Anthraquinones from the roots of Prismatomeris tetrandra

Three new anthraquinones, 1-hydroxy-2,3-dimethoxy-7-methyl-9,10-anthraquinone, 1,3-dihydroxy-5,6-dimethoxy-2-methyl-9,10-anthraquinone, and 3-hydroxy-1,5,6-trimethoxy-2-methyl-9,10-anthraquinone, along with five known anthraquinones were isolated from the roots of Prismatomeris tetrandra. Their structures were determined on the basis of spectroscopic data.     

Anthraquinones from the roots of Prismatomeris malayana

A novel anthraquinone, 1,3-dihydroxy-5,6-dimethoxy-2-methoxymethyl-9,10-anthraquinone (9) and a new natural product, 2-hydroxymethyl-1-methoxy-9,10-anthraquinone (8) were isolated from the roots of Prismatomeris malayana together with seven known anthraquinones, tectoquinone (1), 1-hydroxy-2-methyl-9,10-anthraquinone (2), rubiadin (3), rubiadin-1-methyl ether (4), 1,3-dihydroxy-5,6-dimethoxy-2-methyl-9,10-anthraquinone (5), nordamnacanthal (6), and damnacanthal (7). Their structures were determined on the basis of spectroscopic data. Some of the anthraquinones were tested for anticancer, antifungal, and antimalarial activities.     

Antibacterial activity of anthraquinone derivatives from Heterophyllaea pustulata (Rubiaceae)

Photosensitizing anthraquinones isolated from Heterophyllaea pustulata Hook f. (Rubiaceae), namely soranjidiol, rubiadin, damnacanthal and 5,5'-bisoranjidiol, showed antibacterial activity (bacteriostatic/bactericide) on Staphylococcus aureus. The mechanism of action seems to involve an increase in the levels of superoxide anion (O(2)(·-)) and/or singlet molecular oxygen ((1)O(2)). Moreover, the effect of actinic irradiation as a boosting agent for the production of both reactive species of oxygen as well as its influence on antibacterial activity was assessed. The routine susceptibility assay (minimum inhibitory concentration determination) was carried out by means of the broth macrodilution method. Bactericide activity was determined counting the colony-forming units per milliliter (cfu/mL) in plate. The O(2)(·-) production was determined by means of an indirect photobiological assay (Nitroblue Tetrazolium test), and the production of (1)O(2) was followed using an indirect steady-state method, with methionine as the (1)O(2) chemical quencher.     

Prenylated xanthone derivatives with antiplasmodial activity from Allanblackia monticola STANER L.C

Further study of the methanol extract of the stem bark of Allanblackia monticola STANER L.C. resulted in the isolation of a new prenylated xanthenedione, designated allanxanthone C, together with the five known xanthones, garciniafuran, tovophyllin A, rubraxanthone, norcowanin and mangostin and one saponin, stigmasterol-3-O-beta-D-glucopyranoside. The structure of the new compound was established by detailed spectroscopic analysis to be 1,2-dihydro-3,6,8-trihydroxy-1,1,7-tri(3-methylbut-2-enyl)xanthen-2,9-dione (3-hydroxyapetalinone C). The methanol extract and pure compounds were tested on two strains of Plasmodium falciparum, F32 (chloroquine sensitive) and FcM29 (chloroquine resistant). The IC50 values obtained ranged from 0.6 to 8.9 microg/ml. Their cytotoxicity was estimated on human melanoma cells (A375) and the cytotoxicity/antiplasmodial ratio was found to be between 15.45 and 30.46. The antimicrobial activities against a range of microorganisms of the crude extract and some of these compounds are also reported.     

HPLC-DAD-SPE-NMR isolation of tetracyclic spiro-alkaloids with antiplasmodial activity from the seeds of Erythrina latissima

Abstract

Seven tetracyclic spiro-alkaloids, i.e. glucoerysodine (1), erysodine (2), epi-erythratidine (3), erysovine (4), erythratidine (5), erysotrine (6) and erythraline (7) were isolated from the seeds of Erythrina latissima by means of conventional separation methods and HPLC-DAD-SPE-NMR. Their structures were elucidated by spectroscopic means. This is the first report on the isolation of compounds 3, 5 and 6 from this plant. Antiplasmodial activity against the chloroquine-resistant strain Plasmodium falciparum K1 and cytotoxicity against MRC-5 cells (human fetal lung fibroblast cells) was assessed in vitro. Erysodine (2) and erysovine (4) showed moderate activity (IC₅₀ 6.53?µM and 4.05?µM, respectively), compared with the standard chloroquine (IC₅₀ = 0.14?µM). No cytotoxicity was observed in a concentration up to 64.0?µM.     

New Chemical Constituents from Borreria verticillata (Rubiaceae)

A phytochemical study on Borreria verticillata has led to the isolation of two novel simple indole alkaloids, 6‐methoxy‐4‐(3‐methylbut‐2‐en‐1‐yl)‐1H‐indole, named verticillatine A ( 1 ), and 1‐(1H‐indol‐6‐yl)‐3‐methylbutan‐1‐one, named verticillatine B ( 2 ), one new iridoid, 6′‐O‐(2‐glyceryl)scandoside methyl ester ( 3 ), with the glycerol unit linked to a glucose unit, and two known ones, asperuloside ( 4 ) and scandoside methyl ester ( 5 ). The structures of these compounds were elucidated on the basis of spectroscopic‐data analyses, mainly ¹H‐ and ¹³C‐NMR, including 2D experiments (¹H,¹H‐COSY, NOESY, HMBC, and HMQC), and HR‐ESI‐MS.     

Triterpenoid acids and lactones from the leaves of Fadogia tetraquetra var. tetraquetra (Rubiaceae)

Four triterpenoids isolated from the leaves of Fadogia tetraquetra var. tetraquetra, 3beta-hydroxy-11alpha, 12alpha-epoxyoleanan-28,13beta-olide (1), 3beta-hydroxyurs-11-en-28,13beta-olide (2), oleanolic acid (3), and ursolic acid (4), were evaluated for their antiviral and antibacterial properties. Compound 4 showed potent activity against the Semliki Forest virus with an IC50 of 14.7 microM, but was also found to be significantly cytotoxic (68% reduction in cell viability after 24 hours exposure at 50 microM) towards baby hamster kidney (BHK21) host cells. A viability assay on the mammalian human hepatocellular carcinoma (Huh-7) cell line showed no significant effects on intracellular ATP content after 48 hours exposure to compounds 1-4 at this concentration. Compound 4 also inhibited Staphylococcus aureus (MIC 12.5 microM), but was inactive against Enterobacter aerogenes, Escherichia coli, and Pseudomonas aeruginosa. Compounds 1-3 were inactive against all tested bacterial strains at 50 microM concentration.     

A new iridoid from Guettarda grazielae M.R.V. Barbosa (Rubiaceae)

Chromatographic fractionation of the chloroform extracts from the stem bark and stems of Guettarda grazielae resulted in the isolation of a new iridoid (guettardodiol, 1) and the secoiridoid sarracenin (2), described for the first time in this genus. The structural elucidation of these compounds was based on spectroscopic analyses (IR, MS as well as 1-D and 2-D NMR experiments).     

New Antifungal Terpenoid Glycosides from Alibertia edulis (Rubiaceae)

Phytochemical investigation from the stems of Alibertia edulis led to the isolation and identification of a new iridoid 6β‐hydroxy‐7‐epigardoside methyl ester ( 1 ) and a new saponin 3β‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl]‐28‐O‐β‐D ‐glucopyranoside pomolate ( 2 ), along with three known compounds, shanzhiside methyl ester ( 3 ), ixoside ( 4 ), and 3,4,5‐trimethoxyphenyl 1‐O‐β‐D ‐apiofuranosyl‐(1→6)‐O‐β‐D ‐glucopyranoside ( 5 ). The structures of 1 and 2 were established on the basis of their spectroscopic data. Iridoid 1 and saponin 2 exhibited moderate inhibitory activities against Candida albicans and C. krusei in a dilution assay.     

Anthraquinones, Cdc25B phosphatase inhibitors, isolated from the roots of Polygonum multiflorum Thunb

Three anthraquinones, Cdc25B phosphatase inhibitors, were isolated from the methanolic extract of the roots of Polygonum multiflorum Thunb. (Polygonaceae). Anthraquinones, physcion (1), emodin (2), and questin (3), inhibited the enzymatic activity of Cdc25B phosphatase with IC(50) values of 62.5, 30, and 34 microg mL(-1), respectively. Emodin (2) and questin (3) strongly inhibited the growth of human colon cancer cells, SW620 with GI(50) values of 6.1 and 0.9 microg mL(-1), respectively. Commercially available anthraquinones, chrysophanol (4), and rhein (5) also inhibited Cdc25B phosphatase with IC(50) values of 10.7 and 22.1 microg mL(-1), respectively.     

In vitro antiplasmodial and cytotoxic activities of sesquiterpene lactones from Vernonia fimbrillifera Less. (Asteraceae)

Due to the in vitro antiplasmodial activity of leaf extracts from Vernonia fimbrillifera Less. (Asteraceae), a bioactivity-guided fractionation was carried out. Three sesquiterpene lactones were isolated, namely 8-(4’-hydroxymethacrylate)-dehydromelitensin (1), onopordopicrin (2) and 8α-[4’-hydroxymethacryloyloxy]-4-epi-sonchucarpolide (3). Their structures were elucidated by spectroscopic methods (1D and 2D NMR and MS analyses) and by comparison with published data. The isolated compounds exhibited antiplasmodial activity with IC₅₀ values ≤ 5 μg/mL. Cytotoxicity of the compounds against a human cancer cell line (HeLa) and a mouse lung epithelial cell line (MLE12) was assessed to determine selectivity. Compound 3 displayed promising selective antiplasmodial activity (SI > 10).     

Dammarane-Type Triterpenoid from the Stem Bark of Aglaia elliptica (Meliaceae) and Its Cytotoxic Activities

Two new dammarane-type triterpenoid fatty acid ester derivatives, 3β-oleate-20S-hydroxydammar-24-en (1) and 3β-oleate-20S,24S-epoxy-25-hydroxydammarane (2) with a known dammarane-type triterpenoid compound, such as 20S-hydroxydammar-24-en-3-on (3), were isolated from the stem bark of Aglaia elliptica (C.DC.) Blume. The chemical structures were determined by spectroscopic methods, including FTIR, NMR (one and two-dimensional), and HRESITOF-MS analysis, as well as chemical derivatization and comparison with previous literature. Furthermore, the synthetic analog resulting from transesterification of 1 and 2 also obtained 3β,20S-dihydroxy-dammar-24-en (4) and 20S,24S-epoxy-3β,25-dihydroxydammarane (5), respectively. The cytotoxic effect of all isolated and synthetic analog compounds was evaluated using PrestoBlue reagent against MCF-7 breast cancer cell and B16-F10 melanoma cell lines. The 20S-hydroxydammar-24-en-3-on (3) showed the strongest activity against MCF-7 breast cancer and B16-F10 melanoma cell, indicating that the ketone group at C-3 in 3 plays an essential role in the cytotoxicity of dammarane-type triterpenoid. On the other hand, compounds 1 and 2 had very weak cytotoxic activity against the two cell lines, indicating the presence of fatty acid, significantly decreasing cytotoxic activity. This showed the significance of the discovery to investigate the essential structural feature in dammarane-type triterpenoid, specifically for the future development of anticancer drugs.     

Neonaucline, a new indole alkaloid from the leaves of Ochreinauclea maingayii (Hook. f.) Ridsd. (Rubiaceae)

A new indole alkaloid; neonaucline (1), along with six known compounds-Cadamine (2), naucledine (3), harmane, benzamide, cinnamide and blumenol A-were isolated from the leaves of Ochreinauclea maingayii (Rubiaceae). In addition to that of compound 1, (13)C-NMR data of cadamine (2) and naucledine (3) were also reported. Structural elucidations of these alkaloids were performed using spectroscopic methods especially 1D- and 2D-NMR, IR, UV and LCMS-IT-TOF. The excellent vasorelaxant activity on isolated rat aorta was observed for the alkaloids 1-3 after injection of each sample at 1 × 10(-5) M.     

Anti-inflammatory and antiproliferative activities of Ixora brevifolia Benth. (Rubiaceae)

The crude extract and fractions from the branches of Ixora brevifolia, a tree found in the Brazilian Cerrado, were tested for anti-inflammatory and in vitro antiproliferative effects. The crude extract and n-hexane fraction exhibited significant inhibition of ear oedema in mice, while n-hexane-precipitated and chloroform fractions strongly inhibited the myeloperoxidase activity in ear tissue. The n-hexane and n-hexane-precipitated fractions showed strong growth inhibition for glioma cell line and the hydromethanolic fraction inhibited the growth of leukaemia cell line.     

Iridoids and anthraquinones from the Malaysian medicinal plant,Saprosma scortechinii (Rubiaceae)

A further investigation of the leaves and stems of Saprosma scortechinii afforded 13 compounds, of which 10 are new compounds. These were elucidated as the bis-iridoid glucosides, saprosmosides G (1) and H (2), the iridoid glucoside, 6-O-epi-acetylscandoside (3), and the anthraquinones, 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone (4), 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (5), 1,3-dihydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (6), 1,3,6-trihydroxy-2-methoxymethyl-9,10-anthraquinone (7), 1-methoxy-3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (8), 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone 3-O-beta-primeveroside (9), and 3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (10). Structure assignments for all compounds were established by means of mass and NMR spectroscopies, chemical methods, and comparison with published data. The new anthraquinones were derivatives of munjistin and lucidin.     

The glycosides of the roots from Gongronema taylorii (Schltr. & Rendle) Bullock)

The roots of Gongronema taylorii are rich in glycosides. These glycosides form a complex mixture of substances, of which some are closely related. From this mixture, six more or less pure but amorphous glycosides could be separated. Mild acid hydrolysis followed by alkaline hydrolysis led to the isolation of 5α-dihydrosarcostin ( 1 ) and some tayloron ( 3 ), whose probable structures have been reported earlier. In the original mixture, these genins are esterified predominantly with benzoic and cinnamic acids, and are also bound through glycosidic linkages to a series of sugars of which the following four could be identified by paper and thin layer chromatography: cymarose, digitoxose, oleandrose and pachybiose. Pachybiose and its two anomeric methyl glycosides have been isolated for the first time in a cristalline state.     

Anti-infective assessment of Senecio smithioides (Asteraceae) and isolation of 9-oxoeuryopsin,a furanoeremophilane-type sesquiterpene with antiplasmodial activity

The search for anti-infective activity in the antipyretic plant Senecio smithioides was conducted. Petroleum ether (PE), dichloromethane (CH₂Cl₂), ethyl acetate (EtOAc) and hydroethanolic (96% EtOH) extracts, and compounds 9-oxoeuryopsin (1), epoxydecompostin (2) and senecionine (3) were obtained from the aerial parts. All extracts and 1 were tested against chloroquine-resistant strain of Plasmodium falciparum (ref. chloroquine), Trypanosoma cruzi (ref. nifurtimox), Leishmania braziliensis, Leishmania amazonensis and Leishmania donovani (ref. pentamidine), Staphylococcus aureus and Escherichia coli (ref. gentamicin) and, Neurospora crassa and Candida albicans (ref. ketoconazole). The PE extract exhibited the strongest in vitro activity against Plasmodium falciparum IC₅₀ < 1.0 μg/mL. 1 was established as a potent antiplasmodial compound with an IC₅₀ = 1.2 μg/mL, 5.2 μM. Other antiparasitic activities were recorded for all extracts and 1. Antibacterial and antifungal activity was negligible.     

A New ent‐Kaurane Diterpene from Stems of Alibertia macrophylla K. Schum. (Rubiaceae)

Phytochemical investigations of the stems of a specimen of Alibertia macrophylla led to the isolation and characterization of the new diterpene ent‐kaurane‐2β,3α,16α‐triol ( 1 ), along with triterpenes 2 – 8 , iridoids 9 – 12 , and phenolic acids 13 – 15 . The structure of 1 was established based on spectroscopic studies (¹H‐ and ¹³C‐NMR, IR, and HR‐ESI‐MS). This is the first report of the isolation of a diterpene from the Alibertia genus in Rubiaceae.     

Triterpene saponins with XOD inhibitory activity from the roots of Ilex pubescens

A new triterpene saponin with 28-nor-urs-12(13),18(17)-dien-3β-ol as aglycone,named ilexsaponin C(1) was isolated from the roots of Ilex pubescens,together with three known saponins 2,3 and 4.The structure of 1 was elucidated on the basis of spectral analysis including 1D and 2D NMR and HR-ESI-MS.Saponins 1 and 4 exhibited significant XOD inhibitory activity in the test.     

Anti-inflammatory activity of saponins from roots of Impatiens parviflora DC.

Abstract

Two triterpene saponins (IPS-1, IPS-2) for the first time were isolated from the roots of Impatiens parviflora DC. (Balsaminaceae). Their anti-inflammatory activity was evaluated by means of two in vitro models: anti-hyaluronidase and anti-denaturation assays. Both saponins were shown to be potent hyaluronidase inhibitors that affect the enzyme in a dose-dependent manner. The anti-hyaluronidase effect of IPS-2 (IC₅₀?=?286.7?µg/mL) was higher than that of the reference drug: escin (IC₅₀?=?303.93?µg/mL). Both saponins protected bovine serum albumin from heat-induced denaturation in a dose-dependent manner. IPS-1 demonstrated higher anti-denaturation effect (IC₅₀?=?86.7?µg/ml) than IPS-2 (IC₅₀?=?109.76?µg/mL) or the standard drug: acetylsalicylic acid (IC₅₀?=?262.22?µg/mL). In conclusion, potent activity of IPS-1, IPS-2 in both in vitro assays shows that saponins from I. parviflora have anti-inflammatory activity. The obtained results allow to suggest that such compounds may be beneficial in inflammatory conditions, especially associated with excessive degradation of hyaluronic acid.