Malonylated glycerolipids from the glandular trichome exudate of Ceratotheca triloba.

Chemical investigation of the glandular trichome exudate from Ceratotheca triloba (Pedaliaceae) led to the identification of nine 1-O-acetyl-2-O-[(R)-3-acetyloxy-fatty acyl]-3-O-malonylglycerols. Among these, 1-O-acetyl-2-O-[(R)-3-acetyloxyicosanoyl]-3-O-malonylglycerol (7) was the most abundant constituent (41%), followed by 1-O-acetyl-2-O-[(R)-(3-acetyloxyoctadecanoyl)-3-O-malonylglycerol (2; 21%). Compounds having iso- and anteiso-type structures in the 3-acetyloxy-fatty acyl groups in the fatty acyl moiety were also characterized as minor constituents. This is the first report of the isolation of malonylated glycerolipids as natural products.

Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer.

Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components.

Papyriferic acid, an antifeedant triterpene from birch trees, inhibits succinate dehydrogenase from liver mitochondria.

Papyriferic acid (PA) is a triterpene that is secreted by glands on twigs of the juvenile ontogenetic phase of resin producing tree birches (e.g., Betula neoalaskana, B. pendula) and that deters browsing by mammals such as the snowshoe hare (Lepus americanus). We investigated the pharmacology of PA as a first step in understanding its antifeedant effect. After oral administration to rats, PA and several metabolites were found in feces but not urine, indicating that little was absorbed systemically. Metabolism involved various combinations of hydrolysis of its acetyl and malonyl ester groups, and hydroxylation of the terpene moiety. The presence of a malonyl group suggested a possible interaction with succinate dehydrogenase (SDH), a mitochondrial enzyme known to be competitively inhibited by malonic acid. The effect of PA on the oxidation of succinate by SDH was examined in mitochondrial preparations from livers of ox, rabbit, and rat. In all three species, PA was a potent inhibitor of SDH. Kinetic analysis indicated that, unlike malonate, PA acted by an uncompetitive mechanism, meaning that it binds to the enzyme-substrate complex. The hydrolysis product of PA, betulafolienetriol oxide, was inactive on SDH. Overall, the evidence suggests that PA acts as the intact molecule and interacts at a site other than the succinate binding site, possibly binding to the ubiquinone sites on complex II. Papyriferic acid was potent (K(iEIS) ranged from 25 to 45 microM in the three species) and selective, as malate dehydrogenase was unaffected. Although rigorous proof will require further experiments, we have a plausible mechanism for the antifeedant effect of PA: inhibition of SDH in gastrointestinal cells decreases mitochondrial energy production resulting in a noxious stimulus, 5-HT release, and sensations of nausea and discomfort. There is evidence that the co-evolution of birches and hares over a large and geographically-diverse area in Northern Europe and America has produced marked differences in the formation of PA by birches, and the tolerance of hares to dietary PA. The present findings on the metabolic fate and biochemical effects of PA provide a rational basis for investigating the mechanisms underlying differences among populations of hares in their tolerance of a PA-rich diet.

Inhibitory activities of lichen-derived compounds against methicillin- and multidrug-resistant Staphylococcus aureus.

The inhibitory effects of selected phenolic lichen substances were tested against a panel of methicillin- and multidrug-resistant Staphylococcus aureus. Depsidones with long alkyl chains on both of the aromatic rings were consistently active against the strains tested, comparable to or better than the level of clinically used antibacterial drugs. A similar level of activity was also observed for rhizocarpic acid. The previously described cytotoxic pentacyclic compound hybocarpone was by far the most active, exhibiting minimum inhibitory concentrations (MICs) of 4-8 microg/mL (8.13-16.3 microM) against a range of multidrug efflux pump expressing strains of S. aureus.

Two matrix metalloproteinases inhibitors from Ferula persica var. persica.

Matrix metalloproteinases (MMPs) play a role in several physiologic and pathologic events. There is some evidence indicating the involvement of MMPs in tumor invasion and inflammatory diseases. Here we studied the chloroform extract of Ferula persica var. persica. The influence of these extracts vs. a reference drug, diclofenac sodium, on MMP production by the fibrosarcoma cell line was investigated using an in vitro cytotoxicity assay, sodium dodecyl sulfate-polyacrylamide, and gelatin zymography. The total extract of the roots was found to exhibit a selective inhibitory effect on tumor cell invasion. The bioactivity-guided fractionation of this extract led to the isolation of two compounds. These compounds showed highest MMP inhibitory effect at minimal toxic dose levels. Using conventional spectroscopy methods, the active fractions were identified as t-butyl 3-[(1-methylthiopropyl)dithio]-2-propenyl malonate (persicasulphide B) and umbelliprenin, previously isolated from F. persica var. latisecta. Since inhibition of MMP activity has been employed in modality therapy in diseases such as cancer, this compound might be promising in the preparation of anti-MMP therapeutic derivatives.

Acylated anthocyanins from the violet-blue flowers of Orychophragonus violaceus.

Three acylated cyanidin 3-sambubioside-5-glucosides (1-3) were isolated from the violet-blue flowers of Orychophragonus violaceus, and their structures were determined by chemical and spectroscopic methods. Two of those acylated anthocyanins (1 and 3) were cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-acyl)-beta-D-glucopyranoside]-5-O-(6-O-malonyl-beta-D-glucopyranoside)s, in which the acyl groups were p-coumaric acid for 1, and sinapic acid for 3, respectively. The last anthocyanin 2 was cyanidin 3-O-[2-O-(2-O-(4-O-(6-O-(4-O-(beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-glucopyranosyl)-trans-caffeoyl)-beta-D-xylopyranosyl)-6-O-(4-O-(beta-D-glucopyranosyl)-trans-feruloyl)-beta-D-glucopyranoside]-5-O-beta-D-glucopyranoside. In these flowers, the anthocyanins 2 and 3 were present as dominant pigments, and 1 was obtained in rather small amounts.

Extraction of isoflavone malonylglucosides from Trifolium pratense L.

Extraction of isoflavone malonylglucosides from red clover (Trifolium pratense L.) is a complicated procedure. This is due to the relatively unstable character of the thermolabile glucoside malonates as well as by action of native beta-glucosidases, resulting in a rapid degradation of malonylated glucosides into their corresponding aglucones. In this study, Tris was identified as a suitable beta-glucosidase inhibitor in red clover extracts, optimized at 350 mM Tris in 80% ethanol at pH 7.2. Extraction of fresh red clover leaves using Tris increased the concentration of malonate conjugated isoflavones approximately 13 to 24 times as opposed to extraction without Tris. A comparison of isoflavone profiles obtained after extraction with and without Tris of different plant organs of red clover and several species within the family Fabaceae suggests that the amount and/or activity of the degenerative beta-glucosidase enzymes vary for the different plant parts of red clover and among the species studied. Therefore, the use of standard extraction methods may well result in overestimation of the concentration of aglucones and consequently underestimation of the malonylglucoside isoflavones concentration depending on the plant species and plant part studied.

Sulfur containing derivatives from Ferula persica var. latisecta.

Two new sulfur containing derivatives, t-butyl 3-[(1-methylpropyl)dithio]-2-propenyl malonate (1), t-butyl 3-[(1-methylthiopropyl)thio]-2-propenyl malonate (2) were isolated from the roots of Ferula persica Willd. var. latisecta D. F. Chamberlain. Their structures were elucidated by spectral methods.

7-O-6'-O-malonylcachinesidic acid, a new macrocyclic iridoid ester of malonic acid from the Tunisian plant Ajuga pseudoiva.

A new iridoid glucoside, 7-O-6'-O-malonylcachinesidic acid (1), was isolated from the leaves of Ajuga pseudoiva and characterized as its triacetyl derivative (1a). Its structure was established by spectroscopic methods and showed an unusual feature, in which an alcoholic function of the iridoid moiety and the primary alcohol of a glucopyranose unit form a 13-membered heterocycle with malonic acid.

[Separation of dicarboxylic acid by thin-layer chromatography].

Dicarboxylic acids (C2-C6) were detected on thin-layer chromatography of silica gel G after developing with V(benzene):V(acetic acid):V(water) = 50:40:10 for an hour by dipping the plate in a very short time. The chromogenic reagent was 0.1% bromocresol green alcohol solution adjusted to pH 7. The acid appeared as yellow spots on a blue background.

Malonofungin: an antifungal aminomalonic acid from Phaeoramularia fusimaculans.

In screening for antifungal metabolites, a novel compound, malonofungin, exhibiting growth inhibitory activity against Botrytis cinerea (grey mould), has been isolated from fermentations of Phaeoramularia fusimaculans CBS 616.87. Its structure is established as (E)-(3R,4S,5S)-5-acetoxy-2-amino-2-carboxy-3,4-dihydroxy-14-oxoicos++ +-6-enoic acid, representing an addition to the rare class of naturally occurring aminomalonic acids. 1H NMR data and extensive use of CD spectroscopy have been utilized to establish the absolute stereochemistry of malonofungin. The structural and biological relationship of malonofungin to previously reported fungal metabolites is discussed.

[Isolation and identification of flavonoids and organic acids from Gynostemma pentaphyllum Makino].

Three constituents were isolated from the aerial parts of Gynostemma pentaphyllum. They were identified as rutin (I), ombuoside (II) and malonic acid (III) by physico-chemical properties and spectroscopic methods. They are reported present in G.pentaphyllum for the first time.

The optimum condition for malonic dialdehyde liberation from smoked fish and curing smoke condensates.

The aim of this study was to establish the conditions for malonic dialdehyde liberation from smoked fish and curing smoke condensates, as well as to determine its content in smoked fish. The specific absorption peaks of coloured solutions of malonic dialdehyde, from curing smoke condensates, with 2-thiobarbituric acid were determined. The conditions for malonic dialdehyde liberation were established, i.e. time and degree of alkaline hydrolysis of condensate, degree of distillation of acidified condensate solution, the conditions of coloured solution development, determination of extinction and method of calculation of malonic dialdehyde content in smoked fish, in individual layers of smoked mackerel fillets. The mechanism of formation of polycyclic aromatic hydrocarbone and hydrogen peroxide or hydroxyl free radicals, formed during pyrolysis of organic compounds in the presence of liberated malonic dialdehyde, was proposed.

Determination of malonaldehyde in biological materials by high-pressure liquid chromatography.

An HPLC method is described for the determination of malonaldehyde in biological materials. The procedure involves extracting the sample with trichloracetic acid, heating the extract with thiobarbituric acid, separating the thiobarbituric acid-malonaldehyde complex on a mu Bondapak C18 column, and measuring the absorbance using a 546-nm interference filter. The method was found to be specific for malonaldehyde in several food and feed samples. Under routine assay conditions, a coefficient of variability of 7.0% was obtained for samples containing 1-2 microgram of malonaldehyde per gram (instrument detection limit 1 ng). This procedure yields lower values for the concentration of malonaldehyde in food samples than the conventional spectrophotometric procedure based on absorbance of the thiobarbituric acid-malonaldehyde complex at 532 nm.

[Distribution of carbenicillin, benzylpenicillin and phenylmalonic acid in an organic solvent-water system]. / Raspredelenie karbenitsillina, benzilpenitsillina i fenilmalonovoi kisloty v sisteme organicheskii rast voritel'-voda.

Distribution of carbenicillin, benzylpenicillin and phenylmalonic acid in butyl acetate-water and methylene chloride-water systems within wide ranges of pH of the aqueous phase was studied. The experimental data were reviewed taking into account the distribution between the phases of the compound molecules and dissociation of the acids in the aqueous solution. The distribution constants of the compound molecules were calculated to be 37 (the literature data), 11.6 and 5.2 for every antibiotic respectively in the first system and 10 and 0.24 for carbenicillin and benzylpenicillin in the second system (the value for phenylmalonic acid was not calculated). When the concentration of carbenicillin in butyl acetate is high, dimerization of the acid molecule in the nonaqueous phase should be taken into the account. The dimerization constant is equal to 16.6 M-1.