D NMR spectroscopic data in combination with NMR chemical shift calculation coupled with DP4+ probability analysis. In an in vitro assay for anti-inflammatory effect, delavatones A and B displayed remarkable suppression on NO production in LPS-induced BV-2 cells at concentrations ranging from 6 μM to 100 μM.     

Thiophenes,polyacetylenes and terpenes from the aerial parts of Eclipata prostrata

One new bithiophenes, 5-(but-3-yne-1,2-diol)-5′-hydroxy-methyl-2,2′-bithiophene (2), two new polyacetylenic glucosides, 3-O-β-d-glucopyranosyloxy-1-hydroxy-4E,6E-tetradecene-8,10,12-triyne (8), (5E)-trideca-1,5-dien-7,9,11-triyne-3,4-diol-4-O-β-d-glucopyranoside (9), six new terpenoid glycosides, rel-(1S,2S,3S,4R,6R)-1,6-epoxy-menthane-2,3-diol-3-O-β-d-glucopyranoside (10), rel-(1S,2S,3S,4R,6R)-3-O-(6-O-caffeoyl-β-d-glucopyranosyl)-1,6-epoxy menthane-2,3-diol (11), (2E,6E)-2,6,10-trimethyl-2,6,11-dodecatriene-1,10-diol-1-O-β-d-glucopyranoside (12), 3β,16β,29-trihydroxy oleanane-12-ene-3-O-β-d-glucopyranoside (13), 3,28-di-O-β-d-glucopyranosyl-3β,16β-dihydroxy oleanane-12-ene-28-oleanlic acid (14), 3-O-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl oleanlic-18-ene acid-28-O-β-d-glucopyranoside (15), along with fifteen known compounds (1, 3–7, and 16–24), were isolated from the aerial parts of Eclipta prostrata. Their structures were established by analysis of the spectroscopic data. The isolated compounds 1–9 were tested for activities against dipeptidyl peptidase IV (DPP-IV), compound 7 showed significant antihyperglycemic activities by inhibitory effects on DPP-IV in human plasma in vitro, with IC₅₀ value of 0.51 μM. Compounds 10–24 were tested in vitro against NF-κB-luc 293 cell line induced by LPS. Compounds 12, 15, 16, 19, 21, and 23 exhibited moderate anti-inflammatory activities.