Modified limonoids from the leaves of Sandoricum koetjape

Three trijugin-type limonoids, sandrapins A, B and C, were isolated from the leaves of Sandoricum koetjape and their structures, which are related to capensolactones, were elucidated by a detailed 2D-NMR spectroscopic analysis.     

Limonoids from the stem bark of Cedrela odorata

Four nomilin/obacunol derivatives and a swietenolide derivative, together with seven known limonoids, were isolated from stem bark of Cedrela odorata and their structures established by spectroscopic methods. Antifeedant activity of the isolated compounds was also tested.     

Degraded limonoids from Melia azedarach and biogenetic implications

The unique series of C-2'-acylated C-glycosylflavones is extended by the discovery of the C-8-glucosyl derivatives 2'-O-galloylvitexin and 2'-O-galloylorientin and their C-6 analogues 2'-O-galloylisovitexin and 2'-O-galloylisoorientin, representing the first described O-galloyl-C-glycosylflavones. They are accompanied in the aerial parts of Pelargonium reniforme by the known non-galloylated parent analogues vitexin, orientin, isovitexin and isoorientin, as well as several known flavonoid-O-glycosides. The structures of these compounds were established from spectroscopic studies. Differentiation between C-glycosylation at C-6 and C-8 is discussed on the basis of the effects of dynamic rotational isomerism.     

Mexicanolide limonoids from the Madagascan Meliaceae Quivisia papinae

An investigation of the seeds of the Madagascan Meliaceae Quivisia papinae has yielded five mexicanolide group limonoids, together with two known mexicanolide limonoids and two known triterpenoids. Quivisianolide A 9 possesses a hitherto unreported 9alpha,11alpha-epoxide ring, quivisianolide B 10 the corresponding delta(9(11)) double bond, and quivisianone 11 is a 17-keto seco-ring D compound.     

Phragmalin-type limonoids from the mangrove plant Xylocarpus granatum

Five new phragmalin-type limonoids, xyloccensins Q-U (1-5), along with xyloccensin P were isolated from the stem bark of the mangrove plant Xylocarpus granatum. Their structures were elucidated on the basis of extensive 1D and 2D NMR as well as IR and MS spectroscopic data analyses.     

Phragmalin limonoids from Chukrasia tabularis

Six phragmalin limonoids, named tabulalin and tabulalides A-E, were isolated from the root bark of Chukrasia tabularis (Meliaceae). Their structures were determined by spectroscopic methods, and their antifeedant properties evaluated.     

Structural elucidation of limonoids and steroids from Trichilia connaroides

Six limonoids, trijugins D-H (1-5) and methyl 8alpha-hydroxy-8,30-dihydroangolensate (6), two degraded limonoids, trichiconnarins A and B (7-8), and a pregnane steroid, 3beta,4alpha-dihydroxypregnan-21-one (9), along with the known trijugin C (10) and 3beta,4alpha-dihydroxypregnan-16-one (11) were isolated from twigs and leaves of Trichilia connaroides. Their structures were established on the basis of extensive spectroscopic analysis.     

Ring A-seco mosquito larvicidal limonoids from Turraea wakefieldii

Five novel limonoids, 1-5, were isolated from the root bark of Turraea wakefieldii and were characterized as tecleaninoid derivatives. This is the first report of the natural occurrence of tecleanin-type limonoids with a five-membered-ring A-seco structure for which we propose the name neotecleanins. The relative stereochemical structures of compounds 1-5 were established on the basis of NMR spectroscopy. The absolute stereochemical structure of 5 was confirmed by X-ray diffraction methods. In mosquito larvicidal assays, compounds 1, 2 and 4 showed dose-dependent larvicidal activity against larvae of Anopheles gambiae s.s.     

Tetracyclic triterpenoids from the leaves of Azadirachta indica

Two new tetracyclic triterpenoids zafaral [24,25,26,27-tetranorapotirucalla-(apoeupha)-6alpha-methoxy-7alpha-acetoxy-1,14-dien-3,16-dione-21-al] (1) and meliacinanhydride [24,25,26,27-tetranorapotirucalla-(apoeupha)-6alpha-hydroxy,11alpha-methoxy-7alpha,12alpha-diacetoxy,1,14,20(22)-trien-3-one] (2) have been isolated from the methanolic extract of neem leaves along with two known constituents nimocinol and isomeldenin. Their structures and the relative configurations were determined by spectroscopic methods ((1)H and (13)C NMR, IR, and MS) and 2D NMR experiments.     

Mechanisms of the vasorelaxant effect of 1-hydroxy-2, 3, 5-trimethoxy-xanthone, isolated from a Tibetan herb, Halenia elliptica, on rat coronary artery

1-Hydroxy-2, 3, 5-trimethoxyxanthone (HM-1) is a xanthone isolated from Halenia elliptica, a Tibetan medicinal herb. HM-1 (0.33-42.1 microM) produced a concentration-dependent relaxation in rat coronary artery rings pre-contracted with 1 microM 5-hydroxytryptamine (5-HT), with an EC(50) of 1.67+/-0.27 microM. Removal of the endothelium significantly affected the vasodilator potency of HM-1, resulting in 46% decrease in E(max) value. The endothelium-dependent effects of HM-1 was confirmed when its vasorelaxant effect was inhibited after addition of nitric oxide synthase (NOS) inhibitor N(omega)-nitro-l-arginine methyl ester (100 microM) or the soluble guanylate cyclase inhibitor 1H-[1, 2, 4] oxadiazolo [4,3-alpha] quinoxalin-1-one (ODQ, 10 microM). Atropine (100 nM), flurbiprofen (10 microM), propranolol (100 microM), pyrilamine (10 microM), cimetidine (10 microM) and SQ22536 (100 microM) had no effect on the vasorelaxant activity of HM-1 indicated the non-involvement of other receptor/enzyme systems. In endothelium-denuded coronary artery rings, the vasorelaxant effect of HM-1 was unaffected by potassium channel blockers such as tetraethylammonium (10 mM), iberiotoxin (100 nM), barium chloride (100 microM) and 4-aminopyridine (1 mM). The involvement of Ca(2+) channel in 5-HT-primed artery ring preparations incubated with Ca(2+)-free buffer was confirmed when HM-1 (9.93 microM) partially abolished the CaCl(2)-induced vasoconstriction (87% inhibition in intact-endothelium artery rings; 50% inhibition in endothelium-denuded rings). In the KCl-primed preparations incubated with Ca(2+)-free buffer, HM-1 (9.93 microM) produced a 27.3% inhibition in endothelium-denuded rings. HM-1 (3.31-33.1 microM) had minimal relaxant effects (14.4%-20.3%) on the contractile response generated by 10 microM phorbol 12,13-diacetate (PDA) in Ca(2+)-free solutions, suggesting minimal effects on intracellular Ca(2+) mechanisms. These findings suggest the vasodilator action of HM-1 involved both an endothelium-dependent mechanism involving NO and an endothelium-independent mechanism by inhibiting Ca(2+) influx through L-type voltage-operated Ca(2+) channels; a minor contribution to the effects of HM-1 may be related to inhibition of the protein kinase C-mediated release of intracellular Ca(2+) stores.     

Steroids from the leaves of Chinese Melia azedarach and their cytotoxic effects on human cancer cell lines

Three new (1-3) and several known (4-6) steroids were isolated from the leaves of Chinese Melia azedarach. The structures of the new compounds were elucidated by means of spectroscopic methods including 2D NMR techniques and mass spectrometry to be (20S)-5,24(28)-ergostadiene-3β,7α,16β,20-tetrol (1), (20S)-5-ergostene-3β,7α,16β,20-tetrol (2), and 2α,3β-dihydro-5-pregnen-16-one (3). The cytotoxicities of the isolated compounds against three human cancer cell lines (A549, H460, U251) were evaluated; only compounds 1, 2, and (20S)-5-stigmastene-3β,7α,20-triol (4) were found to show significant cyctotoxic effects with IC₅₀s from 12.0 to 30.1 μg/mL.     

C,O-bisglycosylapigenins from the leaves of Rhamnella inaequilatera

From the leaves of Rhamnella inaequilatera, three flavone C,O-bisglycosides, rhamnellaflavosides A, B and C, were isolated and their structures were elucidated based on their spectral data and chemical evidence.     

Usage of sewage effluent in irrigation of some woody tree seedlings. Part 3: Swietenia mahagoni (L.) Jacq.

A pot experiment was investigated to study the effect of sewage irrigation treatments (primary and secondary effluents) compared with tap water on the growth and chemical constituents of mahogany seedlings (Swietenia mahagoni (L.) Jacq.) as well as soil chemical properties. The experiment was conducted at a greenhouse in the nursery of Timber Trees Research Department of Sabahia, Horticultural Research Station in Alexandria, Egypt, from June 2003 to December 2004 for three irrigation periods (6, 12 and 18 months). The sewage effluent waters were taken from oxidation ponds located in New Borg EL-Arab city and used directly for irrigation.The primary effluent treatment was superior than other treatments in improving the growth parameters (plant height, stem diameter, leaf area, leaves number, fresh and dry weights of leaves, shoots and roots and shoot/root ratio) and showed the highest concentration and total uptake of N, P, K, Cd, Ni, Pb and Fe in plant parts, followed by secondary effluent then tap water. The data revealed that soil salinity in terms of electrical conductivity of saturated paste (EC), CaCO₃%, organic matter% and soluble anions and cations were influenced significantly by primary or secondary effluent treatment. The data also showed that the use of sewage effluent for irrigation increased N, P, K and DTPA-extractable-heavy metals (Cd, Cu, Ni, Pb, Fe, Mn and Zn). The effects of sewage effluent on growth parameters and elements content in plant parts and treated soil were more pronounced as water treatments were used for long period.The results suggested that the use of sewage effluent in irrigating mahogany trees grown on calcareous sandy loam soil was an important agriculture practice for improving soil properties, increasing fuel and timber production, and is an economic and safe way to dispose wastewaters.     

Lasianthionosides A-C, megastigmane glucosides from leaves of Lasianthus fordii

From the leaves of Lasianthus fordii, three megastigmane glucosides, lasianthionosides A, B and C, were isolated together with the known iridoid glucoside, asperuloside, deacetylasperuloside and methyl deacetyl-asperulosidate, and a megastigmane glucoside, citroside A. The structures have been elucidated based on spectroscopic analyses and/or X-ray crystallographic analysis.     

Isolation and characterization of 27-O-demethylrifamycin SV methyltransferase provides new insights into the post-PKS modification steps during the biosynthesis of the antitubercular drug rifamycin B by Amycolatopsis mediterranei S699

The gene rif orf14 in the rifamycin biosynthetic gene cluster of Amycolatopsis mediterranei S699, producer of the antitubercular drug rifamycin B, encodes a protein of 272 amino acids identified as an AdoMet: 27-O-demethylrifamycin SV methyltransferase. Frameshift inactivation of rif orf14 generated a mutant of A. mediterranei S699 that produces no rifamycin B, but accumulates 27-O-demethylrifamycin SV (DMRSV) as the major new metabolite, together with a small quantity of 27-O-demethyl-25-O-desacetylrifamycin SV (DMDARSV). Heterologous expression of rif orf14 in Escherichia coli yielded a 33.8-kDa polyhistidine-tagged polypeptide, which efficiently catalyzes the methylation of DMRSV to rifamycin SV, but not that of DMDARSV or rifamycin W. 27-O-Demethylrifamycin S was methylated poorly, if at all, by the enzyme to produce rifamycin S. The purified enzyme does not require a divalent cation for catalytic activity. While Ca(2+) or Mg(2+) inhibits the enzyme activity slightly, Zn(2+), Ni(2+), and Co(2+) are strongly inhibitory. The K(m) values for DMRSV and S-adenosyl-L-methionine (AdoMet) are 18.0 and 19.3 microM, respectively, and the K(cat) is 87s(-1). The results indicate that DMRSV is a direct precursor of rifamycin SV and that acetylation of the C-25 hydroxyl group must precede the methylation reaction. They also suggest that rifamycin S is not the precursor of rifamycin SV in rifamycin B biosynthesis, but rather an oxidative shunt-product.     

Polyoxypregnane glycosides from the flowers of Dregea volubilis

Three novel polyoxypregnane glycosides, volubiloside A, B and C (1-3), were isolated from the flowers of Dregea volubilis Linn., and their structures were elucidated as drevogenin D-3-O-beta-D-glucopyranosyl (1-->4)-6-deoxy-3-O-methyl-beta-D-allopyranosyl (1-->4)-beta-D-cymaropyranosyl (1-->4)-beta-D-cymaropyranoside, drevogenin D-3-O-beta-D-glucopyranosyl (1-->4)-6-deoxy-3-O-methyl-beta-D-allopyranosyl (1-->4)-beta-D-cymaropyranosyl (1-->4)-beta-D-digitoxopyranoside and drevogenin P-3-O-beta-D-glucopyranosyl (1-->4)-6-deoxy-3-O-methyl-beta-D-allopyranosyl (1-->4)-beta-D-cymaropyranosyl (1-->4)-beta-D-cymaropyranoside, respectively, on the basis of extensive NMR experiments, MALDI-TOF MS, and some chemical strategies.     

Isotheasaponins B1-B3 from Camellia sinensis var. sinensis tea leaves

Three saponins, isotheasaponins B1-B3, were isolated from the leaves of the tea plant Camellia sinensis var. sinensis, and their structures were determined to be theasapogenol B [beta-D-galactopyranosyl(1-->2)][beta-D-xylopyranosyl(1-->2)-alpha-L-arabinopyranosyl(1-->3)]-beta-D-gulcopyranosiduronic acid with two acyl groups by spectroscopic analysis.