4-Pyridyl carbonyl compounds as thrips lures: effectiveness for Western flower thrips in y-tube bioassays

In a search for chemical lures to manage the cosmopolitan crop pest western flower thrips (WFT), Frankliniella occidentalis, a Y-tube olfactometer was used to screen 20 compounds, including 18 4-pyridyl compounds. Comparison of Y-tube results for New Zealand flower thrips (NZFT), Thrips obscuratus, with field trapping data for ethyl nicotinate and ethyl isonicotinate, suggested that the minimum attractive dose (MAD) of an odor compound, where significantly ( p < 0.05) more than 50% of thrips walked up the odor-laden arm, provided a measure for selecting compounds to evaluate for potential lure efficacy in the field. Eighteen synthetic 4-pyridyl compounds were tested on female WFT in a Y-tube olfactometer and four 4-pyridyl carbonyl compounds had MADs lower than the known WFT attractants p-anisaldehyde (MAD 10 (-3) microL) and ethyl nicotinate (10 (-2) microL): methyl isonicotinate (10 (-6) microL), ethyl-2-chloropyridine-4-carboxylate (10 (-6) microL), ethyl isonicotinate (10 (-4) microL) and methyl 4-pyridyl ketone (10 (-5) microL). The suitability of MAD for selecting compounds for further evaluation of practical lure efficacy is discussed. Comparisons of activities within homologous series of esters and ketones showed that attractant activity decreased with chain length. 4-Formyl pyridine was an attractant at a dose of 10 (-5) microL, but was repellent at higher doses (10 (-2)-10 degrees microL).     

Isolation and characterization of novel benzoates, cinnamates, flavonoids, and lignans from Riesling wine and screening for antioxidant activity.

A German Riesling wine has been fractionated with the aid of countercurrent chromatography. After purification by HPLC, the structures of 101 compounds were established by mass spectrometry and NMR spectroscopy. Seventy-three of the isolated compounds exhibited a phenolic or benzylic structure. Fifty-four compounds were reported for the first time as Riesling wine constituents. New compounds identified in this work included twelve benzoic and cinnamic acid derivatives. In addition to two isomeric (E)-caffeoyl ethyl tartrates, the glucose esters of (E)-cinnamic, (E)-p-coumaric, and (E)-ferulic acid, as well as the 4-O-glucosides of (E)- and (Z)-ferulic acid, have been identified for the first time in Riesling wine. The structures of two additional phenylpropanoids were elucidated as 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-propan-1-one and 2,3-dihydroxy-1-(4-hydroxy-3-methoxyphenyl)-propan-1-one. Moreover, two ethyl esters, i.e., ethyl protocatechuate and ethyl gallate, as well as the glucose ester of vanillic acid, were newly detected in Riesling wine. Novel representatives in the flavonoid group were dihydrokaempferol, dihydroquercetin, and four dihydroflavonol glycoconjugates, i.e., the 3-O-glucosides of dihydrokaempferol and dihydroquercetin, as well as the 3-O-xyloside and the 3'-O-glucoside of dihydroquercetin. Additionally, six novel lignans, i.e., lariciresinol 4-O-glucoside, three isolariciresinol derivatives, and two secoisolariciresinols, as well as three neolignans were isolated. Structural elucidation of the newly isolated wine constituents is reported together with the determination of their antioxidant activity.     

Precursors and formation of pyrithione and other pyridyl-containing sulfur compounds in drumstick onion, Allium stipitatum

Two novel, structurally unusual cysteine derivatives were isolated from the bulbs of Allium stipitatum (Allium subg. Melanocrommyum) and shown to be S-(2-pyridyl)cysteine N-oxide and S-(2-pyridyl)glutathione N-oxide. The former compound is the first example of a naturally occurring alliinase substrate that contains an N-oxide functionality instead of the S-oxide group. In addition, S-methylcysteine S-oxide (methiin) and S-(methylthiomethyl)cysteine 4-oxide (marasmin) were found in the bulbs. Presented data suggest that the previously reported identification of S-(2-pyridyl)cysteine S-oxide was most likely erroneous. The alliinase-mediated formation of pyridyl-containing compounds following disruption of A. stipitatum bulbs was studied by a combination of HPLC-MS, HPLC-PDA, DART-MS, and NMR techniques. It was found that no pyridyl-containing thiosulfinates are present in homogenized bulbs in detectable quantities. Instead, various pyridine N-oxide derivatives are formed, including N-hydroxypyridine-2(1H)-thione (pyrithione), 2-(methyldithio)pyridine N-oxide, 2-[(methylthio)methyldithio]pyridine N-oxide, di(2-pyridyl) disulfide N-oxide, and di(2-pyridyl) disulfide N,N'-dioxide. This represents the first report of pyrithione formation as a natural product.     

Flufenerim, a novel insecticide acting on diverse insect pests: biological mode of action and biochemical aspects

A new chemical compound was tested for its insecticidal activity against several major insect pests. The compound, called "flufenerim", has a core pyrimidine structure and an unknown mode of action and showed potent activity against the sweet potato whitefly Bemisia tabaci (Gennadius), the green peach aphid Myzus persicae (Sulzer), and the African cotton leafworm Spodoptera littoralis (Boisduval); however, it did not show any activity against two thrips species: western flower thrips Frankliniella occidentalis (Pergande) and tobacco thrips Thrips tabaci (Lindeman). The compound was relatively potent against the three tested pests and caused mortality rates that reached up to 100% at concentrations under 10 mg of active ingredient (ai) L(-1). The action of the compound was very fast, and mortality was observed within 48 h after exposure of the insects to treated leaves. A unique characteristic of this compound is its very short residual activity, which approximates to 4 days after application under laboratory conditions and to 2 days under outdoor conditions for both B. tabaci and S. littoralis. Although this new compound's mode of action is yet unknown, its rapid and potent action against sap-sucking pests suggests that it acts on a very important target site in the insect body and possibly could be applied very close to harvesting.     

Characterization of aroma compounds in apple cider using solvent-assisted flavor evaporation and headspace solid-phase microextraction

The aroma-active compounds in two apple ciders were identified using gas chromatography-olfactometry (GC-O) and GC-mass spectrometry (MS) techniques. The volatile compounds were extracted using solvent-assisted flavor evaporation (SAFE) and headspace solid-phase microextraction (HS-SPME). On the basis of odor intensity, the most important aroma compounds in the two apple cider samples were 2-phenylethanol, butanoic acid, octanoic acid, 2-methylbutanoic acid, 2-phenylethyl acetate, ethyl 2-methylbutanoate, ethyl butanoate, ethyl hexanoate, 4-ethylguaiacol, eugenol, and 4-vinylphenol. Sulfur-containing compounds, terpene derivatives, and lactones were also detected in ciders. Although most of the aroma compounds were common in both ciders, the aroma intensities were different. Comparison of extraction techniques showed that the SAFE technique had a higher recovery for acids and hydroxy-containing compounds, whereas the HS-SPME technique had a higher recovery for esters and highly volatile compounds.     

Evaluation of Gossypium arboreum L. Germplasm for resistance to thrips

Summary As part of a project to assess the U.S. Asiatic Cotton Germplasm Collection as a source of genes for pest resistance, forty-three accessions of Gossypium arboreum L. were evaluated for resistance to thrips. Thrips, Thysanoptera spp., are a minor, but widespread pest on cotton, G. hirsutum L. and G. barbadense L. Accessions were planted in free-choice field tests in 1988, 1989, and 1990 at the Cotton Branch Experiment Station, Marianna, Arkansas. Damage ratings, based on a scale of 0 (no damage) to 7 (severe damage), were made approximately one month after planting. Relative score was computed by dividing the rating of each accession by the rating of the reference, G. hirsutum Stoneville 506. The relative score averaged over all G. arboreum accessions by year varied with the year, but was less than 100 (relative score for Stoneville 506) in each case. When data were combined for all three years, twenty-five accessions were significantly better than Stoneville 506. Introgression of the better accessions into G. hirsutum is now in progress.Abbreviations NPGS National Plant Germplasm System - STV 506 G. hirsutum Stoneville 506     

Characterization of odor-active compounds in guava wine

The volatile compounds of guava wine were isolated by continuous solvent extraction and analyzed by GC-FID and GC-MS. A total of 124 volatile constituents were detected, and 102 of them were positively identified. The composition of guava wine included 52 esters, 24 alcohols, 11 ketones, 7 acids, 6 aldehydes, 6 terpenes, 4 phenols and derivatives, 4 lactones, 4 sulfur-compounds, and 5 miscellaneous compounds. The aroma-active areas in the gas chromatogram were screened by application of the aroma extract dilution analysis and by odor activity values. Twelve odorants were considered as odor-active volatiles: (E)-β-damascenone, ethyl octanoate, ethyl 3-phenylpropanoate, ethyl hexanoate, 3-methylbutyl acetate, 2-methyltetrahydrothiophen-3-one, 2,5-dimethyl-4-methoxy-3(2H)-furanone, ethyl (E)-cinnamate, ethyl butanoate, (E)-cinnamyl acetate, 3-phenylpropyl acetate, and ethyl 2-methylpropanoate.     

西花蓟马成虫在日光温室内的分布和日活动规律

利用蓝色粘虫板在山东省青州市高柳镇日光温室内研究了西花蓟马(Frankliniella occidentalis)成虫在2009年3月下旬茄子植株上的分布和日活动规律。结果表明,西花蓟马成虫数量在日光温室内由北向南依次减少,北边平均每日诱集量为65.3头·组-1,中间为40.0头·组-1,南边为20.4头·组-1,南北蓝板每日平均诱集量间存在显著差异。日光温室内东西方向上西花蓟马成虫分布表现为由中间向东西两边逐渐增多。在垂直方向上,西花蓟马成虫在茄子所有叶片上均有分布。蓝板对西花蓟马成虫的诱集量从7:00开始逐渐增多到15:00达到最大值,而后逐渐减少,每天有1个活动高峰。另外,蓝板南面(330.6头·d-1)诱集量显著高于北面(242.2头·d-1),东面(343.8头·d-1)显著高于西面(208.0头·d-1)。     

Comparing factors associated with total and dead sooty shearwater bycatch in New Zealand trawl fisheries

Incidental capture of seabirds is a conservation concern because such periodic ‘bycatch’ may cause population declines. Not all birds die upon capture, but distinctions between total and dead captures are rarely done. Thus, it is currently unclear whether using total captures is an adequate simplification, for example when studying factors associated with bycatch. We investigated this question by analysing total and dead procellariiform seabird captures of 663 trawling operations between 1996 and 2008 in the Exclusive Economic Zone of New Zealand. As potential factors associated with bycatch, we considered eleven technical and seven environmental characteristics recorded by onboard observers during commercial trawling. A total of 1 231 procellariids were recovered as bycatch, with sooty shearwaters (Puffinus griseus) comprising 98% of the bycatch sample. Our analyses indicated that specific technical (headline height) and environmental factors (month, daylight, sea state, area code) influenced both total and dead captures of sooty shearwaters, with similar results for both response variables. Using total captures may thus be an adequate simplification in the interpretation of sooty shearwater captures in New Zealand trawl fisheries, and practices that mitigate the overall capture of birds will be most effective.     

Gas-liquid chromatographic determination of thiabendazole and methyl 2-benzimidazole carbamate in fruits and crops.

A method is described for the electron capture gas-liquid chromatographic determination of thiabendazole and methyl 2-benzimidazole carbamate (MBC) after derivatization with pentafluorobenzyl bromide (PFB-Br). The samples are extracted with ethyl acetate, and the residual thiabendazole, benomyl, and MBC are isolated by liquid-liquid extraction into dilute HCl. After neutralization and re-extraction with ethyl acetate, thiabendazole and MBC are reacted with PFB-Br to form the PFB derivatives. Alumina column chromatography was used to clean up extracts, and the derivatives could be detected as low as 5-10 pg. Recoveries were 95-98% from fruits fortified with 0.3-2.0 ppm thiabenzadole; recoveries were 91-97% when 0.05-1.0 ppm benomyl/MBC were added to fruits/crops. The PFB derivatives were identified by gas-liquid chromatography-mass spectrometry.     

Soil phosphorus characterisation by 31p nuclear magnetic resonance

Abstract

Five New Zealand topsoils, including three sampled under introduced pasture and two in native tussock grasslands, were extracted with 0.5 M NaOH, and the different classes of phosphorus compounds in the extracts distinguished by ³¹p nuclear magnetic resonance (n.m.r.).

Inorganic orthophosphate and orthophosphate monoesters were the major forms of phosphorus in all soil extracts. The tussock‐grassland soil extracts showed the greatest diversity of phosphorus forms, and included compounds with n.m.r. signals ascribed to phosphonates, a previously unreported form of soil phosphorus.     

西花蓟马孤雌产雄生殖繁育的后代种群生命表的建立

孤雌生殖是西花蓟马(Frankliniella occidentalis)繁殖的一种重要方式。前期研究发现,西花蓟马在高温下,雌性的存活率远大于雄性。为探究高温处理后仅有雌性西花蓟马孤雌产雄的情况下其后代建立种群的可能性,试验设定:高温(45℃,2 h)处理西花蓟马单个雌性个体,分别进行孤雌产雄生殖后,雄性子代(F1代)与其母系回交产生F2代;高温(45℃,2 h)处理西花蓟马多个雌性个体,进行孤雌产雄生殖后,雄性子代(F1代)与亲代多个雌性个体共存情况下进行交配产生F2代。两组处理模式下建立F2代实验种群生命表。结果表明,上述两种处理模式,母代雌性个体与子代雄性个体交配后均可产生后代,雄性F1代与其母系回交产生的F2代的雌雄性比为1.05∶1;与亲代多个雌性个体共存下交配产生的F2代性比为1.55∶1。雄性F1代与其母系回交产生的F2代的平均单雌产卵量(F)和内禀增长率(rm)显著小于与亲代多个雌性个体共存下交配产生的F2代(P0.05);各龄期的平均发育历期、平均产卵前期和平均总产卵前期2个繁殖力参数以及净生殖率(R0)、平均世代周期(T)2个种群参数,前者则比后者长(P0.05);另周限增长率(λ)两者之间无显著差异。研究表明西花蓟马在孤雌产雄状态下仍然可以在短期建立种群,具有较强的抗高温能力和繁殖能力,为其成功入侵奠定了生态学基础。     

Cultivar and growing region determine the antioxidant polyphenolic concentration and composition of apples grown in New Zealand

Evidence suggests that increasing consumption of fruit and vegetables contributes to improved health and well-being by providing protection from diseases including various cancers and cardiovascular disease. Although there is uncertainty about which components generate this effect, an attractive hypothesis is that the antioxidants are at least partly responsible. We measured the polyphenolic concentrations in 10 different apple cultivars grown commercially in New Zealand, each sourced from three different geographic regions. Our results showed that the concentration of polyphenolics varied among the apple cultivars, with Pacific Queen containing 2.7 times the amount of polyphenolics found in Cox's Orange. Furthermore, there were significant differences in polyphenolic concentrations in fruit from different regions for some cultivars but not for others. We also measured the polyphenolic concentrations in apple skin and flesh and found that on average 46% of the polyphenolics in whole apples were in the skin. Essentially all of the flavonols (quercetin derivatives) were present in the skin. To maximize the intake of apple polyphenols, it is necessary to consume apples of cultivars with high polyphenolic concentrations such as Pacific Queen and include the skin. Our results also showed that there is potential for promoting apple fruit from specific geographical regions because they contained elevated concentrations of antioxidant polyphenolic compounds.     

Synthesis and herbicidal activities of novel 3-N-substituted amino-6-methyl-4-(3-trifluoromethylphenyl)pyridazine derivatives

4-(3-Trifluoromethylphenyl)pyridazine is a new series of compounds with bleaching and herbicidal activities. Starting from ethyl 2-(3-trifluoromethylphenyl)acetate, an important intermediate 7 was synthesized in five steps with a moderate total yield of 51.5% in a safe and practical way. Twenty-six novel 3-N-substituted amino-6-methyl-4-(3-trifluoromethylphenyl)pyridazine derivatives were synthesized and evaluated through a Spirodela polyrrhiza test and greenhouse test. Some compounds can completely inhibit Chl at 1 microg/mL and exhibit equal or higher herbicidal activities with the commercial bleaching herbicide diflufenican against dicotyledonous plants at a rate of 75 g/ha.     

Gas chromatographic analysis of milk for deoxynivalenol and its metabolite DOM-1

A gas chromatographic method is described for the determination of deoxynivalenol (DON) and its metabolite DOM-1 in milk. Milk samples were extracted with ethyl acetate on a commercially available disposable extraction column, followed by hexane-acetonitrile partitioning. Final purification was accomplished on a reverse phase C-18 cartridge. The trimethylsilyl ether (TMS) derivatives of DON were prepared, chromatographed on an OV-17 column, and quantitated with an electron capture detector. Chromatography of the TMS derivatives of milk extracts was compared to that of the corresponding heptafluorobutyryl derivatives. The limit of detection using TMS derivatives was 1 ng/mL for both toxins with recoveries averaging 82% +/- 9% at 2.5 and 10 ng/mL milk for DON and 85% +/- 6% at 10 ng/mL for DOM-1.     

Aroma compounds of fresh milk from New Zealand cows fed different diets

Volatile compounds were extracted from fresh milk produced by New Zealand cows using the newly developed solvent-assisted flavor evaporation (SAFE) technique. The two samples that were used came from cows that had been fed on different diets and represented the considerably different flavors of Northern hemisphere and New Zealand milk. Using gas chromatography-olfactometry (GC-O), 71 aroma compounds were found from the milk extracts, 66 of which were identified. Nearly all of the aroma compounds were common to both extracts, despite the two milk samples having quite different flavors. Only one compound, gamma-12:2 lactone, was significantly odor-active for the extract of milk from cows fed a supplement diet, but was not found for the extract of milk from cows fed a pasture diet. Thus, differences in milk flavor are primarily caused by concentration differences of a common set of flavor compounds, rather than by the occurrence of compounds uniquely associated with a particular feed.     

Volatile constituents of fermented sugar baits and their attraction to lepidopteran species

The volatile compounds emanating from four fermented sugar baits, palm sugar, golden cane syrup, port wine, and molasses, were isolated by headspace sampling and analyzed by gas chromatography-mass spectrometry. Three classes of compounds including esters, alcohols, and aromatic compounds were identified in the headspace of the four fermented sugar baits. There was a high degree of qualitative similarity between the headspace contents of the four fermented sugar baits, although quantitatively they varied considerably. Ethyl acetate, 3-methylbutanol, ethyl hexanoate, 2-phenylethanol, ethyl octanoate, ethyl (E)-4-decenoate, ethyl decanoate, and ethyl dodecanoate were the major compounds identified in the headspace of the four fermented sugar baits. The efficacy of the four fermented sugar baits was investigated in field trapping experiments. Fermented palm sugar and golden cane syrup were superior in attracting significant numbers of moths as compared to port wine and molasses. Fermented molasses was the least attractive among the four baits. Over 90% of the insects caught were noctuids with Graphania mutans and Tmetolophota spp. being the main noctuids captured (over 55%) in the four fermented sugar baits. Male and female G. mutans were equally attracted to the four sugar baits. A number of tortricid species were also trapped.     

Odor potency of aroma compounds in Riesling and Vidal blanc table wines and icewines by gas chromatography-olfactometry-mass spectrometry

This study aimed to elucidate the odor potency of aroma compounds in Riesling and Vidal blanc (syn. Vidal) table wines and icewines from the Niagara Peninsula using stir bar sorptive extraction-gas chromatography-olfactometry-mass spectrometry. Dilution analysis determined the most odor-potent compounds in Vidal and Riesling icewines (n = 2) and table wines (n = 2) from a commercial producer. The top 15 odor-potent compounds in each wine were identified and quantified, resulting in 23 and 24 compounds for Riesling and Vidal, respectively. The most odor-potent compounds were β-damascenone, decanal, 1-hexanol, 1-octen-3-ol, 4-vinylguaiacol, ethyl hexanoate, and ethyl 3-methylbutyrate. In general, icewines had higher concentrations of most aroma compounds compared to table wines. Through computation of odor activity values, the compounds with the highest odor activity for the icewines were β-damascenone, 1-octen-3-ol, ethyl octanoate, cis-rose oxide, and ethyl hexanoate. In table wines the highest odor activity values were found for ethyl octanoate, β-damascenone, ethyl hexanoate, cis-rose oxide, ethyl 3-methylbutyrate, and 4-vinylguaiacol. These findings provide a foundation to determine impact odorants in icewines and the effects of viticultural and enological practices on wine aroma volatile composition.     

Butyltin and phenyltin compounds in river i bay sediments of Tokyo

The occurrence and current status of butyltin and phenyltin compounds were investigated in sediments collected from the Arakawa and Sumida Rivers and Tokyo Bay in 2000. A series of butyltin and phenyltin compounds, including monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) was detected by gas chromatography-mass spectrometry (GC-MS). The total concentrations of the butyltin (MBT + DBT + TBT) and phenyltin (MPT + DPT + TPT) compounds ranged from 25.7 to 116 and from non-detectable levels to 22.4 ng g' (as Sn), respectively. The concentrations of the organotin (OT) compounds in sediments were relatively lower than those of the samples collected in 1984. OT compounds accounted for 124% (as Sn) of total Sn in the sediments. Among the OT compounds investigated, MBT was the most prevalent in the sediments.     

Specificity of codling moth (Lepidoptera: Tortricidae) for the host plant kairomone, ethyl (2E,4Z)-2,4-decadienoate: field bioassays with pome fruit volatiles, analogue, and isomeric compounds

Codling moth, Cydia pomonella (L.), is a severe pest of apples, pears, and walnuts worldwide, and new approaches for precise monitoring and management would be beneficial. Ninety-two pome fruit volatiles were formulated in 23 distinct blends, of which a single 4-component blend of 10-carbon esters showed the only significant attraction of moths in field bioassays conducted in both walnut and apple orchards. A single constituent of this blend, ethyl (2E,4Z)-2,4-decadienoate--the "pear ester", was the major contributing attractant. The pear ester attracted both male and female moths in combined numbers that were comparable to the attractiveness of conspecific sex pheromone. Structure-activity tests were conducted in a series of orchard trials to determine the specificity of attraction of codling moths to the pear ester kairomone. No analogue 10-carbon alcohols, aldehydes, acetates, or other esters elicited significant moth capture responses. Tests with various analogue esters with alcohol chain length moiety substitutions of the (2E,4Z)-2,4-decadienoic acid elicited differential capture responses, with the ethyl exceeding the propyl, methyl, butyl, and hexyl analogues. The (E,Z) geometric isomers of this series of (2E,4Z)-2,4-decadienoic acid esters far exceeded the attractiveness of the (E,E) isomers. The pear ester is a potent attractant of both males and females, and codling moths are highly discriminating and specific in their structure-activity-based attraction to this pear-derived kairomone. These specificity attributes should allow this host plant kairomone to contribute to new abilities for female monitoring and the potential of development of novel and highly selective control practices that should decrease the current dependence on the use of broad-spectrum insecticides.