Behavioral and neurosensory responses of the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae), to fluorinated analogs of aldehyde components of its pheromone

Competitive field tests with -fluorinated analogs of compounds III and IV (III--F and IV--F, respectively) of the boll weevil,Anthonomus grandis Boh., aggregation pheromone showed these compounds, when combined with the other pheromone components [(±)-I and II], to be as attractive as grandlure [(+)-I, II, and III+IV]. Dose-response curves constructed from electroantennograms of male boll weevils to serial stimulus loads of III, IV, III--F, IV--F, and the corresponding acyl fluorinated analogs (III-acyl-F and IV-acyl-F) showed the -fiuorinated analogs to be as active as the pheromone components (threshold=0.1 g), while the acyl fluorinated analogs had a 10-100 x higher threshold (=1-10 g). Single-neuron recordings showed that IV neurons and II neurons (Dickens, 1990) responded to IV--F and III--F, respectively, while IV-acyl-F and III-acyl-F were inactive. Since a previous study showed compounds I, II, and IV to be essential for behavioral responses in the field, it seems likely that the activity of the -fluorinated analogs observed here is due to the stimulation of IV neurons by IV--F as indicated in single neuron recordings.     

Isolation and identification of male medfly attractive components inLitchi chinensis stems andFicus spp. stem exudates

Short-range attraction/feeding stimulation of male Mediterranean fruit flies [Ceratitis capitata (Wiedemann), (Diptera: Tephritidae)] to a stem extract of a host plant,Litchi chinensis Sonn. (Sapindaceae), and to milky exudates from stems of nonhost plants,Ficus retusa L. andF. benjamina L. (Moraceae), were attributed to the presence of the sesquiterpene -copaene. The presence of -copaene in the milky exudate from stems ofF. benghalensis L. is also suggested as eliciting similar behavioral responses in male medflies. The presence of minor quantities of -ylangene in the plants and its contributory effects to the behavioral response of male medflies is discussed. Short-range attraction/feeding stimulation of male medflies to equal amounts of -ylangene-free -copaene samples (94.5%+), prepared from -copaene-enriched angelica seed oil and copaiba oil, respectively, showed no difference in intensity of response. -Ylangene elicited a slightly less intense response for male medflies than -copaene.Names of products in this paper are included for the benefit of the reader and do not imply endorsement or preferential treatment by USDA.     

Response ofScolytus multistriatus (Coleoptera: Scolytidae) to α- and δ-multistriatin in Switzerland

Laboratory bioassays and field tests demonstrated that a Swiss population ofS. multistriatus responded much more strongly to - than to -miltistriatin in combination with 4-methyl-3-heptanol and -cubebene. High concentrations of brevicomin appeared to replace -multistriatin in evoking a response byScolytus species, but this effect can be explained by the fact that the brevicomin was contiminated with small amounts of -multistriatin. Frontalin, another bicyclic ketal, showed no biological activity. Field tests indicated thatS. pygmaeus aggregates to the same attractant mixture asS. multistriatus. S. scolytus also responded preferentially to this mixture, but the relative amounts of -multistriatin to 4-methyl-3-heptanol do not appear to be as important as forS. multistriatus.     

Synthesis and characterization of α-methylstyrene-butadiene-α-methylstyrene linear block copolymers

Summary -methylstyrene-butadiene- -methylstyrene linear block copolymers with a pure block structure were prepared by sec-butyllithium and coupling agent in a four-step process. Their morphology is built up of microdomains of poly- -methylstyrene, including the unbonded segments, dispersed in a polybutadiene matrix. Cylindrical domains arranged in a hexagonal lattice or irregularly shaped domains in a disordered phase are observed, depending on the molecular weight of the poly- -methylstyrene segment.     

Identification and Function of Prothoracic Exocrine Gland Steroids of the Dytiscid Beetles Graphoderus cinereus and Laccophilus minutus

The chemical composition of the prothoracic defensive secretion of the water beetles Graphoderus cinereus and Laccophilus minutus was examined by gas chromatographic–mass spectrometric analysis of trimethylsilylated gland extracts. The main components are 3,11-dihydroxy-5-pregnan-20-one in G. cinereus and 3,12-dihydroxy-5-pregnan20-one in L. minutus. Fully saturated pregnanes have not been found in the prothoracic defensive glands of dytiscids before. Based on tests with synthetic compounds, their biological role was examined in a feeding assay with the minnow Phoxinus phoxinus. Agar pellets containing either steroid strongly deterred feeding.     

Enhancement of βα-recrystallization in β-form isotactic polypropylene during heating after roll deformation

Summary -form isotactic polypropylene shows -recrystallization behavior (recrystallization from - to -form) during slow heating. This is enhanced by deformation. -form specimen with uniaxially oriented lamellae was deformed by rolling, and -recrystallization was studied by DSC and x-ray diffraction. The result showed that (1) — recrystallization is promoted with the degree of deformation. (2) Deformed specimen shows -recrystallization from considerably low temperature compared with the undeformed one. (3) The recrystallized -form is c-axis-oriented along the roll direction. From these results the -recrystallization mechanism was discussed in view of -nucleus formation by deformation.     

Condensation polymerization of α,α′-dimethoxycarbonyl-p-xylylenedicyanide (α,α’) and oxidation to a quinodimethane polymer

Summary , -di(methoxycarbonyl)-p-xylylenedicyanide and oxydiethanol were treated with Ti(OBu)₄ to produce a linear soluble polyester. Long reaction times led to the formation of an insoluble cross-linked polymer by reaction of the cyano groups.Treatment of the soluble polyester with N-cholrosuccinimide and Et₃N resulted in oxidation to a quinodimethane polymer.     

Differential metabolism of 1,8-cineole in insects

In order to compare the metabolism of 1,8-cineole in the pyrgo beetle, Paropsisterna tigrina, three other herbivorous insect species, Faex nigroconspersa, Chrysophtharta bimaculata, and Oxyops vitiosa, were fed 1,8-cineole leaf diets. F. nigroconspersa adults excreted predominantly 9-hydroxy-1,8-cineole (36.2% of the volatile constituents) with some 2-hydroxy-1,8-cineole (11.4%). In contrast, larvae excreted predominantly 2-hydroxy-1,8-cineole (27.4%) and smaller proportions of 9-hydroxy-1,8-cineole (5.2%) and 3-hydroxy-1,8-cineole (4.3%). C. bimaculata adults excreted predominantly 3-hydroxy-1,8-cineole (16.5%). Oxyops vitiosa adults, on a lower 1,8-cineole diet, excreted predominantly 2,9-dihydroxy-1,8-cineole (4.2%) and 2-hydroxy-1,8-cineole (3.5%), with smaller proportions of 3-hydroxy-1,8-cineole (1.1%) and 9-hydroxy-1,8-cineole (0.5%). This is the first reported occurrence of a dihydroxycineole as an insect metabolite. Gas chromatographic and mass spectral data for hydroxycineoles are recorded and interspecific metabolite variation discussed.     

Musk deer (Moschus moschiferus): Reinvestigation of main lipid components from preputial gland secretion

The qualitative and quantitative composition of the principal lipid constituents of Siberian musk deer (Moschus moschiferus) preputial gland secretion, main odor carriers and potential precursors of odorous substances, was investigated by means of high-performance liquid chromatography. Free fatty acids and phenols (10%), waxes (38%), and steroids (38%) were found to be the main groups of the secretion lipids. Cholestanol (I), cholesterol (II), androsterone (III), ⁴-3-hydroxy-17-ketoandrostene (IV), 5, 3-hydroxy-17-ketoandrostane (V), 5, 3, 17-dihydroxyandrostane (VI), 5, 3, 17-dihydroxyandrostane (VII), and 5, 3, 17-dihydroxyandrostane (VIII) were isolated from the steroid fraction and their structures confirmed by IR, PMR, and mass spectra. 3-Methylpentadecanone (muscone) was not identified among the secretion lipids. Preputial gland secretion stimulated sex behavior of musk deer females.     

Mature Atlantic Salmon (Salmo salar L.) Male Parr Are Attracted to Ovulated Female Urine but Not to Ovarian Fluid

The behavioral responses to urine and ovarian fluids from conspecific and heterospecific ovulated females were studied in mature Atlantic salmon (Salmo salar) male parr in a two-choice fluviarium. The males reacted differently to the stimulants. They spent more time in water scented by urine from salmon or brown trout (Salmo trutta L.) females compared to the time in water with ovarian fluids from salmon females. Furthermore, the males were attracted to salmon female urine (different from an indifferent reaction). Males exposed to urine of either species had higher plasma concentrations of testosterone (T) compared to unexposed controls. Measurement of the concentrations of prostaglandin F₂ (PGF₂) and its major metabolite 15-ketodihydro-prostaglandin F₂ (15-ketodihydro-PGF₂) showed that the concentrations of the substances were higher in ovarian fluids of both species compared to those in urine. PGF₂ showed a greater difference between ovarian fluid and urine than its major metabolite. The results suggest that urine of both species, in contrast to ovarian fluid, contain substances that attract mature Atlantic salmon male parr and that the active substances are neither PGF₂ nor 15-keto-PGF₂.     

Response of the European elm bark beetle,Scolytus multistriatus (Coleoptera: Scolytidae), to isomers and components of its pheromone

Laboratory bioassays (two methods) and field tests demonstrated synergistic action of the three components [(–)-4-methyl-3-heptanol (I); (–)-2,4-dimethyl-5-ethyl-6,8-dioxabicylo[3.2.1]octane (-multistriatin) (II); and (–)--cubebene (III)] of the pheromone bouquet ofScolytus multistriatus. Individually and in pairs the components were slightly attractive; I+II was clearly the most active doublet. Indirect evidence indicates that only one of the four enantiomers of I is active. Of the , , and isomers of II, only the is active. With the addition of compound I, slightly attractive extract from mated females became nearly as active as extract from virgin females.     

Synthesis,electroconductivity and third-order nonlinear optical property of poly(2-isopropoxy-5-methoxy-1,4-phenylenevinylene)

Summary Asymmetrically disubstituted poly(2-isopropoxy-5-methoxy-1,4-phenylene-vinylene), PIMPV, was prepared in thin films via organic-soluble precursor polymer method. These polymer films could be easily stretched up to 7 times, and the drawn films of the PIMPV could be doped with FeCl₃ and I₂ to give conductivities of 26.9 and 11.3 Scm^-1, respectively. The third-order nonlinear optical susceptibility of the polymer was determined using third harmonic generation(THG) method at 1907 nm, fundamental wavelength. Measured ⁽³⁰⁾ (-3: , , ) value was 3.7x10^-12 esu.     

Synthesis of monocarboxylic polyoxyethylenes

Summary The various methods of synthesis which can be used to prepare -carboxy polyoxyethylenes are reviewed. The synthesis and the purification of -methoxy -carboxy polyoxyethylenes ( ) are reported. The process consists of the reaction of halogenoacetic acids with an -methoxy -sodium hydroxylate polyoxyethylene followed by a purification by extraction. ,-dimethoxy and -methoxy -ethyl carboxylate polyoxyethylenes were synthesized.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Synergistic Effect of Ethanol to α-Pinene in Primary Attraction of the Larger Pine Shoot Beetle, Tomicus piniperda

-Pinene and ethanol were released in the approximate proportions 1:0.1, 1:0.9 and 1:9 (at 21°C). Ethanol, released in the range of 3–279 mg/day, generally synergized the attraction of T. piniperda to -pinene (30 mg/day at 21°C), although attraction to the mixtures varied within and between years. The low release rate of ethanol together with -pinene attracted a significantly higher number of beetles than -pinene alone in 1995, April of 1996, and in 1997. Lures with the medium release rate of ethanol were the most attractive only in March of 1996. The high dose of ethanol significantly synergized attraction to -pinene in 1995 and 1997. The variable attraction of T. pinipeda to ethanol and -pinene at various release rates and proportions may be due to the temperature dependent nature of beetle antennal sensitivity. At ambient temperatures of 10–13°C. T. piniperda was most attracted to the lures with -pinene and high release rates of ethanol, at 14–17°C it was most attracted to those with medium release rates of ethanol, and at 18°C and higher it was most attraacted to those with low release rates of ethanol.     

An investigation of the interaction of potassium ions with poly(dimethylsiloxane)

The interactions of potassium ions with , -hydroxy-terminated and , -trimethylsilyl-terminated poly(dimethylsiloxanes) (PDMS) have been investigated. After mixing with potassium hydroxide followed by partial extraction, the , -hydroxy-terminated PDMS samples gave elastomeric materials which are thought to result from aggregation of terminal potassium silanolate ion pairs. Uniaxial tensile testing of these materials was carried out at 298 K. The , -trimethylsilyl-terminated PDMS, when mixed with potassium hydroxide, however, gave completely soluble material following identical solvent extraction procedures.     

Alleviation of α-tomatine-induced toxicity to the parasitoid,Hyposoter exiguae,by phytosterols in the diet of the host,Heliothis zea

The solitary, endoparasitic ichneumonid,Hyposoter exiguae (Viereck) is a parasitoid of the tomato fruitworm,Heliothis zea (Boddie). However, the parasitoid is deleteriously affected by the tomato glycoalkaloid, -tomatine, ingested from hosts (H. zea) fed on artificial diets or semipurified extracts of tomato plants that contained -tomatine. -Tomatine causes prolonged larval development; disruption or prevention of pupal eclosion; deformation of antennal, abdominal, and genital structures; and reduction in adult weight and longevity of the parasitoid. These toxic effects are exacerbated when the dietary dose of -tomatine is increased from 12 mol to 20 mol/g dry wt of diet. However, the toxicity of -tomatine is attenuated in parasitoids reared from hosts fed on artificial diets that contain equimolar or supramolar amounts of 3-OH-sterols admixed with -tomatine. Further, the toxicity of extracts from the foliage of different cultivars of tomatoes toH. exiguae is contingent upon the composite levels of -tomatine and total phytosterol (free and esterified). Cultivars with a low total sterol-tomatine ratio are more toxic toH. exiguae. The possible mode of action of -tomatine toxicity toH. exiguae by disruption of sterol metabolism is discussed.     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

The effect of carbon black filling and cross-linking in stretched SBR networks: a 2H-NMR study

Summary The line splitting v in ²H-NMR spectra of deuterated benzene in stretched crosslinked SBR depended linearly on the classical stretch term ² – 1/ for samples with and without carbon black filling. The ratio LS = v/(² – 1/) was measured in dependence on the solvent fraction . The extrapolated value L of this ratio at =0 gave a linear dependence on the inverse molecular mass 1/M_c of inter-crosslink chains. This was expected according to a simple model of chain dynamics and offers a further NMR-method for M_c-determination even in filled networks. However, the slope of the L(1/M_c)-line increases with an addition of carbon black which indicates a higher molecular order. Three reasons for this could be discussed. However, one of them is preferable.     

Electrochemical behaviour of viologen-cyclodextrin inclusion complexes. The case of non-alkyl group substituted viologen

The electrochemical behavior of non-alkyl substituted viologen, 4,4-dibenzyl bipyridinium (BzV), 4,4-dicyanophenyl bipyridinium (CyV) and -,-,-cyclodextrin (, , -CD) was studied using cyclic voltammetry and a spectroelectrochemical method. It was found that BzV and Fe(CN) ₆ ^4– formed a charge-transfer (CT) complex with a ratio of 21 and the colour of the solution faded with the addition of an electrolyte. This behaviour is the same as in then-heptyl viologen and ferrocyanide system [1]. BzV, -CD and -CD formed an inclusion complex only in the reduced state, whilst BzV and -CD formed an inclusion complex in both the oxidized and the reduced state. An EC scheme in which a chemical reaction follows an electrochemical reaction was considered to predominate in the BzV and -, -CD systems, while a CE scheme in which a chemical reaction preceded an electrochemical reaction predominated in the BzV and -CD system. On the other hand, CyV was found to form an inclusion complex with -, -, -CD in both the oxidized and the reduced states. therefore a CE scheme was considered to predominate in the CyV--, -, -CD systems.