Perezone and its phenyl glycine derivative induce cytotoxicity via caspases on human glial cancer cells.

The new phenyl glycine derivative of perezone was obtained in a single reaction step in . 80% yield which showed remarkable cytotoxic activity against the astrocytoma U-251 cell line. After 24 h of exposure, both perezone (IC = 6.

Minimizing the risk of deducing wrong natural product structures from NMR data.

There continues to be a disturbing number of natural products reported in the literature whose structures are incorrect. At least in part, this reflects the fact that many natural product chemists have limited formal nuclear magnetic resonance training. Gaps in training and lack of awareness regarding the challenges and ambiguities associated with two-dimensional nuclear magnetic resonance data interpretation can easily lead to errors in structure elucidation.

Synthesis, Crystallography, and Anti-Leukemic Activity of the Amino Adducts of Dehydroleucodine.

Dehydroleucodine is a bioactive sesquiterpene lactone. Herein, four dehydroleucodine amino derivatives were synthesized using the amines proline, piperidine, morpholine, and tyramine, and spectroscopic methods and single-crystal X-ray diffraction unambiguously established their structures. The cytotoxic activity of these compounds was evaluated against eight acute myeloid leukemia cell lines, and their toxicity to peripheral blood mononuclear cells was also determined.

Full Structural Characterization of Homoleptic Complexes of Diacetylcurcumin with Mg, Zn, Cu, and Mn: Cisplatin-level Cytotoxicity in Vitro with Minimal Acute Toxicity in Vivo.

At the present time, scientists place a great deal of effort worldwide trying to improve the therapeutic potential of metal complexes of curcumin and curcuminoids. Herein, the synthesis of four homoleptic metal complexes with diacetylcurcumin (DAC), using a ligand designed to prevent the interaction of phenolic groups, rendering metal complexes through the β-diketone functionality, is reported. Due to their physiological relevance, we used bivalent magnesium, zinc, copper, and manganese for complexation with DAC.

The role of computer-assisted structure elucidation (CASE) programs in the structure elucidation of complex natural products.

Covering: up to the end of December, 2018 There are still a disturbing number of incorrect natural product structure elucidations reported in the literature. The use of Computer-Assisted Structure Elucidation (CASE) programs can minimize this risk by generating all structures that are consistent with the input data and by ranking these structures in order of probability. They can successfully determine structures for complex natural products, with the possible exception of compounds with very few protons.

The influence of sulfur configuration in H NMR chemical shifts of diasteromeric five-membered cyclic sulfites.

The effect of the stereochemistry of the sulfur atom on H chemical shifts of the diasteromeric pair of cyclic sulfites of 4-[methoxy(4-nitrophenyl)methyl]-5-phenyl-1,3,2-dioxathiolan-2-oxide was investigated. The complete H and C NMR spectral assignment was achieved by the use of one-dimensional and two-dimensional NMR techniques in combination with X-ray data. A correlation of experimental data with theoretical calculations of chemical shift tensors using density functional theory and topological theory of atoms in molecules was made.

Resin glycosides from Ipomoea tyrianthina and their sedative and vasorelaxant effects.

The methanol-soluble extract from the root of Ipomoea tyrianthina was studied in order to isolate compounds with activity on the central nervous system and vasorelaxant effects. Chromatographic methods were used to isolate and purify seven new glycolipids (2-8). The structures of compounds 1-8 were elucidated by a combination of NMR spectroscopy and mass spectrometry.

CRAPT: an improved version of APT with compensation for variations in JCH.

A modified version of the attached proton test (APT) sequence for (13)C spectral editing, which we call CRisis-APT (CRAPT), is developed and tested on representative organic compounds. CRAPT incorporates (13)C compensation for refocusing inefficiency with synchronized inversion sweeps (CRISIS) pulses in combination with (1)H broadband inversion pulses to give improved compensation for variations in (1)JCH along with improved refocusing efficiency. It is shown that CRAPT gives edited (13)C spectra with only small losses in sensitivity (between 8% and 15% for strychnine, 1, menthol, 2, cholecalciferol, 3, and isotachysterol, 4), compared with basic (13)C spectra obtained on the same compounds.

Using NMR to identify and characterize natural products.

Over the past 28 years there have been several thousand publications describing the use of 2D NMR to identify and characterize natural products. During this time period, the amount of sample needed for this purpose has decreased from the 20-50 mg range to under 1 mg. This has been due to both improvements in NMR hardware and methodology.

The potential of Cyathus africanus for transformation of terpene substrates.

The insecticidal sesquiterpenes cadina-4,10(15)-dien-3-one and aromadendr-1(10)-en-9-one were administered to the fungus Cyathus africanus ATCC 35853. Biotransformation of the former produced (4R)-9α-hydroxycadin-10(15)-en-3-one, while the latter gave 2β-hydroxyaromadendr-1(10)-en-9-one, 2α-hydroxyaromadendr-1(10)-en-9-one and 10α-hydroxy-1β,2β-epoxyaromadendran-9-one. The bioconversion of santonin led to the production of two analogues, 11,13-dihydroxysantonin and the hitherto unreported 8α,13-dihydroxysantonin, while cedrol yielded 3β,8β-dihydroxycedrane and 3α,8β-dihydroxycedrane.

Variable-temperature ¹H-NMR studies on two C-glycosylflavones.

Two known C-glycosylflavones, swertisin and embinoidin, were isolated from the leaves of Anthurium aripoense, and characterized by room temperature 1D and 2D NMR experiments. At this temperature, the ¹H- and ¹³C-NMR spectra of these C-glycosylflavones revealed doubling of signals, which suggested the presence of two rotamers in solution. Variable-temperature (VT) ¹H-NMR studies supported this hypothesis.

Entrapment of mycelial fragments in calcium alginate: a general technique for the use of immobilized filamentous fungi in biocatalysis.

Transformation reactions on 3β,17β-dihydroxyandrost-5-ene using free fungal cells were compared with those carried out by macerated mycelia, immobilized in calcium alginate beads. Six fungi were utilized in this study, namely Rhizopus oryzae ATCC 11145, Mucor plumbeus ATCC 4740, Cunninghamella echinulata var. elegans ATCC 8688a, Aspergillus niger ATCC 9142, Phanerochaete chrysosporium ATCC 24725 and Whetzelinia sclerotiorum ATCC 18687.

Stemodin-derived analogues with lipid peroxidation, cyclooxygenase enzymes and human tumour cell proliferation inhibitory activities.

A series of analogues, derived from the antiviral and cytotoxic diterpene stemodin, were prepared and evaluated for their lipid peroxidation (LPO), cyclooxygenase enzyme-1 (COX-1) and -2 (COX-2), and tumour cell proliferation inhibitory activities. Oxidation of stemodin produced stemodinone, which was then converted to stemod-12-en-2-one. Reaction of the latter under Petrow conditions (bromine; silver acetate/pyridine) yielded mainly dibrominated abeo-stachanes.

Limonoids from Meliaceae with lipid peroxidation inhibitory activity.

In this study the antioxidant activity of natural limonoids from Meliaceae swietenolide (1), 3,6-O,O-diacetylswietenolide (2), swietenine (3), swietemahonin G (4) and 2-hydroxyswietenine (5) were investigated along with the semi-synthetic analogues (6-25) of compounds 1, 3-4. Lipid peroxidation (LPO) inhibitory assays revealed 85.6, 13.

Sesquiterpene lactones from Gynoxys verrucosa and their anti-MRSA activity.

Ethnopharmacological Relevance: Because of its virulence and antibiotic resistance, Staphylococcus aureus is a more formidable pathogen now than at any time since the pre-antibiotic era. In an effort to identify and develop novel antimicrobial agents with activity against this pathogen, we have examined Gynoxys verrucosa Wedd (Asteraceae), an herb used in traditional medicine in southern Ecuador for the treatment and healing of wounds.

Materials And Methods: The sesquiterpene lactones leucodine (1) and dehydroleucodine (2) were extracted and purified from the aerial parts of Gynoxys verrucosa, and their structure was elucidated by spectroscopic methods and single-crystal X-ray analysis.

Hydroxylation of steroids by Fusarium oxysporum, Exophiala jeanselmei and Ceratocystis paradoxa.

The potential of Fusarium oxysporum var. cubense UAMH 9013 to perform steroid biotransformations was reinvestigated using single phase and pulse feed conditions. The following natural steroids served as substrates: dehydroepiandrosterone (1), pregnenolone (2), testosterone (3), progesterone (4), cortisone (5), prednisone (6), estrone (7) and sarsasapogenin (8).

Tetranortriterpenoids from Spathelia sorbifolia (Rutaceae).

Two new tetranortriterpenoids were obtained by chromatography of the acetone extract of the wood of Spathelia sorbifolia L.; these compounds were characterized as their p-bromobenzoyl derivatives (2, 3). This extract also yielded a known tetranortriterpenoid and the chromones allopteroxylin, spatheliabischromene and anhydrosorbifolin.

The signal/noise of an HMBC spectrum can depend dramatically upon the choice of acquisition and processing parameters.

The effect of various acquisition and processing parameters on the sensitivity of HMBC spectra for typical organic molecules has been systematically investigated. For molecules in the 200-600 molecular weight range, an acquisition time of 0.2 to 0.

Analysis of Salvia coccinea from Jamaican populations.

This is the first report of a phytochemical investigation of Jamaican populations of a local folk medicinal plant Salvia coccinea (Lamiaceae/Labiatae). Apart from the presence of 3-sitosterol, phytochemical profiling of the aerial parts yielded compounds other than those previously reported from Indian and Italian populations. The triterpenes betulinic acid and betulin, the phytosterols beta-sitosterol and beta-sitosterol-3-O-beta-D-glucopyranoside, as well as the steroid precursor squalene were isolated.

Sesquiterpene and acyclic diterpenes from Hyptis verticillata Jacq.

From the methanolic extract of the plant Hyptis verticillata Jacq, was isolated five compounds: the novel compounds cadina-10(15)-en-3-one and 3,7,11,15-tetramethylhexadec-1-en-3-ol and the known compounds 3,7,11,15-tetramethylhexadec-2-en-1-ol, 7,11,15-trimethyl-3-methylenehexadecane-1,2-diol and myo-inositol. All structures were established by spectroscopic means.

Abietane diterpeniods from Hyptis verticillata.

Seven abietane diterpenoids were isolated from the roots of Hyptis verticillata (Labiatae). One is a novel natural product, 7-acetoxy-16-benzoxy-12-hydroxyabieta-8,12-diene-11,14-dione (1), while the other six known compounds are 11,14 dihydroxy-12-methoxyabieta-8,11,13-triene-7-one (2), 11,14-dihydroxy-12-methoxy- 18(4-->3betaH) abeo-abieta-4(19),8,11,13-tetraene-7-one (3), 7-acetoxy-12-methoxyabieta-8,12-diene-11,14-dione (4), royleanone (5), 7,6-dehydroroyleanone (6) and 7-acetoxyhorminone (7). All structures were elucidated by spectroscopic and mass spectrometric means.

Crotogossamide, a cyclic nonapeptide from the latex of Croton gossypifolius.

A new cyclic nonapeptide, crotogossamide (1), was isolated from the latex of Croton gossypifolius. Its structure was elucidated by use of 1D and 2D NMR and MS and by hydrolysis followed by GC-MS analysis as cyclo(-Gly(1)-Ala(2)-Ser(3)-Gly(4)-Leu(5)-Asn(6)-Gly(7)-Ile(8)-Phe(9)-). This is the first report of a cyclic peptide from a Croton species.

Steroid hydroxylation by Whetzelinia sclerotiorum, Phanerochaete chrysosporium and Mucor plumbeus.

The fungi Whetzelinia sclerotiorum ATCC 18687, Phanerochaete chrysosporium ATCC 24725 and Mucor plumbeus ATCC 4740 were examined for their ability to perform steroid biotransformations under single phase, pulse feed conditions. The steroids 3beta-hydroxyandrost-5-en-17-one (dehydroepiandrosterone) (1), 17beta-hydroxyandrost-4-en-3-one (testosterone) (5), 3beta-hydroxypregn-5-en-20-one (pregnenolone) (3), pregn-4-ene-3,20-dione (progesterone) (9), 17alpha,21-dihydroxypregn-4-ene-3,11,20-trione (cortisone) (11), 17alpha,21-dihydroxypregna-1,4-diene-3,11,20-trione (prednisone) (14), and 3-hydroxyestra-1,3,5(10)-trien-17-one (estrone) (15) were fed to each fungus. The production of a number of novel metabolites is reported.