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Wood pellets were pyrolyzed using a microwave oven and different microwave power, apparatus set-up and microwave absorbers (none, Fe, and carbon). Pyrolysis was realized in a short time in the presence of Fe or carbon while it was incomplete if the absorber was not present. Furthermore when the absorber was present the shape of the pellets remained unaltered while if the absorber was not employed pellets were disaggregated. Three fractions were collected from each pyrolysis: a gas, a liquid also called bio-oil and a solid called bio-char. The bio-oil contained two phases and they were quantitatively characterized through a GC/MS-FID procedure using an internal standard according to a previously reported method. HPLC/MS, FTIR and 1 H NMR spectroscopy were also employed for characterization of these liquids. Cellulose pyrolysis products were present in the upper phase such as water, acetic acid, furans (such as furfural), carbohydrates and their derivatives. Compounds from pyrolysis of lignin such as phenols and veratric acid were present in the bottom phase. The microwave assisted pyrolysis showed the possibility to efficiently convert wood pellets in different products. The main economical important components may be separated and used as chemicals, natural drugs or pesticides, while the remaining components, the solid and the gas may be used for energy production (solid and bio-oil). Solid may be also used for carbon sequestration.

A simple procedure was suggested for the chromatographic analyses of bio-oils from pyrolysis of various feedstock employing different technologies. An acetonitrile solution of each bio-oil was prepared without any extraction or other sample pretreatments. Preliminary thin layer chromatography showed a large number of compounds having a broad range of retention factors (Rfs) among 0–1. Products having a retention factor over 0.9 were mainly detected by GC while some other compounds were only identified by HPLC. GC/MS-FID analysis was used to identify and quantify compounds using peak areas and relative response factors (RRFs). A new equation was proposed to estimate RRFs of compounds identified via their MS spectra when experimental RRFs were not readily available. The novel procedure was employed to characterize bio-oils from pyrolysis of wood of different source or obtained using different pyrolysis procedure. Using this RRF method guaiacol, furfural, butan-2-one, levoglucosan, acetic acid and many other compounds were quantified in bio-oil samples. Different amount of them were found as a function of the type of wood, and pyrolysis conditions adopted. For instance levoglucosan was the main compound using carbon as MW absorber however acetic acid was prevalent when a MW absorber was not employed and both of them were absent in bio-oils from classical heating. The HPLC/MS of bio-oils showed cyclohexancarboxylic acid, 1,2,4-trimethoxybenzene and 2,6-dimethylphenol among the main products present in all bio-oils. On the contrary 4-hydroxyacetophenone and (3,4,5-trimethoxy) acetophenone were present in bio-oil from pyrolysis of wood using MW oven and 2,5-furandiylmethanol when a MW oven without any absorber was employed. Cyclohexanone was present in bio-oils obtained with a thermal heating or a MW oven without any absorber.

The number of multidrug resistant (MDR) microorganisms is increasing and the antimicrobial resistance expressed by these pathogens is generating a rising global health crisis. In fact, there are only a few antimicrobial agents left that can be used against MDR bacteria and fungi.In this study, the antimicrobial activities of selected natural products from the flora of Northern Ontario against selected microorganisms are reported.Plants were collected from Sault Ste. Marie, Ontario, Canada, and ethanol extracts were prepared using EtOH:H2O (1:1, v/v). Fungal cultures used in this study were Candida albicans ATCC 10231 and Schizosaccharomyces octosporus. Bacterial cultures employed included Staphylococcus aureus ATCC 29213, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853, Mycobacterium phlei ATCC 11758, and Streptococcus lactis ATCC 19435. The microplate resazurin assay was used to screen for antimicrobial activity.Extracts of four plant species Chimaphila umbellata L. (Pyrolaceae), Betula papyrifera Marshall (Betulaceae), Rhus typhina L. (Anacardiaceae), and Fraxinus pennsylvanica Marshall (Oleaceae), and six compounds (gallic acid, ethyl gallate, caffeic acid, sinapic acid, gentisic acid, and chlorogenic acid) demonstrated antibacterial or antifungal activities with MICs ranging from 62.5 to 1000 µg/mL, respectively, for a chemical fraction of an extract from Betula papyrifera against the bacterium S. aureus.The present study has shown that certain plant extracts and select fractions and standard chemical compounds exhibit antimicrobial effects. Prince's Pine, Chimaphila umbellate, White Birch, Betula papyrifera, Staghorn Sumac, Rhus typhina, and Green Ash, Fraxinus pennsylvanica were the principal extracts exhibiting notable antibacterial and/or antifungal activities; while gallic acid, ethyl gallate, and caffeic acid demonstrated antibacterial activities and sinapic acid, gentisic acid, and chlorogenic acid demonstrated antifungal activities.

A challenge in recent years has been the rational use of forest and agriculture residues for the production of bio-fuel, biochemical, and other bioproducts. In this study, potentially useful compounds from pyrolytic lignins were identified by HPLC-MS/MS and untargeted metabolomics. The metabolites identified were 2-(4-allyl-2-methoxyphenoxy)-1-(4-hydroxy-3-methoxyphenyl)-1-propanol, benzyl benzoate, fisetinidol, phenyllactic acid, 2-phenylpropionic acid, 6,3′-dimethoxyflavone, and vanillin. The 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity (DPPH), trolox equivalent antioxidant capacity (TEAC), and total phenolics content (TPC) per gram of pyrolytic lignin ranged from 14 to 503 mg ascorbic acid equivalents, 35 to 277 mg trolox equivalents, and 0.42 to 50 mg gallic acid equivalents, respectively. A very significant correlation was observed between the DPPH and TPC (r = 0.8663, p ≤ 0.0001), TEAC and TPC (r = 0.8044, p ≤ 0.0001), and DPPH and TEAC (r = 0.8851, p ≤ 0.0001). The polyphenolic compounds in the pyrolytic lignins which are responsible for radical scavenging activity and antioxidant properties can be readily profiled with HPLC-MS/MS combined with untargeted metabolomics. The results also suggest that DPPH, TEAC, and TPC assays are suitable methods for the measurement of antioxidant activity in a variety of pyrolytic lignins. These data show that the pyrolytic lignins can be considered as promising sources of natural antioxidants and value-added chemicals.

Insecticide synergists biochemically inhibit insect metabolic enzyme activity and are used both to increase the effectiveness of insecticides and as a diagnostic tool for resistance mechanisms. Considerable attention has been focused on identifying new synergists from phytochemicals with recognized biological activities, specifically enzyme inhibition. Jack pine (Pinus banksiana Lamb.), black spruce (Picea mariana (Mill.) BSP.), balsam fir (Abies balsamea (L.) Mill.), and tamarack larch (Larix laricina (Du Roi) Koch) have been used by native Canadians as traditional medicine, specifically for the anti-inflammatory and antioxidant properties based on enzyme inhibitory activity. To identify the potential allelochemicals with synergistic activity, ethanol crude extracts and methanol/water fractions were separated by Sephadex LH-20 chromatographic column and tested for in vitro glutathione S-transferase (GST) inhibition activity using insecticide-resistant Colorado potato beetle, Leptinotarsa decemlineata (Say) midgut and fat-body homogenate. The fractions showing similar activity were combined and analyzed by ultra pressure liquid chromatography-mass spectrometry. A lignan, (+)-lariciresinol 9′-p-coumarate, was identified from P. mariana cone extracts, and L. laricina and A. balsamea bark extracts. A flavonoid, taxifolin, was identified from P. mariana and P. banksiana cone extracts and L. laricina bark extracts. Both compounds inhibit GST activity with taxifolin showing greater activity compared to (+)-lariciresinol 9′-p-coumarate and the standard GST inhibitor, diethyl maleate. The results suggested that these compounds can be considered as potential new insecticide synergists.

We conducted two trapping experiments in green ash plantations in Ontario, Canada to compare the response of the emerald ash borer (EAB), Agrilus planipennis, to (Z)-3-hexenol (Z3-6:OH) and manuka oil. In the first experiment, Z3-6:OH (7.6 mg/day) in purple prism traps hung 1.5 m above ground caught significantly more EAB than the unbaited controls, with male catches significantly greater than female catches at two locations. Manuka oil (50 mg/day) attracted equal numbers of males and females but they were significantly greater than the controls at only one location. Adding (Z)-3-hexenal or (Z)-3-hexenyl acetate in binary or ternary combinations with Z3-6:OH did not enhance trap catch. In the second experiment, Z3-6:OH released at two rates (7.6 or 80 mg/day) in light green prism traps placed in the ash canopy also caught significantly more males than females and more males than the unbaited controls or manuka oil-baited traps. Manuka oil had no significant effect on catches relative to the controls. Combining Z3-6:OH with manuka oil did not enhance catches of EAB. We conclude that there was a strong male-biased EAB response to Z3-6:OH lures, whereas manuka oil, when effective, attracted both sexes equally. Z3-6:OH in light green prism traps in the canopy is an effective lure for EAB, particularly for males. J. Appl. Entomol.

Methyl gallate was found in ethanolic extracts of red maple (Acer rubrum L.), silver maple (A. saccharinum L.) and sugar maple (A. saccharum Marsh) leaves, but more was present in methanolic extracts. The increased amount of methyl gallate in methanolic extracts was accompanied by a disappearance of m-digallate. It is concluded that only some of the methyl gallate detected in methanolic extracts is an artefact as a result of methanolysis of m-digallate. Its presence in ethanolic extracts is evidence that it is also a natural constituent of maple leaves.

Maple syrup of four grades (extra-light, light, medium, and dark) of the 2007 crop was provided by three local (St. Joseph’s Island, Ontario, Canada) producers. Twenty-four phenolic compounds were isolated from a medium-grade syrup and identified on the basis of spectral and chemical evidence. They were (a) benzoic acid and several hydroxylated and methoxylated derivatives (gallic acid, 1-Ogalloyl-β-D-glucose, γ -resorcylic acid); (b) cinnamic acid derivatives (p-coumaric acid, 4-methoxycinnamic acid, caffeic acid, ferulic acid, sinapic acid, and the ester chlorogenic acid); (c) flavonoids, the flavanols catechin and epicatechin, and the flavonols kaempferol and its 3-O-β-D-glucoside, 3O-β-D-galactoside, quercetin and its 3-O-β-D-glucoside, 3-O-β-L-rhamnoside and 3-O-rhamnoglucoside (rutin). Traces obtained at 280 and 350 nm in HPLC runs of the ethyl acetate–soluble fractions of eight samples indicated the presence of many more phenolic substances, most at very low concentration with some varibilities in peak heights, but not in retention times, among the syrups. In view of the well-established antioxidant activity these substances possess, it is suggested that it is the complexity of the mixture rather than any one compound that may serve to counter the unhealthful presence of the high concentration of sugars in the syrup.

Purpling of the needles of jack pine seedlings in forest tree nurseries in the autumn is a result of the production of at least five anthocyanin pigments: cyanidin 3-O-glucoside (~80%), delphinidin 3-O-glucoside (~8%), peonidin 3-O-glucoside (~8%), petunidin 3-O-glucoside (~3%) and malvidin 3-O-glucoside (trace). The twigs subtending the needles also produce a similar range of pigments. The entire spectrum of pigments is produced from the time of the first exposure to freezing temperatures. Proanthocyanidins are a prominent feature of the needle phenolics and the question of their possible involvement in the purpling phenomenon following exposure to sub-zero temperatures is raised. The red colour of the hypocotyl of the newly germinated seedling is also a result of a similar mixture of pigments.Key words: Pinus banksiana, Pinaceae, jack pine seedlings, anthocyanin pigmentation, hypocotyl, proanthocyanidins.

Insecticide synergists biochemically inhibit insect metabolic enzyme activity and are used both to increase the effectiveness of insecticides and as a diagnostic tool for resistance mechanisms. Considerable attention has been focused on identifying new synergists from phytochemicals with recognized biological activities, specifically enzyme inhibition. Jack pine (Pinus banksiana Lamb.), black spruce (Picea mariana (Mill.) BSP.), balsam fir (Abies balsamea (L.) Mill.), and tamarack larch (Larix laricina (Du Roi) Koch) have been used by native Canadians as traditional medicine, specifically for the anti-inflammatory and antioxidant properties based on enzyme inhibitory activity. To identify the potential allelochemicals with synergistic activity, ethanol crude extracts and methanol/water fractions were separated by Sephadex LH-20 chromatographic column and tested for in vitro glutathione S-transferase (GST) inhibition activity using insecticide-resistant Colorado potato beetle, Leptinotarsa decemlineata (Say) midgut and fat-body homogenate. The fractions showing similar activity were combined and analyzed by ultra pressure liquid chromatography-mass spectrometry. A lignan, (+)-lariciresinol 9'-p-coumarate, was identified from P. mariana cone extracts, and L. laricina and A. balsamea bark extracts. A flavonoid, taxifolin, was identified from P. mariana and P. banksiana cone extracts and L. laricina bark extracts. Both compounds inhibit GST activity with taxifolin showing greater activity compared to (+)-lariciresinol 9'-p-coumarate and the standard GST inhibitor, diethyl maleate. The results suggested that these compounds can be considered as potential new insecticide synergists.

An ethanolic extract of borage meal was fractionated (fractions I–VI) on a Sephadex LH-20 column. All fractions tested positive for phenolics, but were negative for condensed tannins. Silica gel thin-layer chromatography (TLC) of fractions allowed the location of one and two strong antioxidative spots in fractions I and IV, respectively. Other fractions produced spots containing either weak antioxidative compounds or compounds with low concentrations. High performance liquid chromatography of the three major TLC spots in fractions I and IV showed the presence of one phenolic compound in each spot. Ultraviolet, proton nuclear magnetic resonance and proton-proton correlation spectroscopies, as well as electron impact-mass spectrometry, allowed the identification of three phenolic acids, namely rosmarinic acid in fraction I, and syringic and sinapic acids in fraction IV. These three compounds contributed to 3.9% of the dry mass of the crude extract whereas their total contribution in the meal was 0.6% (w/w).

Leaves of Cucumis sativus plants treated with silicon and infected with Sphaerotheca fuliginea yielded five new acylated flavone C-glycosides identified as isovitexin 2"-O-(6"'-(E)-p-coumaroyl)glucoside (6), isovitexin 2"-O-(6"'-(E)-p-coumaroyl)glucoside-4'-O-glucoside (7), isovitexin 2"-O-(6"'-(E)-feruloyl)glucoside-4'-O-glucoside (11), isoscoparin 2"-O-(6"'-(E)-p-coumaroyl)glucoside (9), and isoscoparin 2"-O-(6"'-(E)-feruloyl)glucoside-4'-O-glucoside (12). The known flavone-glycosides isovitexin (1), saponarin (2), saponarin 4'-O-glucoside (3), vicenin-2 (4), apigenin 7-O-(6"-O-p-coumaroylglucoside) (5), isovitexin 2"-O-(6"'-(E)-feruloyl)glucoside (8) and isoscoparin 2"-O-(6"'-(E)-feruloyl)glucoside (10), were also identified in this plant material.

An ethanolic extract of red maple (Acer rubrum L.) leaves (RME) applied to trembling aspen (Populus tremuloides Michx.) leaves reduced feeding in choice test assays with forest tent caterpillar larvae (Malacosoma disstria Hbn.) (FTC), whereas a trembling aspen foliage extract, similarly applied, stimulated feeding. Compounds isolated from the RME were gallic acid, methyl gallate, ethyl gallate, m-digallate, ethyl m-digallate, 1-O-galloyl-beta-D-glucose, 1-O-galloyl-alpha-L-rhamnose, kaempferol 3-O-beta-D-glucoside, kaempferol 3-O-beta-D-galactoside, kaempferol 3-O-beta-L-rhamnoside, kaempferol-3-O-rhamnoglucoside, quercetin 3-O-beta-D-glucoside, quercetin 3-O-beta-L-rhamnoside and quercetin 3-O-rhamnoglucoside, (-)-epicatechin. (+)-catechin and ellagic acid. All of the gallates, (-)-epicatechin, and kaempferol 3-O-beta-L-rhamnoside deterred feeding on trembling aspen leaf disks when applied at 0.28 mg/cm2. The two digallates deterred feeding by 90% and were the most effective. HPLC analysis indicated that ethyl m-digallate is present in amounts 10-100 x higher in RME (approximately 2.5-250 mg/g) than any other compound. Thus, ethyl m-digallate appears to be the major compound protecting red maple from feeding by FTC, with a minor contribution from other gallates.

From literature describing medicinal usage of plants by First Nations Peoples in eastern Canada, 18 eastern Canadian plants were selected and tested for their antifungal activities. Eight randomly selected tropical plants were also tested for comparative purposes. Four groups of plants were obtained: popular antimicrobial-remedy (n=6), popular non-antimicrobial-remedy (n=6), random temperate (n=6) and random tropical (n=8). Extracts from these plants were tested in disk assays as growth inhibitors of six fungi known to be opportunistic human pathogens (Saccharomyces cerevisiae, Cryptococcus neoformans, Candida albicans, Aspergillus fumigatus, Microsporum gypseum and Trichophyton mentagrophytes). Of the four plant groups tested, extracts from the popular antimicrobial-remedy group were significantly more effective at inhibiting fungal growth based on both overall antifungal activity and number of fungal species inhibited.

Liquid chromatography coupled to mass spectrometry (LC-MS), using atmospheric pressure chemical ionisation (APCI), was found to complement data obtained from diode array detection enabling common flavonoids in Ocimum gratissimum var. gratissimum to be characterised at the analytical level without complete purification, or even to be characterised in crudely purified ethanolic extracts. Xanthomicrol, cirsimaritin, rutin, kaempferol 3-O-rutinoside and vicenin-2 were identified as the major flavonoids, whereas luteolin 5-O-glucoside, luteolin 7-O-glucoside, apigenin 7-O-glucoside, vitexin, isovitexin, quercetin 3-O-glucoside and isothymusin were detected as minor constituents. First-order positive ion APCI-MS provided not only the pseudomolecular ion of flavonoid O-glycosides, but also an ion corresponding to the aglycone and an intermediate ion if more than one sugar was attached to the flavonoid. Information on the type and sequence of sugars was therefore obtained without the need to undertake MS2 product ion analyses. Product ion analysis was useful for confirming the glycoside fragmentation observed in first-order MS, especially with co-eluting compounds, and for obtaining fragmentation patterns of either free aglycones or the aglycone moiety of flavonoid O-glycosides; the latter could be used to support the aglycone identification achieved from the UV spectra. Negative ion APCI-MS was found useful for flavone C-glycosides and gave very characteristic product ions due to fragmentation of the C-sugars. For flavonoid O-glycosides analysed in the negative ion mode, there was evidence that the position and nature of the attached sugars could influence the aglycone product ion formed by MS2 analysis and hence its product ion spectrum. APCI is considered to be a more useful ion source than electrospray in the chemotaxonomic study of flavonoids. Copyright © 2000 John Wiley & Sons, Ltd.

The controversial role of silicon in plant disease resistance, described mostly as a passive mechanical protection, has been addressed. Conclusive evidence is presented that silicon is involved in the increased resistance of cucumber to powdery mildew by enhancing the antifungal activity of infected leaves. This antifungal activity was attributable to the presence of low-molecular-weight metabolites. One of these metabolites, described here as a phytoalexin, was identified as a flavonol aglycone rhamnetin (3,5,3′,4′-tetrahydroxy-7-O-methoxyflavone). This is the first report of a phytoalexin for this chemical group in the plant kingdom and of a flavonol phytoalexin in cucumber, a chemical defense long believed to be nonexistent in the family Cucurbitaceae. The antifungal activity of leaf extracts was better expressed after acid hydrolysis, extending to another plant species the concept that some phytoalexins are synthesized as glycosylated phytoalexins or their precursors.

Early instars of gypsy moth (Lymantria dispar L.) generally do not feed on pine (Pinus) species, perhaps due to secondary compounds found in pines. To test this hypothesis, ethanolic extracts from jack pine (Pinus banksiana Lamb), red pine (Pinus resinosa Ait.), scotch pine (Pinus sylvestris L.) and white pine (Pinus strobus L.) (Pinaceae) needles were prepared. Extracts from all four pine species, when incorporated into artificial diet, significantly reduced weight and increased mortality for 2nd instars. A purified ethanolic fraction from jack pine (fractionated on a polyvinylpolypyrrolidine (PVPP) column with a 100% water to 100% ethanol gradient), containing phenolics and flavonol glycosides significantly reduced growth and increased mortality of gypsy moth 2nd instars. Eight flavonol glycosides were isolated from the four pine species, two of which (rutin and quercetin-3-0-glucoside) were common to all four species. These two compounds, and the aglycone quercetin, when incorporated into diet, significantly reduced growth of gypsy moth 2nd instars. These results suggest that early instars of gypsy moth are sensitive to pine flavonols, and the presence of these compounds may be one reason they do not generally feed on pines until later instars.

Two C-6 and C-8 methyl flavonols were isolated from a fungus and identified for the first time. The fungus Colletotrichum dematium f.sp. epilobii is a disease of fireweed, Epilobium angustifolium L. ssp. angustifolium (family Onagraceae); both disease and plant are indigenous to Canada. C. dematium secretes several metabolites when grown in liquid culture. Two novel natural product compounds: 5,4′-dihydroxy-3,7,8-trimethoxy-6-C-methylflavone and 5,4′-dihydroxy-3,6,7-trimethoxy-8-C-methylflavone were isolated from ethyl acetate extracts of liquid culture filtrates. Structures were confirmed on the basis of UV 1H NMR, 13C NMR spectroscopy, as well as mass spectroscopic techniques and represent the first report of C-methylflavonols produced by fungi. © 1997 Published by Elsevier Science Ltd. All rights reserved

A standard buffer (5 mM phosphate at pH 7) which is used to extract protein from insect eggs provided complete protein solubility for eggs from three of four tree-feeding lepidopteran species: obliquebanded leaf roller (Choristoneura rosaceana), forest tent caterpillar (Malacosoma disstria), and the eastern tent caterpillar (Malacosoma americanum). Under the same extraction protocol, egg proteins from the gypsy moth (Lymantria dispar), remained nearly insoluble. An array of methods typically used to solubilize insect egg proteins were tried and all but the most denaturing (2% SDS) were ineffective. Extraction buffers with typically high pH values were then evaluated. The results indicated that 1) solubility of gypsy moth egg proteins was pH dependent, and full solubility of most egg proteins required the extraction buffer to have a pH of 12 or more prior to the addition of eggs. We also determined that 2) the gypsy moth egg has a buffering capacity which must be surpassed for complete protein extraction, 3) low salt/high pH buffers gave slightly higher total protein values than did high salt/high pH buffers, 4) parental nutritional history (host species utilized) and egg developmental state (pre-embryonatedvs postembryonated/pre-hatch) were unrelated to the requirements for complete egg protein solubilization, and 5) the presence of soluble phenolics, compounds that have the potential to bind to protein and cause insolubility, was confirmed for the gypsy moth egg with 2-D paper chromatography and several other tests. Based on these results, we present a hypothesis about the cause of egg protein insolubility in the gypsy moth.

Seven compounds incorporated into an artificial diet at concentrations of 1, 10 and 100 mg g −1 were evaluated for their effect on growth and mortality of the European corn borer Ostrinia nubilalis (Hubner). At all three concentrations the flavanone pinocembrin, two flavan-3-ols, catechin and epicatechin, and the flavonols, quercetin, rhamnetin, quercitrin and rutin significantly reduced the growth of larvae after only eight days of feeding. By day 18, only larvae fed pinocembrin had a survival rate in excess of 50% at all concentrations. Flavonols were the most toxic, ec 50 (effective concentration to reduce growth relative to controls by 50%) values evaluated on day 8 ranged from 0.17 to 7.4 mg g −1 ; estimated lc 50 (lethal concentration resulting in 50% larval mortality evaluated on day 18) values ranged from 0.16 to 12 mg g −1 . The results suggest the potential of flavonoids for reducing the growth and survivorship of the European corn borer.

Needles from seedlings and mature trees of Pinus banksiana and from mature trees of P. contorta were analysed for their flavonol contents. In P. banksiana needles, seven flavonol glycosides were identified at all ages: kaempferol 3- O β- d -(6″-p-coumaroyl) glucoside, quercetin 3- O β- d -(6″-p-coumaroyl) glucoside, the 3- O -glucoside and the 3- O -galactoside respectively of kaempferol and quercetin, as well as smaller amounts of quercetin 3,3′di- O -glucoside. Needles of mature P. contorta trees also have seven flavonol glycosides but only four in common with P. banksiana : the galactosides and the diglucoside are present only in the latter.

Leaves of Acer rubrum L. afforded the novel 1-O-galloyl-α- l -rhamnose as well as 1-O-galloyl-β- d -glucose; gallic acid; methyl gallate; ethyl gallate; m-digallate and ethyl digallate. Their structures were established on the basis of spectral and chemical evidence.

Antioxidant efficacy of defatted almond whole seed, brown skin, and green shell cover extracts was evaluated by monitoring inhibition of human low-density lipoprotein (LDL) oxidation, inhibition of DNA scission, and metal ion chelation activities. The total phenolic contents of ethanolic extracts of brown skin and green shell cover of almond were 10 and 9 times higher than that of the whole seed, respectively. Brown skin extract at 50 ppm effectively inhibited copper-induced oxidation of human LDL cholesterol compared to whole seed and green shell cover extracts, which reached the same level of efficacy at 200 ppm. Green shell cover extract at 50 ppm level completely arrested peroxyl radical-induced DNA scission, whereas 100 ppm of brown skin and whole seed extracts was required for similar efficiencies. All three almond extracts exhibited excellent metal ion chelation efficacies. High-performance liquid chromatographic (HPLC) analysis revealed the presence of quercetin, isorhamnetin, quercitrin, kaempferol 3-O-rutinoside, isorhamnetin 3-O-glucoside, and morin as the major flavonoids in all extracts.

The principal sex pheromone component of the whitemarked tussock moth (WMTM), Orgyia leucostigma, was recently identified as (Z,Z)-6,9-heneicosadien-11-one (Z6Z9-11-one-21Hy). However, it is thermally unstable and quickly degrades under field conditions so that baited traps are effective for only one night. We have developed a solution to this problem that combines two techniques: (1) the use of a stable pheromone precursor, (Z,Z)-6,9-heneicosadien-11-one ethylene ketal, which is hydrolyzed to the dienone by an acidic aqueous solution (2% p-toluenesulfonic acid in 35% aqueous sorbitol), and (2) use of a small, off-the-shelf, autonomous pump (the Med-e-Cell Infu-disktrade mark) to deliver the precursor continuously to a suitable substrate where it is converted rapidly into the attractive dienone pheromone component. The pump and hydrolysis substrate fit inside sticky traps and because generation and release of pheromone is continuous, the instability of the pheromone is not an issue. In electroantennogram bioassays, dose-dependent responses were obtained with 1 to 1000 ng of hydrolyzed ketal on filter paper, but no response was obtained to 1000 ng of the ketal itself. In wind tunnel bioassays, males were attracted to lures emitting the dienone pheromone component generated from 0.1 to 100 ng of the hydrolyzed ketal. Field tests in 2004 and 2005 showed that sticky traps fitted with the pump delivering the ketal (0.1-1 microg/microL in heptane) at 10 microL/hr to a cotton pad soaked with the hydrolyzing solution were attractive to male WMTM. No moths were caught in controls or traps baited with (Z)-6-heneicosen-11-one. An average of 0.51 moths per trap night was caught over an 18-night period in 2005. The results represent a first step toward developing a sensitive and practical monitoring tool for the WMTM by using a ketal precursor of its unstable dienone pheromone component.

Leaves of Chrysanthemum morifolium cv. Ramat were extracted sequentially with hexane, ethyl acetate, and methanol. The methanol fraction, when incorporated into artificial diet was found to reduce the growth of cabbage looper (Trichoplusia ni Hubner) larvae at concentrations between 500 and 5000 ppm of diet. Fractionation of the methanol extract on a Sephadex column yielded five fractions, three of which reduced the weight of larvae relative to the control. One fraction was analyzed using high performance liquid chromatography (HPLC) and found to contain three main constituents. These compounds were purified using a combination of gel permeation chromatography on Sephadex LH20 and HPLC, and analyzed by 1H and 13CNMR as well as undergoing chemical and physical analyses. The compounds were identified as: 1, chlorogenic acid (5-O-caffeoylquinic acid); 2, 3,5-O-dicaffeoylquinic acid; and 3, 3', 4',5-trihydroxyflavanone7-O-glucuronide (eriodictyol7-O-glucuronide). At concentrations between 100 to 1000 ppm these compounds reduced both growth and photosynthesis of Lemna gibba L. with the order of efficacy being: flavanone > chlorogenic acid > 3,5-O-dicaffeoylquinic acid. Furthermore, when incorporated separately into artificial diet these compounds, at 10 to 1000 ppm, enhanced or reduced growth of the cabbage looper (Trichoplusia ni) and gypsy moth (Lymantria dispar L.).

The whitemarked tussock moth (WMTM), Orgyia leucostigma (J. E. Smith), is a major pest of coniferous and deciduous trees in eastern Canada. Chemical identification of its sex pheromone depended primarily on GC-EAD and HPLC analysis, with confirmation of behavioral activity by wind tunnel and field tests. We identified (Z,Z)-6,9-heneicosadien-11-one (Z,Z-6,9-ket) at 4-5 ng/female as the only essential sex pheromone component. Also detected in female extracts were (Z)-6-heneicosen-11-one (Z6-ket) at 2.5 ng/female, (Z,E)-6,8-heneicosadien-11-one (Z,E-6.8-ket) at about 0.5 ng/female, and a trace amount of (Z,E)-6,9-heneicosadien-11-one. Traps containing as little as 1 microg of Z,Z-6,9-ket attracted males at low population levels, indicating it is a potent sex attractant. Traps baited with Z6-ket attracted few males, and in windtunnel bioassays it was at least 100-fold less attractive to males than Z,Z-6,9-ket. No improvement in trap catch occurred with the addition of Z6-ket in various binary mixtures with Z,Z-6,9-ket, including the female ratio, and a ternary mixture of Z,Z-6.9-ket, Z6-ket, and Z,E-6,8-ket in the 9:5:1 ratio detected in females was no better than Z,Z-6,9-ket alone. We attribute the presence of Z,E-6,8-ket and Z,E-6,9-ket in female extracts to the spontaneous and rapid stereospecific isomerization of Z,Z-6,9-ket at room temperature. Male flight began at sunset but peaked during the second half of the night.

Seventeen flavonoid glycosides were isolated and identified from Artemisia judaica : the 7-glucoside, 7-glucuronide, 4′-glucoside, 7-gentiobioside

Ten flavonoid glycosides were isolated and identified from Artemisia monosperma : vicenin-2, lucenin-2, acacetin 7-glucoside, acacetin 7-rutinoside, the 3-glucosides and 3-rutinosides of quercetin and patuletin, and the 5-glucosides of quercetin and isorhamnetin. From Artemisia herba-alba eight flavonoid glycosides were isolated and identified: isovitexin, vicenin-2, schaftoside, isoschaftoside and the 3-glucosides and 3-rutinosides of quercetin and patuletin.