New reports of cyanolipids from sapindaceous plants

Several previously uninvestigated species of the Sapindaceae were examined and found to contain cyanolipids and cyanogenic compounds. Several species from the Melianthaceae, Meliosmaceae and Hippocastanaceae were devoid of these substances.     

Novel synthesis of new pyrazole thioglycosides as pyrazomycin analogues

This study reports a novel method for the synthesis of a new class of pyrazole thioglycosides 7a-h as pyrazomycin analogues. These series of compounds were designed through the reaction of sodium 2-cyano-3-oxo-3-(4-substitutedphenylamino)prop-1-ene-1,1-bis(thiolate) salts 2 with phenyl hydrazine in ethanol at room temperature to give the corresponding sodium 5-amino-4-(substitutedphenylcarbamoyl)-1-phenyl-1H-pyrazole-3-thiolates 3a-d. The latter compounds were treated with tetra-acetylated glycosyl bromides 4a,b in DMF at ambient temperature to give the corresponding pyrazole thioglycosides 6a-h. Treatment of pyrazole salts 3a–d with hydrochloric acid at room temperature afforded the corresponding 3-mercaptopyrazole derivatives 5. The latter compounds were treated with tetra-acetylated glycosyl bromides 4 in sodium hydride-DMF to tolerate the S-glycosyl 6a-h compounds. Ammonolysis of the latters afforded the corresponding free thioglycosides 7a-h. The structures of the reaction products were elucidated based on spectral data and elemental analysis.     

Evaluation of the enantiomers of 1-octen-3-ol and 1-octyn-3-ol as attractants for mosquitoes associated with a freshwater swamp in Florida, U.S.A

Field studies were conducted at wooded wetlands in Gainesville, FL, U.S.A., to assess responses of natural populations of adult mosquitoes (Diptera: Culicidae) to American Biophysics MM-X and Coleman MD-2500 traps baited with enantiomers of 1-octen-3-ol, a naturally occurring compound, and 1-octyn-3-ol, a closely related synthetic compound. Overall, the same species of mosquitoes were attracted by all enantiomers, although the (R)-(+) isomer of octenol generally attracted more species, and it is the isomer produced in greatest proportion in nature. Traps baited with the R-enantiomer caught greater numbers of mosquitoes than those baited with the S-enantiomer of each compound, whereas traps baited with S-enantiomers were equally or slightly less attractive than those baited with carbon dioxide only.     

DNA and cholesterol biosynthesis in synchronized embryonic rat fibroblasts: I. Temporal relationships between HMG-CoA reductase activity,sterol biosynthesis and thymidine incorporation into DNA

Temporal relationships between hydroxymethylglutaryl-CoA reductase activity, biosynthesis of C₂₇ sterols, and [³H]thymidine incorporation into DNA were studied in a rat embryo fibroblast cell line synchronized by double thymidine block and cultured in cholesterol-containing medium. Cyclic variations of HMG-CoA reductase activity and C₂₇ sterols occurred, with two maxima in S and G₂M phases; the relative shortness of the G₁ phase (3 h) in these cells could be responsible for the shift of sterol synthesis in the S phase. No noticeable variation of the individual C₂₇ sterols was observed during the entire cell cycle. In each experiment, there was a good linear correlation between HMG-CoA reductase activity and C₂₇ sterol synthesis, but from one experiment to another, a given level of enzymatic activity led to varying levels of [2-¹⁴C]acetate incorporation into sterols. In our experimental conditions, total HMG-CoA reductase activity is measured, and the preceding observation could be explained by a varying degree of phosphorylation of the enzyme depending on the metabolic state of the cells at the start of the experiment. The cyclic variations of the enzyme activity seem to be due more to increased synthesis at given times of the cycle than to periodic dephosphorylation. We question the existence of a relationship between cell division and cyclic sterol synthesis occurring in cells cultured in cholesterol-containing medium.     

Cyanogenic and other glucosides in a neo-guinean bug Leptocoris isolata: Possible precursors in its host-plant

Two new glucosides, 3-β-d-glucopyranosyloxy-4-methyl-2(5H)-furanone and 4-β-d-glucopyranosyloxy-3-hydroxymethyl-butyronitril-2-en, were isolated from the hemolymph of adult Leptocoris isolata (Heteroptera). Besides these two compounds, the cyanogenic glucoside cardiospermin was found in whole adult bug extracts. The larvae contain the last two named compounds and a mixture of cyanolipids. Only the latter was found in the fruit of Allophylus cobbe, the host-plant of the insect. The possible relationship between the insect glucosides and the host-plant cyanolipids as well as their biological role is discussed.     

1-cyanoepithioalkanes: Major products of alkenylglucosinolate hydrolysis in certain cruciferae

Autolysis of glucosinolates in several crucifers produced 1-cyano-2,3-epithio-propane and 1-cyano-3,4-epithiopentane, in addition to the previously described 1-cyano-3,4-epithiobutane.     

Cyanolipids in Cordia verbenacea—a correction

Seeds of materials previously identified as Cordia verbenacea were re-examined and found to be from a sapindaceous plant, probably of the genus Allophyllus. The anomalous occurence of cyanolipids in this member of the Boraginaceae is thus resolved.     

Triterpenoids of Salvia horminum,constitution of a new diol

Lupeol, lup-(20)29-ene-2α,3β-diol and a new triterpenic alcohol olean-(13)18-ene-2β,3β-diol were isolated from the petrol extract of air dried Salvia horminum and their structures were determined.     

Characterization of Volatile Compounds in Astraeus spp.

Astraeus spp. is consumed in several regions of Southeast Asia. C₈ compounds, including 1-octen-3-ol, are the main volatile compounds in fresh Astraeus spp. Other compounds typical of edible mushrooms, such as terpenoids and sulfur-containing compounds, were not detected in fresh Astraeus spp. The amounts of fatty acids, including linoleic acid, substantially decreased after homogenization of fresh Astraeus spp. This high metabolic activity possibly correlates with formation of the C₈ volatiles. Heating the mushrooms produced cyclohexene compounds, 2-n-pentyl-furan, furanyl compounds, and benzaldehyde.     

Triterpenoids from two Mallotus species: a nor-triterpene and two new acids

The carbonyl compound, previously isolated from the stems of Mallotus paniculatus, has been proved to be 29-nor-21αH-hopane-3,22-dione. The light petrol extracts of both the leaves and stems of M. hookerianus have been found to contain friedelin, friedelan- 3β-ol and sitosterol, and the ethanol extract of the former two new triterpene acids, 3-oxours-12-ene-27,28-dioic and 3β,28-dihydroxyurs-12-en-27-oic acids.     

Flavan-3-ols from the barks of Barringtonia acutangula

1. Download : Download full-size image

     

21-hydroxypregna-1,4-diene-3,11,20-trione: A biliary metabolite of a cartilaginous fish, Raja sp.

21-Hydroxypregna-l,4-diene-3,ll,20-trione was isolated from skate bile and as an in vivo metabolite of ³H-lα-hydroxycorticosterone. Identity was established by chromatography and derivatization to constant ³H/¹⁴C ratio and mass spectrometry of the 20,21-acetonide. The new steroid was present in the free form and as the glucuronoside.     

Discovery of (E)-1-amino-4-phenylbut-3-en-2-ol derivatives as novel neuraminidase inhibitors

Neuraminidase has been considered as an important target for designing agents against influenza viruses. In a discovery of anti-influenza agents with epigoitrin as the initial lead compound, a series of 1-amino-2-alkanols were synthesized and biologically evaluated. The in vitro evaluation indicated that (E)-1-amino-4-phenylbut-3-en-2-ol (C1) had better inhibitory activities than 2-amino-1-arylethan-1-ol derivatives. To our surprise, sulfonation of C1 with 4-methoxybenzenesulfonyl chloride afforded more active inhibitor II with up to 6.4?μM IC₅₀ value against neuraminidase. Furthermore, docking of inhibitor II into the active site of NA found that the H atoms in both NH₂ and OH groups of inhibitor II were the key factors for potency. Molecular docking research did not explained very well the observed structure-activity relationship (SAR) from amino acid residue level, but also aided the discovery of (E)-1-amino-4-phenylbut-3-en-2-ol derivatives as novel and potent NA inhibitors.     

Resolution of (±)-trans-2-phenylcyclohexan-1-ol by lipases from Candida rugosa: effect of catalyst source and reaction conditions

Candida rugosa lipase resolved trans-2-phenylcyclohexan-1-ol. A commercial and a laboratory preparation were compared and better results were obtained with the latter (E >200). Both enzyme preparations were strongly dependent on the substrate concentration for their enantioselectivity. This effect could be due to the presence of an esterase activity unspecific for trans-2-phenylcyclohexan-1-ol. © Rapid Science Ltd. 1998     

Nor-sterols in Axinella proliferans, sponge from the Indian Ocean

An examination of the sterol mixture of the sponge Axinella proliferans collected in the Indian Ocean led to the isolation of nine A-nor-sterols, including two rare nor-sterols with a D-ring unsaturation. The known 3β-(hydroxymethyl)-A-nor-5α-cholest-15-ene has been identified by a comparison with mass spectrum and ¹H and ¹³C nuclear magnetic resonance (NMR) data of the sterol isolated from Homoaxinella trachys, a marine sponge collected in the Indian Ocean. A new sterol, 3β-(hydroxymethyl)-A-nor-5α-cholest-14-ene-16α-ol, has been identified by their mass and two-dimensional NMR spectra compared with those of the D-ring unsaturated sterol, 5α-cholest-14-ene-3β,16α-diol isolated from the Mediterannean sponge Topsentia aurantiaca.     

1-Cyano-3,4-epithiobutane: A major product of glucosinolate hydrolysis in seeds from certain varieties of Brassica campestris

A new hydrolysis product derived from 3-butenylglucosinolate in seeds of certain strains of Brassica campestris Yellow Sarson is described. The structure, 1-cyano-3,4-epithiobutane is proposed. If the seeds are heated at 115° for 30 min before hydrolysis, 3-butenyl isothiocyanate is the main product.     

New flavans isolated from the leaves and stems of Cratylia mollis (Leguminosae)

Cratylia mollis Mart ex. Benth is a species belonging to the Leguminosae family that exists throughout South America, and it is one of the most abundant plants in northeastern Brazil, especially in the semiarid region. This plant is popularly known as “camaratu” and “camaratuba”, and the leaves and stems of this species are used as a substitute for cattle's alimentation during the dry season. The chemical investigation of the methanolic extract from leaves and stems of C. mollis led to the isolation of new flavans named 4,2′,3′-trihydroxy-4′-methoxy-6,7-(methylenedioxy) isoflavan, 7,2′-dihydroxy-6-methoxyflavan, 7,3′-dihydroxy-6,2′-dimethoxyflavan, 7-hydroxy-6-methoxyflavan, 2′-hydroxy-6,7-(methylenedioxy) flavan, 2R*,3S*-7,2′-dihydroxy-6-methoxy-flavan-3-ol, and 2R*,3S*-7,3-dihydroxy-6,2′-dimethoxyflavan-3-ol and an unusual flavan (11H-benzofuro[3,2-b][1] benzopyran-2-methoxy,3-hydroxy,5a,10a-dihydro) named (3R*,2R*)-3-O-2′-7-hydroxy-6-methoxyflavan. The structures of the new compounds were determined using spectroscopic methods.     

Studies with a cloned Escherichia coli C 2-oxo-hept-3-ene-1,7-dioate hydratase gene

Abstract A cloned gene specifying the 2-oxo-hept-3-ene-1,7-dioate (OHED) hydratase of Escherichia coli C was used to produce large amounts of the hydratase enzyme. The enzyme was purified to homogeneity by a simple two-step procedure and some of its properties investigated. The first 34 residues at the amino terminus were sequenced and a mixture of oligonucleotides corresponding to the first six amino acid residues was constructed. This mixture was used as a probe to look for sequence homology in DNA obtained from various related organisms that had OHED hydratase activity. Strong hybridization was seen for E. coli strains B and C but E. coli strain W and Klebsiella pneumoniae M5a1 showed no detectable hybridization.     

Studies on Chemical Constituents of Lipid of Treraella fuciformis

An investigation of the chemical constituents of lipid of Tremella fuciformis Berk. is the central theme of this study. The sterols, fatty acids and phospholipids are separated by recrystallization, column chromatography and preparative thin layer chromatography, and their constituents are then identified by gas liquid chromatography and spectral data (UV, IR, MS and NMR). The results show that sterols comprise 16.8% ergosterol, 28.5% ergosta-5,7-dien-3β-ol and 54.7% ergost-7-en-3β-ol; fatty adds comprise 1.32%tmdeeanoic acid, 2.37% laurie acid, 1.28% tridecanoic acid, 0.09% myristic acid, 5.43% pentadecanoic acid, 17.20% palmitic acid, 3.11% stearic acid, 2.37% palmitoleic acid, 38.83% oleic acid and 27.98% linoleic acid; phospholipids comprise phosphatidylethanolamine, phosphatidylcholine phosphatidyl glycerol, phosphatidylserine and phosphati- dylinositol. Altogether there are seventeen constituents in the lipid.     

Eight-carbon volatiles in mushrooms and fungi: properties, analysis, and biosynthesis

Eight-carbon volatiles are ubiquitous among fungi and characteristic of the fungal aroma. They are the product of the oxidation and cleavage of the fatty acid linoleic acid and are classified as oxylipins, molecules taking part in a wide range of biological processes. Their involvement in the fungal aroma, interactions with pests and pathogens, and reproductive events are reviewed here, as well as the enzymic systems involved in their biosynthesis.