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A nematicidal toxin was purified fromPleurotus ostreatus NRRL 3526 grown on moistened, autoclaved wheat straw for 30 days at room temperature (21-33°C). The active compound, at a concentration of 300 ppm, immobilized 95% of test nematodes (Panagrellus redivivus) within 1 hr. Immobilized nematodes did not recover, even after being rinsed with deionized water. The toxin was identified astrans-2-decenedioic acid.

An isomeric mixture of linoleic acid hydroperoxides, 13‐hydroperoxy‐cis‐9,trans‐11‐octadecadienoic acid (79%) and 9‐hydroperoxy‐cis‐12,trans‐10‐octadecadienoic acid (21%), was decomposed homolytically by Fe(II) in an ethanol‐water solution. In one series of experiments, the hydroperoxides were decomposed by catalytic concentrations of Fe(II). The 10−5 M Fe(III) used to initiate the decomposition was kept reduced as Fe(II) by a high concentration of cysteine added to the reaction in molar excess of the hydroperoxides. Nine different monomeric (no detectable dimeric) fatty acids were identified from the reaction. Analyses of these fatty acids revealed that they were mixtures of positional isomers identified as follows: (I) 13‐oxo‐trans,trans‐(andcis,trans‐) 9,11‐octadecadienoic and 9‐oxo‐trans,trans‐ (andcis,trans‐) 10,12‐octadecadienoic acids; (II) 13‐oxo‐trans‐9,10‐epoxy‐trans‐11‐octadecenoic and 9‐oxo‐trans‐12, 13‐epoxy‐trans‐10‐octadecenoic acids; (III) 13‐oxo‐cis‐9,10‐epoxy‐trans‐11‐octadecenoic and 9‐oxo‐cis‐12, 13‐epoxy‐trans‐10‐octadecenoic acids; (IV) 13‐hydroxy‐9,11‐octadecadienoic and 9‐hydroxy‐10,12‐octadecadienoic acids; (V) 11‐hydroxy‐trans‐12, 13‐epoxy‐cis‐9‐octadecenoic and 11‐hydroxy‐trans‐9, 10‐epoxy‐cis‐12‐octadecenoic acids; (VI) 11‐hydroxy‐trans‐12, 13‐epoxy‐trans‐9‐octadecenoic and 11‐hydroxy‐trans‐9,10‐epoxy‐trans‐12‐octadecenoic acids; (VII) 13‐oxo‐9‐hydroxy‐trans‐10‐octadecenoic acids; (VIII) isomeric mixtures of 9, 12, 13‐dihydroxyethoxy‐trans‐10‐octadecenoic and 9, 10, 13‐dihydroxyethoxy‐trans‐11‐octadecenoic acids; and (IX) 9, 12, 13‐trihydroxy‐trans‐10‐octadecenoic and 9, 10, 13‐trihydroxy‐trans‐11‐octadecenoic acids. In another experiment, equimolar amounts of Fe(II) and hydroperoxide were reacted in the absence of cysteine. A large proportion of dimeric fatty acids and a smaller amount of monomeric fatty acids resulted. The monomeric fatty acids were examined by gas liquid chromatography‐mass spectroscopy. Spectra indicated that the monomers were largely similar to those produced by the Fe(III)‐cysteine reaction.

Hydroperoxide lyase (HPLS) activity in soybean (Glycine max) seed/seedlings, leaves, and chloroplasts of leaves required detergent solubilization for maximum in vitro activity. On a per milligram of protein basis, more HPLS activity was found in leaves, especially chloroplasts, than in seeds or seedlings. The total yield of hexanal from 13(S)-hydroperoxy-cis-9,trans-1 1-octadecadienoic acid (13S-HPOD) from leaf or chloroplast preparations was 58 and 66 to 85%, respectively. Because of significant competing hydroperoxide-metabolizing activities from other enzymes in seed/seedling preparations, the hexanal yields from this source were lower (36-56%). Some of the products identified from the seed or seedling preparations indicated that the competing activity was mainly due to both a hydroperoxide peroxygenase and reactions catalyzed by lipoxygenase. Different HPLS isozyme compositions in the seed/seedling versus the leaf/chloroplast preparations were indicated by differences in the activity as a function of pH, the Km values, relative V .. with 13S-HPOD and 13(S)-hydroperoxy-cis-9,trans-1 ,cis-15-octadecatrienoic acid (13S-HPOT), and the specificity with different substrates. With regard to the latter, both seed/seedling and chloroplast HPLS utilized the 13S-HPOD and 13S-HPOT substrates, but only seeds/ seedlings were capable of metabolizing 9(S)-hydroperoxy-trans-10,cis-12-octadecadienoic acid into 9-oxononanoic acid, isomenc nonenals, and 4-hydroxynonenal. From 13S-HPOD and 13S-HPOT, the products were identified as 12-oxo-cis-9-dodecenoic acid, as well as hexanal from 13S-HPOD and cis-3-hexenal from 13S-HPOT. In seed preparations, there was partial isomerization of the cis-3 or cis-9 into trans-2 or trans-10 double bonds, respectively.HPLS', an enzyme that cleaves hydroperoxides of polyunsaturated fatty acids into both aldehyde and w-oxoacid fragments, occurs widely in plants. Depending on substrate specificity of HPLS isoenzymes for isomeric hydroperoxides of linoleic or linolenic acids, the enzyme produces either green/ ' Abbreviations: HPLS, hydroperoxide lyase; CP-HPLC, chiralphase HPLC; El, electron impact; OTMS, trimethylsilyloxy; rac-HPOD, racemic cis,trans-and trans,trans-diene linoleic acid hydroperoxides; rac-HPOT, racemic cis,cis,trans-triene linolenic acid hydroperoxides; 9S-HPOD, 9(S)-hydroperoxy-trans-10,cis-12-octadecadienoic acid; 13S-HPOD, 13(S)-hydroperoxy-cis-9,trans-11-octadecadienoic acid; 12S-HPOT, 12(S)-hydroperoxy-cis-9,trans-13,cis-1 5-octadecatrienoic acid; 1 3S-HPOT, 1 3(S)-hydroperoxy-cis-9,trans-11 ,cis-5-octadecatrienoic acid; SP-HPLC, straight-phase HPLC; Triton X-1 OOR, Triton X-100 reduced; m/z, mass to charge ratio. beany/grassy odors (hexanal or cis-3-hexenal) from 1 3-hydroperoxides or cucumber/pear odors (cis-3-nonenal or cis-3,cis-6 nonadienal) from 9-hydroperoxides (reviewed in refs. 4 and 15). The corresponding w-oxoacid fragments, 12-oxo-cis-9-dodecenoic acid and 9-oxononanoic acid, have no known function, except the former isomerizes into 12-oxo-trans-10-dodecenoi...

in primitive medical practices of Indonesia and the West Indies as a treatment for tumors, has been investigated employing the seeds from a South American variety and the murine P388 lymphocytic leukemia (PS) for bioassay. The principal antineoplastic constituent (PS, 28% life extension, at 0.25 mg/kg and EDso4.5 X kg/mL) was found to be a new bis-tetrahydrofuran designated rolliniastatin 1. Structural elucidation of rolliniastatin 1 was accomplished by a combination of high resolution nuclear magnetic resonance (300 MHz), mass spectral, and X-ray crystal structure techniques. 1433 (1987).Utilisant les graines d'une variCtC sud-amiricaine de la plante et la murine P388 de IeucCmie lymphocitaire (PS) pour des bioessais, on a CtudiC les propriCtCs de la Rollinin tnucosa (Annonaceae), qui est connue dans les pratiques mCdicales primitives de l'lndonksie et des Antilles pour le traitement des tumeurs. On a trouvC que le principal constituant actif (PS, augmentation de vie de 28%, i 0,25 mg/kg et EDs0 de 4,s X lop5 kg/mL) est un nouveau bis-tktrahydrofuranne que I'on a appelC rolliniastatine 1. On a dCtermink la structure de la rolliniastatine 1 en combinant les techniques de la rCsonance magnkt~que nucICaire i haute rCsolution (300 MHz), du spectre de masse et de la diffraction des rayons-)< par des cristaux uniques.[Traduit par la revue]The Annonaceae (ca. 2,100 species) is composed of shrubs and trees found mainly in tropical regions. The genus Rollinia generally occurs in Central and South America, and R. mucosa (Jacq.) Vaill, also known as Annona mucosa (Jacq.), has been used for the primitive medical treatment of tumors in the West Indies and in Indonesia (2). To assess the potential of this plant in respect to potentially useful antineoplastic components, seeds of Rollirzia mucosa were collected in French Guiana in 1979. The lipophilic extract of these seeds showed activity in the P388 lymphocytic leukemia system, and fractionation of this extract was guided by bioassay using the murine P388 system in vitro.Extraction of Rollinla mucosa seed (600g) with hexane afforded 136 g of oily extract from which rolliniastatin 1 was isolated by a series of chromatographic steps. Steric exclusion chromatography was followed by gradient elution chromatography on silica gel with hexane -ethyl acetate.

It was previously reported that males of the crucifer flea beetle, Phyllotreta cruciferae, feeding on host foliage are attractive to both males and females in the field. Based on this evidence for an aggregation pheromone, volatiles were collected from male and female P. cruciferae feeding on cabbage (Brassica oleracea) and analyzed. For comparison, volatiles were also collected from males and females of three other flea beetle species, Aphthona flava, A. czwalinae, and A. cyparissiae, all feeding on their host, leafy spurge foliage (Euphorbia esula). Six male-specific compounds were isolated from P. cruciferae, and the same compounds plus two additional ones were isolated from males of Aphthona flava, A. czwalinae, and A. cyparissiae. The blends of compounds were relatively consistent within species, but there were characteristic differences between species. Compound structures were studied by mass spectrometry, NMR spectroscopy, UV spectroscopy, polarimetry, chiral and achiral gas chromatography, molecular modeling, and microchemical tests. Three of the compounds were identified as (+)-ar-himachalene; (+)-trans-alpha-himachalene; (+)-y-cadinene. Two others were new enantiomers of himachalene hydrocarbons that were previously identified from the fir trees, Abies alba and Abies nordmanniana. Finally, there were two himachalene alcohols and one norsesquiterpene ketone that is a himachalene analog. Only (+)-ar-himachalene and (+)-y-cadinene are previously known natural products. Electrophysiological activity was demonstrated for five of the compounds. The chemical and electrophysiological patterns are consistent with, but do not prove, a pheromonal function.

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