Antioxidant activity of pea bean (Phaseolus vulgaris L.) extract

Antioxidative activity of pea bean (Phaseolus vulgaris L.) extract was evaluated by using a linoleic acid system, and the methanol extract exhibited strong antioxidative activity as measured by the thiocyanate method. The crude methanol extract was partitioned between then-butanol phase (BP) and the water phase (WP). Then, the antioxidative activity of the BP and the WP was determined by using a linoleic acid system. The WP showed strong antioxidative activity, while BP showed only weak activity as measured by the thiocyanate method. Next, the synergistic antioxidative action of WP with α-tocopherol was examined by using linoleic acid and liposome systems. The WP had a synergistic effect with α-tocopherol in both the food model and liposome systems. For purification and isolation of the antioxidative substances of the pea bean, preparative high-performance liquid chromatography was carried out with an octadecylsilyl column. Five fractions were collected, and antioxidative activity was determined in a linoleic acid system. Although fraction 1 had strong activity by the thiocyanate method, the purification of this active fraction was difficult; therefore, the partly characterized active fraction was investigated. The contents of total phenolics and sugars were 0.31±0.01 mg/g of fraction 1 and 406.1±0.1 mg/g, respectively. The ninhydrin chromogenic reaction was positive, and the ultraviolet absorption spectral λ max value in distilled water was 264.0 nm, indicating that the water-soluble antioxidative components from pea bean may be a new type of antioxidant. Isolation and identification are currently being investigated.     

(3Z,6Z,9Z, 12Z, 15Z)-Pentacosapentaene, a key pheromone component of the fir coneworm moth, Dioryctria abietivorella

The sex pheromone of the fir coneworm moth consists of a blend of (3Z,6Z,9Z,12Z,15Z)-pentacosapentaene and (9Z,11E)-tetradecadienyl acetate. Analogous blends of polyunsaturated, long-chain hydrocarbons with much shorter chain aldehydes or alcohols recently have been discovered in three other moth species in the superfamily Pyraloidea. These combinations of components from two distinct structural classes may represent an important and widespread new pheromone blend motif within the Lepidoptera.     

Rumex obtusifolius L: Release of allelochemical agents and their influence on small-scale spatial distribution of meadow species

DecomposingRumex obtusifolius L. leaves and their extracts were most toxic for germination and root growth of meadow speciesLolium perenne, Trifolium repens, Poa pratensis, andDactylis glomerata after seven days' decomposition, although the toxicity level was, in some cases, still high after 21 days. The hypothesis thatR. obtusifolius exerts allelopathic control over meadow species is supported by small-scale distribution of meadow species in the neighborhood ofR. obtusifolius plants. The area affected and the intensity of the effect both increase with the size of the individualR. obtusifolius plant.     

(6Z,9Z-3R,4S)-Epoxy-heptadecadiene: major sex pheromone component of the larch looper,Semiothisa sexmaculata (Packard) (Lepidoptera: Geometridae)

Gas chromatographic-electroantennographic analysis (GC-EAD) of female larch looper,Semiothisa sexmaculata (Packard), gland extracts revealed two EAD-active compounds. Retention index calculations, GC-mass spectroscopy in selected ion monitoring mode, and GC-EAD analysis of authentic standards identified the compounds as (3Z,6Z,9Z)-heptadecatriene (3Z,6Z,9Z-17H) and (6Z,9Z)-cis-3,4-epoxy-heptadecadiene (6Z,9Z-cis-3,4-epoxy-17H). Chirality determination of the monoepoxydiene in gland extracts was impeded by small quantities, but field experiments indicated that maleS. sexmaculata were most strongly attracted to enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H (69% ee), while maleS. neptaria (Guenée) responded well to various blends of theR,S- and S,R-epoxide enantiomers. Binary combinations of theR,S-epoxide enantiomer with 3Z,6Z,9Z-17H significantly inhibited response by maleS. sexmaculata, but strongly enhanced attraction of sympatric maleS. marmorata Ferguson. Enantiomerically enriched 6Z,9Z-3R,4S-epoxy-17H can be used as a trap bait to monitor populations of the larch-defoliatingS. sexmaculata. Whether 6Z,9Z-3R,4S-epoxy-17H serves as single component sex pheromone inS. sexmaculata or small amounts of 6Z,9Z-3S,4R-epoxy-17H synergize or suppress optimal attraction, will be tested as chirally pure monoepoxydienes become available.     

Chemical composition ofRumex crispus L. seed

Rumex crispus L. seeds harvested in Olavarría (Province of Buenos Aires, Argentina) were extracted with 60–80°C petroleum ether to render 6.0% (dry basis) of a lipid fraction with a 152.4 saponification value and 15.4% unsaponifiable matter. Fatty acid composition obtained by gas-liquid chromatography was: 14:0, 2.7; 16:0, 13.5; 16:1, 1.2; 18:0, 1.2; 18:1, 38.6; 18:2, 36.3; 18:3, 0.5; 20:0, 2.4; 20:2, 0.3; 22:0, 0.9; 22:1, 1.2; and 24:0, 1.2; with traces of 14:1, 15:1, 17:0, and 17:1. Residual meal contained 10.62% crude protein, with a low value of available lysine (3.31 g/16 g N). Ash, crude fiber, sugars, hydrolyzable carbohydrates, total and phytic acid phosphorus, calcium and residual lipids contents are reported here.     

Stegobiol,a new sex pheromone component of drugstore beetle (Stegobium paniceum L.)

New sex pheromone component of femaleStegobium paniceum L. was isolated and identified as 2,3-dihydro-2,3,5-trimethyI-6-(1-methyl-2-hydroxybutyl)-4H-pyran-4-one, stegobiol, by spectral data and chemical conversion from stegobinone. Relative configuration at C-2, C-3, and C-1 was determined as 2S,3R,1S by the conversion from (2S,3R,1R)-stegobinone. This new sex pheromone elicits the pheromonal response from the species.     

Fatty acid and tocopherol contents and oxidative stability of walnut oils

Walnuts (Juglans regia L.) were collected during the 1997 harvest from 13 different cultivars of trees grown in a replicated trial in an experimental orchard at Lincoln University. Two U.S. commercial cultivars (Tehama and Vina), three European commercial cultivars (Esterhazy, G139, G120), and eight New Zealand selections (Rex, Dublin’s Glory, Meyric, Stanley, Mckinster, 150, 151, 153) were evaluated. Total lipids were analyzed for fatty acids by capillary gas chromatography, tocopherols by high-performance liquid chromatography, and oxidation stability by Rancimat. The total oil content of the nuts ranged from 64.2 to 68.9% while the stability of the oil ranged from 3.9 to 7.8 h. The oleic acid content of the oils ranged from 12.7 to 20.4% of the total fatty acids, while 18:2 content ranged from 57.0 to 62.5% and the 18:3 contents ranged from 10.7 to 16.2%. Reduced stability of the oil as measured by the Rancimat method appears to be correlated to higher levels of 18:2 in the extracted oil. The total tocopherol contents of these nuts ranged from 268.5 to 436.0 μg/g oil. γ-Tocopherol dominated the profile while α-tocopherol was only 6% of the total content. Peroxide values of the fresh oil were measured spectrophotometrically to give an indication of the overall stability. The levels of total tocopherols when combined with the level of unsaturation in the oil in a multiple regression analysis had a significant relationship (R ²=45.2%, P<0.001) with the peroxide value in the oil. Presented as a poster at the 89th AOCS Annual Meeting, Chicago, Illinois, May 10–13, 1998.     

Development of 101 Gene-based Single Nucleotide Polymorphism Markers in Sea Cucumber, Apostichopus japonicus

Single nucleotide polymorphisms (SNPs) are currently the marker of choice in a variety of genetic studies. Using the high resolution melting (HRM) genotyping approach, 101 gene-based SNP markers were developed for Apostichopus japonicus, a sea cucumber species with economic significance for the aquaculture industry in East Asian countries. HRM analysis revealed that all the loci showed polymorphisms when evaluated using 40 A. japonicus individuals collected from a natural population. The minor allele frequency ranged from 0.035 to 0.489. The observed and expected heterozygosities ranged from 0.050 to 0.833 and 0.073 to 0.907, respectively. Thirteen loci were found to depart significantly from Hardy-Weinberg equilibrium (HWE) after Bonferroni corrections. Significant linkage disequilibrium (LD) was detected in one pair of markers. These SNP markers are expected to be useful for future quantitative trait loci (QTL) analysis, and to facilitate marker-assisted selection (MAS) in A. japonicus.     

Winter host component reduces colonization by bird-cherry-oat aphid,Rhopalosiphum padi (L.) (homoptera,aphididae), and other aphids in cereal fields

Methyl salicylate, a volatile component ofPrunus padus, the winter host ofRhopalosiphum padi, was found to reduce colonization of the summer host by this aphid. The compound was identified by gas chromatographic analysis coupled with recordings from cells in the primary rhinarium on the sixth antennal segment of the aphid. Methyl salicylate eliminated the attractancy of oat leaves to spring migrants in olfactometer tests. In Sweden, this compound significantly decreased colonization of field grown cereals byR. padi and in the U.K., populations ofSitobion avenae andMetopolophium dirhodum were significantly lower on treated plots.     

Chain-breaking fused heterocyclic antioxidants: Antioxidant activities of 9H-xanthene-2,7-diols and α-tocopherol upon liposomal membranes

We evaluated the antioxidant activities of 9H-xanthene-2,7-diols and α-tocopherol (α-Toc) upon the oxidation of soybean phosphatidylcholine liposomal membranes, induced by 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH) and 2,2′-azobis(2,4-dimethylvaleronitrile (AMVN). The stoichiometric factors of 9H-xanthene-2,7-diols, initiated with water-soluble AAPH and lipid-soluble AMVN, were 1.9–2.7 and 1.2–1.8-fold greater than those of α-Toc, respectively. The consumption profile of the antioxidant confirmed that 9H-xanthene-2,7-diol was completely consumed within the induction period (t _inh) and that the 9H-xanthene-2,7-diol oxidation product was formed. When all oxidation product was depleted, t _inh was terminated, and rapid oxidation occurred. These results suggested that the antioxidant activities of 9H-xanthene-2,7-diol depend not only on the initial hydrogen abstraction from 9H-xanthene-2,7-diol but also on a second hydrogen abstraction from the residual phenolic OH group of the oxidation product. Ascorbic acid (AsA) could not scavenge the radicals by itself in the lipid bilayer. However, when 9H-xanthene-2,7-diol was located in the lipid bilayer, the addition of AsA into the aqueous phase prolonged t _inh and reduced the rate of decay of 9H-xanthene-2,7-diol.     

Antioxidative components,xanthone derivatives,inSwertia japonica Makino

Substances with antioxidative properties were obtained from an ether extract ofSwertia japonica Makino. Six active components of the extract were isolated and identified as methylbellidifolin, methylswertianin, swertianin, bellidifolin, norswertianin and desmethylbellidifolin. These six xanthone derivatives were shown to possess different antioxidant activities by chemiluminescent assay. The antioxidative activities of bellidifolin, norswertianin and desmethylbellidifolin were higher than those of butylated hydroxytoluene (BHT) and α-tocopherol. On autoxidation of methyl linoleate, bellidifolin had activity similar to that of BHT. On the basis of the data present on antioxidative properties and data reported on the mutagenicities of the xanthones, both activities were shown to give a good correlation.     

Stereospecific synthesis of (Z,Z)-3,5-tetradecadienoic acid,a component ofAttagenus elongatulus (Casey) pheromone

A simple stereospecific synthesis of (Z,Z)-3,5-tetradecadienoic acid is described based upon coupling of 1-decyne and 3-butyn-1-ol to give 3,5-tetradecadiyn-1-ol. Subsequent reduction of the diyne to (Z,Z)-3,5-tetradecadien-1-ol and oxidation of the dienol gave the desired acid.Attagenus elongatulus were strongly attracted to the pure acid.     

Introduction of methyl groups to acetate substituted chain of (Z)-5-decenyl acetate,a pheromone component of turnip moth,agrotis segetum: synthesis,single-sensillum recordings,and structure-activity relationships

Methyl-substituted analogs of (Z)-5-decenyl acetate, a pheromone component of the turnip moth,Agrotis segetum, have been synthesized and studied by electrophysiological single-sensillum recordings and molecular mechanics calculations [MM2(85)]. The analogs are monomethyl substituted in the 2, 3, 4, and 5 positions and geminally dimethyl substituted in the 2, 3, and 4 positions. The methyl groups have been employed as space probes to study the degree of steric complementarity between the acetate-substituted alkyl chain of the pheromone component and its receptor. The electrophysiological activities, interpreted in terms of a receptor interaction model, indicate significant steric repulsive interactions between the introduced methyl groups and the receptor. This implies a high degree of complementarity between the acetate-substituted alkyl chain of the natural pheromone component and its receptor.Schiff., Lepidoptera: Noctuidae.     

(7R,8S)-cis-7,8-epoxy-2-methyloctadec-17-ene: a novel trace component from the sex pheromone gland of gypsy moth, Lymantria dispar

Considering the vast Eurasian distribution of gypsy moth, Lymantria dispar (Lepidoptera: Lymantriidae), the many subspecies, and their presence in different lymantriid communities, we tested the hypothesis that L. dispar populations in eastern Asia employ one or more pheromone components in addition to the previously known single component pheromone (7R,8S)-cis-7,8-epoxy-2-methyloctadecane [= (+)-disparlure]. Coupled gas chromatographic–electroantennographic detection (GC–EAD) analyses of pheromone gland extracts of female L. dispar sensu lato (including both AGM and NAGM) on four GC columns (DB-5, DB-23, DB-210, and SP-1000) revealed a new trace component that eluted just before (DB-5; DB-210) or after (DB-23, SP-1000) disparlure, and elicited strong antennal responses. Isolation of this compound by high-performance liquid chromatography and hydrogenation produced disparlure, suggesting that the new component had the molecular skeleton of disparlure, with one or more double bonds. Of all possible monounsaturated cis-7,8-epoxy-2-methyloctadecenes, only cis-7,8-epoxy-2-methyloctadec-17-ene co-chro- matographed with the insect-produced compound on all GC columns and elicited comparable antennal responses. In field experiments in Honshu (Japan) with enantioselectively synthesized compounds, (7R,8S)-cis-7,8-epoxy-2- methyloctadec-17-ene (7R8S-epo-2me-17-ene-18Hy) was weakly attractive to male L. dispar, but was less effective as a trap bait than (+)-disparlure, and failed to enhance attractiveness of (+)-disparlure when tested in blends. The antipode, (7S,8R)-cis-7,8-epoxy-2-methyloctadec-17-ene, was not attractive, and when added to (+)-disparlure and/or 7R8S-epo-2me-17-ene-18Hy reduced attractiveness. Thus, the biological role of 7R8S-epo-2me-17-ene-18Hy remains unclear. It may enhance pheromone attractiveness or specificity in other L. dispar populations within their vast Eurasian distribution.     

Purification of tocopherols and phytosterols by a two-step <Emphasis Type="Italic">in situ</Emphasis> enzymatic reaction

The purification of tocopherols and phytosterols (referred to as sterols) from soybean oil deodorizer distillate (SODD) was attempted. Tocopherols and sterols in the SODD were first recovered by short-path distillation, which was named sODD tocopherol/sterol concentrate (SODDTSC). The SODD-TSC contained MAG, DAG, FFA, and unidentified hydrocarbons in addition to the two substances of interest. It was then treated with Candida rugosa lipase to convert sterols to FA steryl esters, acylglycerols to FFA, and FFA to FAME. Methanol (MeOH), however, inhibited esterification of the sterols. Hence, a two-step in situ reaction was conducted: SODDTSC was stirred with 20 wt% water and 200 U/g mixture of C. rugosa lipase at 30°C, and 2 moles of MeOH per mole of FFA was added to the reaction mixture after 16h. The lipase treatment for 40 h in total achieved 80% conversion of the initial sterols to FA steryl esters, complete hydrolysis of the acylglycerols, and a 78% decrease in the initial FFA content by methyl esterification. Tocopherols did not change throughout the process. To enhance the degree of steryl and methyl esterification, the reaction products, FA steryl esters and FAME, were removed by short-path distillation, and the resulting fraction containing tocopherols, sterols, and FFA was treated with the lipase again. Distillation of the reaction mixture purified tocopherols to 76.4% (recovery, 89.6%) and sterols to 97.2% as FA steryl esters (recovery, 86.3%).     

A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes

Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N₃P₃Cl₄[NH(CH₂)₃O], (1), and N₃P₃Cl₄[NH(CH₂)₃NMe], (2), were used to investigate a possible directing effect of the P-NHR moiety on the formation of products in the nucleophilic substitution reactions with diols such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimethyl-1,3-propanediol. The ³¹P NMR spectra of the reaction mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group.     

Lipid composition and oxidative stability of oils in hazelnuts (Corylus avellana L.) grown in New Zealand

Hazelnut (Corylus avellana L.) samples were collected from six different cultivars of trees grown in an experimental orchard at Lincoln University. Three U.S. commercial cultivars (Butler, Ennis, and Barcelona), two European commerical cultivars (Tonda di Giffoni and Campanica), and one New Zealand selection (Whiteheart) were evaluated. The total oil, stability to oxidation of the oil, and fatty acid, tocopherol, and sterol composition were determined on samples of freshly extracted hazelnut oil. The total oil content of the seeds ranged from 54.6 to 63.2% while the stability of the oil, as measured by the Rancimat test ranged from 15.6 to 25.3 h. The content of the monounsaturated oleic acid in the oils ranged from 73.8 to 80.1% of the total fatty acids, while the tocopherol content ranged from 225.8 to 552.0 mg/g freshly extracted oil. The major desmethylsterols were sitosterol, ranging from 1416 to 1693 μg/g, campesterol, ranging from 78 to 114 μg/g, and Δ5-avenasterol, ranging from 110 to 170 μg/g. The oil extracted from the cultivar Whiteheart was more stable (measured by Rancimat) than the oil from all other cultivars grown at the same location and under the same conditions. Whiteheart contained higher levels of total and γ-tocopherol when compared to the other cultivars. The higher levels of tocopherol in Whiteheart help to explain the greater stability of the oil during the oxidative stress test. These results suggest that nuts from the cultivar Whiteheart could be stored longer than the other nuts tested. Presented as a poster at the 87th AOCS Annual Meeting, Indianapolis, Indiana, April 28–May 1, 1996.     

Response of the elm bark beetle,Scolytus multistriatus (Coleoptera: Scolytidae), to component mixtures and doses of the pheromone,multilure

The response of the elm bark beetle,Scolytus multistriatus (Marsham), was measured to various doses and mixtures of the three components of its aggregation pheromone. The ratio of the components released, particularly heptanol to multistriatin, strongly influenced the number, but not the sex ratio, of beetles that responded. We concluded that a bait that released about 400 100 800 g/day of heptanol-multistriatin-cubebene would be effective in mass-trapping beetles.The use of a trade, firm, or corporation name in this paper is for the information and convenience of the reader. It does not constitute an official endorsement or approval by the Forest Service or the U.S. Department of Agriculture.     

Dodecyl acetate,a second pheromone component of the cabbage looper moth,Trichoplusia ni

Dodecyl acetate was identified as a second component of the sex pheromone ofTrichoplusia ni (Hübner). Dodecyl acetate comprised 9.6% by weight of the total pheromone [(Z)-7-dodecenyl acetate plus dodecyl acetate] extracted from glands and 7.3% by weight of the total pheromone evaporated from the surfaces of glands. Dodecyl acetate appears to function as a short-range pheromone component. Evaporation at female release rates of a 1090 mixture of dodecyl acetate and (Z)-7-dodecenyl acetate in the field caused a significantly greater percentage of males to land on the pheromone source, increased significantly the time they spent on the source, but decreased significantly the time they spent searching for the source when within 50 cm, as compared to (Z)-7-dodecenyl acetate alone.Lepidoptera: Noctuidae.     

Perception byTrogoderma species of chirality and methyl branching at a site far removed from a functional group in a pheromone component

Responses to enantiomers of (Z)- and (E)-trogodermal (14-methyl-8-hexadecenal) suggest that fourTrogoderma species utilize the (R)-(–) configuration at C-14. Removal of the C-14 methyl branch decreased the response. These results demonstrate the high specificity associated with the configuration at a chiral center, or the methyl branch, distant in terms of numbers of bonds from a functional group.Coleoptera: Dermestidae.