Chemical Constituents of the Culture Broth of Panus rudis

In our ongoing search for new secondary metabolites from fungal strains, one novel compound (1) and nine known compounds (2-10) were isolated from the EtOAc-soluble layer of the culture broth of Panus rudis. The culture broth of P. rudis was extracted in acetone and fractionated by solvent partition; column chromatography using silica gel, Sephadex LH-20, and Sephadex G-10; MPLC; and HPLC. The structures of isolated compounds were elucidated by one- and two-dimensional NMR and LC-ESI-mass measurements. One new compound, panepoxydiol (1), and nine known compounds, (E)-3-(3-hydroxy-3-methylbut-1-en-1-yl)-7-oxabicyclo[4.1.0]hept-3-ene-2,5-diol (2), isopanepoxydone (3), neopanepoxydone (4), panepoxydone (5), panepophenanthrin (6), 4-hydroxy-2,2-dimethyl-6-methoxychromane (7), 6-hydroxy-2,2-dimethyl-3-chromen (8), 2,2-dimethyl-6-methoxychroman-4-one (9), 3,4-dihydroxy-2,2-dimethyl-6-methoxychromane (10), were isolated from the culture broth of P. rudis. This is the first report of isolation of a new compound panepoxydiol (1) and nine other chemical constituents (2-5, 7-10) from the culture broth of P. rudis.     

6,7-epoxy-linalool and related oxygenated terpenoids from Carica papaya fruit

Oxygenated terpenoids derived from linalool, a major constituent of papaya fruit volatiles, were studied by HRGC and HRGC-MS. Using a sample preparation technique suitable for the separation and enrichment of polar compounds, the two diastereoisomers of 6,7-epoxy-linalool, 2,6-dimiethyl-octa-1,7-diene-3,6-diol, 2,6-dimethyl-octa-3,7-diene-2,6-diol, (E)- and (Z)-2,6-dimethyl-octa-2,7-diene-1,6-diol and 2,6-dimethyl-oct-7-ene-2,3,6-triol were identified. Additionally, each of four diastereoisomeric epoxy-linalool oxides in their furanoid and pyranoid forms were detected for the first time as natural plant constituents. Biogenetic pathways for formation and metabolism of the oxygenated linalool derivatives are discussed.     

New acyclic sesquiterpenoid derivatives and a monoterpene disaccharide from Dichondra repens Forst.

A new highly oxygenated acyclic sesquiterpenoid (2E, 6E)-8,10,11-trihydroxyl-7,11-dimethyl-3-hydroxymethyl-2,6-dodecadienoic acid (1) and its glucoside (2), together with a new pinane monoterpene disaccharide glucoside 6,6-dimethyl-2-methlenebicyclo [3.1.1]hept-3-O-(6-O-apiofuranosyl)-β-d-glucopyranoside (3) were isolated from hydrophilic extract of Dichondra repens. Their structures were elucidated on the basis of spectroscopic analyses and chemical methods. The three compounds did not show any cytotoxic activity (IC50 > 20 μM) against two human lung cancer cell lines (NCI-H661 and A549).     

Alkylpyrazines in ponerine ants: Their presence in three genera,and caste specific behavioural responses to them in Odontomachus troglodytes

Alkylpyrazines were found in the mandibular gland secretions of three Ethiopian ponerine ants. The major components in Odontomachus troglodytes were 2,6-dimethyl-3-n-butyl- and n-pentylpyrazine; in Anochetus sedilloti 2,6-dimethyl-3-sec-butyl- and 2,5-dimethyl-3-n-pentylpyrazine, and in Brachyponera sennaarensis 2,6-dimethyl-3-n-butyl and n-pentylpyrazines. The male caste in O. troglodytes contained 2,6-dimethyl-3-n-hexyl- and n-butylpyrazine. In O. troglodytes caste-specific behavioural differences were found between males and workers in response to gland equivalent quantities of their pheromones. The fragile males retreated from the alkylpyrazines whereas the workers were attracted to and attacked the pheromone source. Large quantities (5 gland equivalents) of pheromones were also repellent to the workers.     

The effect of 6-deoxy-D-fructose on flavour bioformation from strawberry (Fragaria x ananassa, cv. Elsanta) callus cultures

The biosynthesis of 2,5-dimethyl-4-hydroxy-2H-furan-3-one has been investigated in order to improve the flavour of cultivated strawberries. Callus cultures of strawberries have been established. The probable immediate precursor of 2,5-dimethyl-4-hydroxy-2H-furan-3-one (6-deoxy-D-fructose) has been fed to callus cultures and the levels of the product are compared in cultures fed with precursor and control tissues. The increased levels of 2,5-dimethyl-4-hydroxy-2H-furan-3-one-glucoside in the precursor fed cultures suggests that methylpentoses are key compounds for the biosynthesis of this specific furanone.     

Electrophysiological and Behavioral Responses of Male Fall Webworm Moths (Hyphantria cunea) to Herbivory-Induced Mulberry (Morus alba) Leaf Volatiles

Volatile organic compounds (VOCs) were collected from damaged and intact mulberry leaves (Morus alba L., Moraceae) and from Hyphantria cunea larvae by headspace absorption with Super Q columns. We identified their constituents using gas chromatography-mass spectrometry, and evaluated the responses of male H. cunea antennae to the compounds using gas chromatography-flame ionization detection coupled with electroantennographic detection. Eleven VOC constituents were found to stimulate antennae of male H. cunea moths: β-ocimene, hexanal, cis-3-hexenal, limonene, trans-2-hexenal, cyclohexanone, cis-2-penten-1-ol, 6-methyl-5-hepten-2-one, 4-hydroxy-4-methyl-2-pentanone, trans-3-hexen-1-ol, and 2,4-dimethyl-3-pentanol. Nine of these chemicals were released by intact, mechanically-damaged, and herbivore-damaged leaves, while cis-2-penten-1-ol was released only by intact and mechanically-damaged leaves and β-ocimene was released only by herbivore-damaged leaves. Results from wind tunnel experiments conducted with volatile components indicated that male moths were significantly more attracted to herbivory-induced volatiles than the solvent control. Furthermore, male moths'' attraction to a sex pheromone lure was increased by herbivory-induced compounds and β-ocimene, but reduced by cis-2-penten-1-ol. A proof long-range field trapping experiment showed that the efficiency of sex pheromone lures in trapping male moths was increased by β-ocimene and reduced by cis-2-penten-1-ol.     

Chemical constituents from the roots of Fallopia multiflora var. Ciliinerve

Phytochemical investigations on the roots of Fallopia multiflora var. Ciliinerve led to the isolation of eighteen compounds, including six chromones [2-methyl-5- carboxymethyl-7-hydroxychromone (1), 2-methyl-5-methylcarboxymethyl-7- hydroxychromone (2), 2,5-dimethyl-7-hydroxychromone (3), 2-methyl-5-hydroxymeth-yl-7-hydroxychromone (4), 2-methyl-5-carboxylicacid-7-hydroxy-chromone (5), and 2,5-dimethyl-7-hydroxychromone-7-O-β-D-glucopyranoside (6)], three lignans [Isolariciresinol (8), 5-[4-(3,4-dimethoxyphenyl)-2,3-dimethylbutyl]-1,3-benzodioxole (9), and isolariciresinol-9-O-β-D-xylopyranoside (10)], four anthraquinones [physcion-8-O-β-D-glucopyranoside (11), emodin-8-O-β-D-glucopyranoside (12), Rhein (13), and Chrysophanol (14)], three isobenzofurans [5,7-dihydroxy-isobenzofuran (15), 5-methoxy-7-hydroxy-isobenzofuran (16), and 5-methoxy-isobenzofuran-7-O-β-D-glucoside (17)], one phenolic acid [2,5-diacethylhy-droquinone (7)], and one pyran [Zanthopyranone (18)]. Among them, compounds 1, 3, 6, 13 and 14 were reported from F. multiflora var. Ciliinerve for the first time, compounds 2, 8, 10 and 15–17 were isolated from the genus Fallopia for the first time, and compounds 4, 9 and 18 were isolated for the first time from Polygonaceae family. Furthermore, the isolation of compounds 5 and 7 were reported for the first time in plants. Their structures were identified by spectroscopic methods and compared with those previously published. The chemotaxonomic significance of these isolated compounds has also been discussed.     

Ent-beyerene and ent-atisene diterpenes from viguiera insignis

The new diterpenes, ent-beyer-15-ene-12α,19-diol and ent-atis-13-en-3β,16α-diol, were isolated as minor constituents from the aerial part of Viguiera insignis. The structures were established by biomimetic transformation, spectroscopic means and comparison with closely related compounds.     

Volatile constituents of four Inula species of Bulgarian origin

In this study the volatile components of four Inula species (Inula germanica L., I. bifrons (L.) L., I. ensifolia L., and I. salicina L.) were analysed by GC-FID/MS. A total of 141 chemical compounds were identified. A distinct volatile chemical profiles with high variation in the type of compounds was observed. Inula germanica was rich in oxygenated monoterpenes (54.7%), with cis-carvyl acetate (20.7%) and 1,8-cineole (14.6%) as main components. Sesquiterpenoids dominated in I. bifrons (60.3%), while the relatively high percentage of fatty acids characterized the other two species I. ensifolia and I. salicina (44.1 and 39.8%, respectively). Principal component analysis (PCA) and cluster analysis (CA) were used to investigate the variations in the volatiles of different Inula species.     

Volatile aroma constituents of parsley leaves

The aroma volatiles of a desert parsley were analysed using routine procedures, and 45 constituents were positively identified, including 11 not previously reported as parsley leaf volatiles. One component, 2-(p-tolyl)propan-2-ol, is a new aroma volatile and, together with p-mentha- 1,3,8-triene, may be unique to parsley. Major constituents of the sample were 4-methoxy-6-(prop-2-enyl)benzo-1,3-dioxolan (myristicin) 4,7-dimethoxy-5-(prop-2-enyl)benzo-1,3 dioxolan (apiole), β-phellandrene, p-mentha-1,3,8-triene and 4-isopropenyl-1-methylbenzene. Aroma assessments during GC showed that apiole, in particular, had desirable parsley odour character.     

1,4-Dioxane-2,5-dione-type monomers derived from l-ascorbic and d-isoascorbic acids. Synthesis and polymerisation

l-Ascorbic and d-isoascorbic acids have been used as the starting materials for the preparation of (3R,4′S)-3-(2′,2′-dimethyl-1′,3′-dioxolan-4′-yl)-1,4-dioxane-2,5-dione (IPTA), (3R and S, 4′S,6R)-3-methyl-6-(2′,2′-dimethyl-1′,3′-dioxolan-4′-yl)-1,4-dioxane-2,5-dione (IPTP) and (3R,4′R)-3-(2′,2′-dimethyl-1′,3′-dioxolan-4′-yl)-1,4-dioxane-2,5-dione (IPEA), three novel 1,4-dioxane-2,5-dione-type monomers. Ring-opening homopolymerisation and copolymerisation of the IPTA monomer, derived from l-ascorbic acid, with d,l-lactide have been performed. The polymers were characterised by elemental microanalysis, as well as IR and ¹H and ¹³C NMR spectroscopies. GPC was used to estimate product molecular weights, and thermal studies (DSC and TGA) revealed that all the polymers were amorphous, being stable up to 250 °C under nitrogen.     

Antimicrobial chemicals in hoopoe preen secretions are produced by symbiotic bacteria

Animals frequently use metabolites produced by symbiotic bacteria as agents against pathogens and parasites. Secretions from the preen gland of birds are used for this purpose, although its chemicals apparently are produced by the birds themselves. European hoopoes Upupa epops and green woodhoopoes Phoeniculus purpureus harbour symbiotic bacteria in the uropygial gland that might be partly responsible for the chemical composition of secretions. Here we investigate the antimicrobial activity of the volatile fraction of chemicals in hoopoe preen secretions, and, by means of experimental antibiotic injections, test whether symbiotic bacteria living within the uropygial gland are responsible for their production. Hoopoes produce two different kinds of secretions that differ drastically in their chemical composition. While the malodorous dark secretions produced by nestlings included a complex mix of volatiles, these chemicals did not appear in white secretions produced by non-nesting birds. All volatiles detected showed strong antibacterial activity, and a mixture of the chemicals at the concentrations measured in nestling glands inhibited the growth of all bacterial strains assayed. We found support for the hypothesized role of bacteria in the production of such antimicrobial chemicals because experimental clearance of bacteria from glands of nestlings with antibiotics resulted in secretions without most of the volatiles detected in control individuals. Thus, the presence of symbiotic bacteria in the uropygial gland provides hoopoes with potent antimicrobials for topical use.     

Phytochemical study of Capraria biflora L. aerial parts (Scrophulariaceae) from Martinique island (French West Indies)

Aerial parts of Capraria biflora L. were collected in Martinique (French West Indies) and extracted by methanol. Two original chlorinated iridoids, 3-hydroxymyopochlorin (1) and 5-hydroxyglutinoside (2) were isolated by CPC (centrifugal partition chromatography) and characterized from the extract together with five known iridoid glycosides (3–7), two flavonoid glucuronides (8–9) and the phenylethanoid glycoside verbascoside (10). The structure of these compounds together with their relative configuration was established by spectroscopic data including in particular 1D and 2D NMR experiments (HSQC, HMBC, NOESY) and HRESIMS. Preliminary antibacterial evaluation of 1, 2 and 3 against a panel of Gram-positive and Gram-negative strains has been performed.     

Chemical composition of Crepis foetida L. and C. rubra L. volatile constituents and evaluation of the in vitro anti-inflammatory activity of salicylaldehyde rich volatile fraction

The genus Crepis L. (Asteraceae) comprises more than 200 currently recognized species. Several studies have been conducted on non-volatile phytochemicals of Crepis spp., featuring mainly sesquiterpene lactones and phenolic derivatives. Nevertheless, no report has been made on assessing the volatile constituents of the genus. Therefore, the present study is the first report to the chemical composition of the volatile constituents of two odoriferous Crepis spp., namely C. foetida L. and C. rubra L. Flowers and stems with leaves volatiles were analysed separately by gas chromatography coupled with mass spectrometry. In total, 37 volatile compounds were detected. Salicylaldehyde, carvacrol and aliphatic hydrocarbons are the main components of both C. foetida fractions, however C. rubra flowers are characterized by the abundance of β-sitosterol and eicosanoic acid, while the stems-leaves volatiles revealed to be more complex with hydrocarbons as main constituents.In addition, we investigated the salicylaldehyde rich volatile fraction for its in vitro activity on TNF-α induced ICAM-1 expression.     

Chrysoeriol derivatives and other constituents from Glandularia selloi

Glandularia selloi (Verbenaceae) presents phenylethanoids, iridoids and flavone glycosides as the main constituents. Two novel chrysoeriol derivatives, selloiside A (1) and selloiside B (2) were isolated from the methanolic extract of the aerial parts. Both flavones are acylated disaccharides. Two known compounds, verbascoside (3) and 6β-hydroxy-ipolamiide (4), were isolated from the methanolic extract of the roots. The structures were elucidated using 1D, 2D NMR and MS. Acylflavones have taxonomic significance since they occur mainly is species from the order Lamiales, specifically from the family Lamiaceae, closely related to Verbenaceae. The compounds 1 – 4 and the methanolic extract were investigated for antichemotactic activity.     

Comparative study of the dufour gland secretions of workers of four species of Myrmica ants

The Dufour gland secretions of myrmica rubra, M. ruginodis, M. sabuleti and M. scabrinodis have been studied. The most volatile portions of the secretion of workers of all four species were found to be similar, containing C₂C₄ oxygenated compounds. The less volatile portion consists of a mixture of hydrocarbons. In M. ruginodis this is chiefly a mixture of linear saturated and mono-unsaturated hydrocarbons, similar in composition to that of M. rubra, while in M. sabuleti it consists of (Z,E)-α-farnesene and its homologues, homofarnesene, bishomofarnesene and trishomofarnesene, similar in composition to that of M. scabrinodis. Workers of each species studied were attracted to the Dufour gland volatiles of all four species, these substances chiefly causing an increase in running speed, with the workers not distinguishing between conspecific and allospecific secretions, though small quantitative differences could be demonstrated between the speed and orientation reaction of workers of each species. The less volatile fraction of the Dufour gland secretion is used for territorial marking by foraging workers. This marking is specific for each species except between M. rubra and M. ruginodis.     

Inhibitors of sterol synthesis. Chemical syntheses, properties and effects of 4,4-dimethyl-15-oxygenated sterols on sterol synthesis and on 3-hydroxy-3-methylglutaryl coenzyme A reductase activity in cultured mammalian cells

The chemical syntheses of a number of 4,4-dimethyl substituted 15-oxygenated sterols have been pursued to permit evaluation of their activity in the inhibition of the biosynthesis of cholesterol and other biological effects. Described herein are the first chemical syntheses of 4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-en-3 beta-ol-15-one, 3 beta,15 alpha-diacetoxy-4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-ene, 3 beta-acetoxy-4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-en-15 beta-ol, 4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-ene-3 beta,15 alpha-diol, 4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-ene-3 beta,15 beta-diol, 4,4-dimethyl-14 alpha-ethyl-5 alpha-cholest-7-en-15 alpha-ol-3-one, 3 beta-benzoyloxy-4,4-dimethyl-5 alpha-cholest-8(14)-ene-7 alpha,15 alpha-diol, 7 alpha,15 alpha-diacetoxy-3 beta-benzoyloxy-4,4-dimethyl-5 alpha-cholest-8(14)-ene, 4,4-dimethyl-5 alpha-cholest-8(14)-en-3 beta-ol-15-one and 3 beta,7 alpha,15 alpha-tri-o-bromobenzoyloxy-5 alpha-cholest-8(14)-ene. Also prepared for use in the biological experiments were 4,4-dimethyl-5 alpha-cholest-7-ene-3 beta,15 alpha-diol, 4,4-dimethyl-5 alpha-cholest-8-ene-3 beta,15 alpha-diol and 4,4-dimethyl-5 alpha-cholest-8(14)-ene-3 beta,7 alpha,15 alpha-triol. The effects of twelve 4,4-dimethyl substituted 15-oxygenated sterols and of four 4,4-dimethyl substituted 32-oxygenated sterols on sterol synthesis and on the level of 3-hydroxy-3-methylglutaryl coenzyme A reductase activity were evaluated in mouse L cells. With the exception of 4,4-dimethyl-5 alpha-cholest-8(14)-ene-3 beta,7 alpha,15 alpha-triol, all of the 4,4-dimethyl substituted 15-oxygenated sterols caused a 50% inhibition of sterol synthesis at less than 10(-6) M and six of the 4,4-dimethyl substituted 15-oxygenated sterols caused a 50% inhibition of sterol synthesis at less than 10(-7) M. 4,4-Dimethyl-14 alpha-ethyl-5 alpha-cholest-7-ene-3 beta,15 alpha-diol caused a 50% decrease in sterol synthesis at 10(-8) M. The potencies of the 4,4-dimethyl substituted 15-oxygenated and C-32-oxygenated sterols with respect to inhibition of sterol synthesis and suppression of 3-hydroxy-3-methylglutaryl coenzyme A reductase activity have been compared with those of the corresponding sterols lacking the 4,4-dimethyl substitution.     

Volatile constituents of alphonso mango (mangifera indica)

Concentrates of fresh, ripe Indian Alphonso mango fruit were analysed by HRGC and HRGC/MS. In total, 152 aroma substances were identified, of which 70 are reported for the first time as mango fruit constituent. Quantitative HRGC revealed a considerable quantity of aroma compounds (ca 57 mg/kg fresh fruit pulp) of which 90% consisted of mono- and sesqui-terpene hydrocarbons. Major constituents included (Z)-(44 mg/kg) and (E)-ocimene (3 mg/kg) and 2,5-dimethyl-4-hydroxy-3(2H)-furanone (2 mg/kg)     

Effect of Some Xenobiotics on the Activities of Enzymes Relating to the Glucuronic Acid Pathway and on the Ascorbic Acid Metabolism in Guinea Pigs

An improvement to the aroma and taste of Burley cigarettes was achieved by adding volatiles from roasted, Japanese flue-cured tobacco. The addition of roasted tobacco volatiles was also found to decrease the offensive odor and taste. Among the fractions obtained from silica gel column chromatography of roasted tobacco volatiles, Fr. 8 (diethyl ether elution) exhibited the best improvement to the organoleptic properties of cigarette smoke. A great part of the improvement was attributable to 4-hydroxy-2,5-dimethyl-3(2H)-furanone and 3-hydroxy-4,5-dimethyl-2(5H)-furanone, both found in small amounts in Fr. 8 but possessing a strong impact on the olfactory properties.     

Further iridoids from the roots of Patrinia scabra

Two new iridoids, 1,3-dimethoxy-4,7-dimethyl-octahyhro-cyclopenta[c]pyran-6,7-diol (1) and isovillosol (2), together with two known compounds, were isolated from the roots of Patrinia scabra. Their structures were elucidated by different spectroscopic methods including IR, HRESIMS, 1D and 2D NMR experiments as well as X-ray crystallography.