Laboratory Evidence of 2-Isobutyl-3-methoxypyrazine as a Male-Released Aggregative Cue in Labidostomis lusitanica (Germar) (Coleoptera: Chrysomelidae).

In spite of its incidence on pistachio trees, the chemical ecology of Labidostomis lusitanica (Germar) (Coleoptera: Chrysomelidae) has been neglected so far. In this work, we provide the first evidence of a biologically active male-specific compound that may be promoting field aggregation. Headspace collections through solid-phase microextraction from feral males and females reported the presence of 2-isobutyl-3-methoxypyrazine exclusively in males. Electroantennographic recordings revealed that males and females responded in a dose-dependent manner to increasing stimuli of 2-isobutyl-3-methoxypyrazine, with females overall displaying a higher response than males. In dual-choice tests, both males and females showed a significant preference for the compound in comparison to a pure air stimulus. In light of these results, the possible role of 2-isobutyl-3-methoxypyrazine as an aggregation cue in L. lusitanica is discussed.

Olean (1,7-dioxaspiro[5.5]undecane): A Novel Intraspecific Chemical Cue in Coraebus undatus (F.) (Coleoptera: Buprestidae).

The main aim of this work was to identify semiochemicals from the jewel beetle Coraebus undatus (F.) (Coleoptera: Buprestidae) that may aid in the improvement of current monitoring tools. First, HS-SPME collections revealed that individually sampled adults (>7 days old) of both sexes release the spiroacetal 1,7-dioxaspiro[5.5]undecane (olean). Electroantennographic recordings from both sexes exposed to increasing amounts of olean followed a dose-dependent pattern, with females being more responsive than males to the highest amount of the compound (100 µg). In double-choice assays, adults older than seven days were significantly attracted to olean, whereas this attraction was not detected in insects aged less than seven days. Indeed, a repellent effect was observed in young females. Subsequent field trials employing sticky purple prism traps revealed that there were no differences among the number of insects caught in control and olean-baited traps at two different release rates (0.75 and 3.75 mg/day). Interestingly, all the trapped specimens were determined as mated females, regardless of the presence of olean. Overall, these findings provide a basis for unraveling the chemical ecology of the species, although further research is still needed to determine the specific role of this compound within the chemical communication of the species.

Differential Health Effects on Inflammatory, Immunological and Stress Parameters in Professional Soccer Players and Sedentary Individuals after Consuming a Synbiotic. A Triple-Blinded, Randomized, Placebo-Controlled Pilot Study.

The main objective of this research was to carry out an experimental study, triple-blind, on the possible immunophysiological effects of a nutritional supplement (synbiotic, Gasteel Plus®, Heel España S.A.U.), containing a mixture of probiotic strains, such as Bifidobacterium lactis CBP-001010, Lactobacillus rhamnosus CNCM I-4036, and Bifidobacterium longum ES1, as well as the prebiotic fructooligosaccharides, on both professional athletes and sedentary people. The effects on some inflammatory/immune (IL-1ß, IL-10, and immunoglobulin A) and stress (epinephrine, norepinephrine, dopamine, serotonin, corticotropin-releasing hormone (CRH), Adrenocorticotropic hormone (ACTH), and cortisol) biomarkers were evaluated, determined by flow cytometer and ELISA. The effects on metabolic profile and physical activity, as well as on various parameters that could affect physical and mental health, were also evaluated via the use of accelerometry and validated questionnaires. The participants were professional soccer players in the Second Division B of the Spanish League and sedentary students of the same sex and age range. Both study groups were randomly divided into two groups: a control group-administered with placebo, and an experimental group-administered with the synbiotic. Each participant was evaluated at baseline, as well as after the intervention, which lasted one month. Only in the athlete group did the synbiotic intervention clearly improve objective physical activity and sleep quality, as well as perceived general health, stress, and anxiety levels. Furthermore, the synbiotic induced an immunophysiological bioregulatory effect, depending on the basal situation of each experimental group, particularly in the systemic levels of IL-1ß (increased significantly only in the sedentary group), CRH (decreased significantly only in the sedentary group), and dopamine (increased significantly only in the athlete group). There were no significant differences between groups in the levels of immunoglobulin A or in the metabolic profile as a result of the intervention. It is concluded that synbiotic nutritional supplements can improve anxiety, stress, and sleep quality, particularly in sportspeople, which appears to be linked to an improved immuno-neuroendocrine response in which IL-1ß, CRH, and dopamine are clearly involved.

Inhibitory effect of thymol on pheromone-mediated attraction in two pest moth species.

Plant essential oils are considered as important bio-sources for the development of natural and environmentally safe pest control tools due to their multiple modes of action on insects. In this paper we have evaluated the activity of commercially available thyme oil and its constituents thymol, carvacrol, and p-cymene, as potential disruptants of the pheromone-mediated communication in the major pest moths Spodoptera littoralis Boisduval (Lepidoptera: Noctuidae), and Grapholita molesta (Busck) (Lepidoptera: Tortricidae). In electroantennographic assays, the antennal response of males to thyme oil, thymol, and carvacrol was altered at high doses (103-104 µg), shifting the signal waveform into a biphasic negative-positive potential that caused a decay in the response. In wind tunnel assays, pheromone-mediated attraction of males of both species was interrupted in presence of thyme oil. Further trials demonstrated that thymol alone reduced the number of G. molesta and S. littoralis males landing on the pheromone source. This effect did not differ from that of thyme oil, although the latter provoked a significant reduction on downwind behavior steps in S. littoralis. Overall, our findings provide a preliminary basis for delving into the effect of thyme oil, and especially of its major constituent thymol, as potential mating disruptants of both species.

Two chiral types of randomly rotated ommatidia are distributed across the retina of the flathead oak borer Coraebus undatus (Coleoptera: Buprestidae).

Jewel beetles are colorful insects, which use vision to recognize their conspecifics and can be lured with colored traps. We investigated the retina and coloration of one member of this family, the flathead oak borer Coraebus undatus using microscopy, spectrometry, polarimetry, electroretinography and intracellular recordings of photoreceptor cell responses. The compound eyes are built of a highly unusual mosaic of mirror-symmetric or chiral ommatidia that are randomly rotated along the body axes. Each ommatidium has eight photoreceptors, two of them having rhabdomeres in tiers. The eyes contain six spectral classes of photoreceptors, peaking in the UV, blue, green and red. Most photoreceptors have moderate polarization sensitivity with randomly distributed angular maxima. The beetles have the necessary retinal substrate for complex color vision, required to recognize conspecifics and suitable for a targeted design of color traps. However, the jewel beetle array of freely rotated ommatidia is very different from the ordered mosaic in insects that have object-directed polarization vision. We propose that ommatidial rotation enables the cancelling out of polarization signals, thus allowing stable color vision, similar to the rhabdomeric twist in the eyes of flies and honeybees.

Influence of Age, Host Plant and Mating Status in Pheromone Production and New Insights on Perception Plasticity in Tuta Absoluta.

The tomato leafminer Tuta absoluta Meyrick (Lepidoptera: Gelechiidae) is one of the most important pests of tomato worldwide. However, in spite of its tremendous economic importance, the success of environmentally friendly measures to control the pest is still limited. Study of physiological and behavioral parameters that affect pheromone production has provided useful information for pest management. Our results show no clear difference in pheromone production by females over the period from 2 h before to 2 h after the scotophase. However, pheromone production was clearly dependent on female age, with young females producing the highest amount of each pheromone component 10 days after emergence. In the presence of the host plant (physical contact and olfaction of the plant volatiles), virgin and mated females produced higher amounts of the major component of the pheromone (TDTA) than those in the absence of plant and those devoid of olfaction (antennectomized) but in physical contact with the plant. In electrophysiological experiments, TDTA elicited slightly lower responses on male antennae than the pheromone mixture. When stimulated at certain time intervals after the first exposure to TDTA, male antennae became more sensitive to the stimulus (sensitization effect). For the first time in an insect of the family Gelechiidae, we have found that females are able to detect their own pheromone (autodetection). Altogether, our results may represent a step forward in the knowledge of the chemical communication of this important pest.

Enantioselective Synthesis and Activity of All Diastereoisomers of ( E)-Phytal, a Pheromone Component of the Moroccan Locust, Dociostaurus maroccanus.

The Moroccan locust, Dociostaurus maroccanus (Thunberg, 1815) (Orthoptera: Acrididae), is a polyphagous pest capable of inflicting large losses in agriculture under favorable environmental and climatic conditions. Currently, control of the pest relies solely on the application of conventional insecticides that have negative effects on the environment and human safety. In the search for a more rational, environmentally acceptable approach for locust control, we have previously reported that ( Z/ E)-phytal (1) is a male-produced candidate sex pheromone of this acridid. This molecule, with two stereogenic centers at C-7 and C-11, has four different diastereomers along with the Z/ E stereochemistry of the double bond at C-2. In this paper, we present for the first time the enantioselective synthesis of the four diastereomers of ( E)-phytal and their electrophysiological and behavioral activity on males and females. Our results demonstrate that the ( R, R)-phytal is the most active diastereomer in both assays, significantly attracting females in a double-choice Y olfactometer, and confirming the previous chromatographic assignment as component of the sex pheromone of the Moroccan locust.

Sexual communication in castniid moths: Males mark their territories and appear to bear all chemical burden.

Castniid moths (Lepidoptera: Castniidae) display a butterfly-like reproductive behavior, i.e., they use visual stimuli for mate location and females have apparently lost their pheromone glands in an evolutionary context. In this paper we report for the first time the identification of three new compounds, namely n-octadecyl acetate, (Z)-9-octadecenyl acetate and (E,Z)-2,13-octadecadienyl acetate, in males of the Castniid Palm Borer, Paysandisia archon, which could be involved in its short-range courtship behavior, and also shed light on recent controversies on the sexual behavior of the species. The compounds are produced in a ring-shaped gland of the male terminalia and have occasionally been detected in very minor amounts (ng) in ovipositor extracts of females, but only while mating or just after copulation. We also report that males use the already known (E,Z)-2,13-octadecadienol to mark their territory by rubbing their midlegs against the upper side of nearby leaves, especially palm leaves. This compound, produced in large amounts, is mostly concentrated in the midleg basitarsi and its maximum production is detected on the sexually mature 1-day-old specimens. In addition, analysis of male wings extracts confirms the presence of Z,E and E,E-farnesals, which are mostly produced in the median band of hindwings of 48-53 h-old insects. The biological significance of farnesals in this species is unknown. Our results point out that the chemical communication of P. archon relies mostly on males, which appear to bear all chemical burden in this respect.

MALDI-TOF MS Imaging evidences spatial differences in the degradation of solid polycaprolactone diol in water under aerobic and denitrifying conditions.

Degradation of solid polymers in the aquatic environment encompasses a variety of biotic and abiotic processes giving rise to heterogeneous patterns across the surface of the material, which cannot be investigated using conventional Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) that only renders an "average" picture of the sample. In that context, MALDI-TOF MS Imaging (MALDI MSI) provides a rapid and efficient tool to study 2D spatial changes occurred in the chemical composition of the polymer surface. Commercial polycaprolactone diol (average molecular weight of 1250Da) was selected as test material because it had been previously known to be amenable to biological degradation. The test oligomer probe was incubated under aerobic and denitrifying conditions using synthetic water and denitrifying mixed liquor obtained from a wastewater treatment plant respectively. After ca. seven days of exposure the mass spectra obtained by MALDI MSI showed the occurrence of chemical modifications in the sample surface. Observed heterogeneity across the probe's surface indicated significant degradation and suggested the contribution of biotic processes. The results were investigated using different image processing tools. Major changes on the oligomer surface were observed when exposed to denitrifying conditions.

Synthesis, Functional Assays, Electrophysiological Activity, and Field Tests of Pheromone Antagonists of the Tomato Leafminer, Tuta absoluta.

The tomato leafminer, Tuta absoluta, is one of the major pests of tomato and other Solanaceae in many regions worldwide. In the search for new strategies to control this pest, we present herewith the stereoselective synthesis, electrophysiological activity, functional analysis, and field tests of new chemicals as possible antagonists of the sex pheromone of the leafminer. The chemicals are methyl ketone (MK) and trifluoromethyl ketone (TFMK) structural analogues of both components of the pheromone. Most of the chemicals exerted per se some electrophysiological activity and inhibited the electroantennographic response to the pheromone when vapors of the inhibitor were passed over the antennae. Except TFMK 3, which elicited a modest effect, the compounds did not exhibit antiesterase activity on the pheromone-degrading enzymes of the antennae, but in the field the chemicals, particularly MK 5, notably decreased the number of catches when mixed with the pheromone in 1:1 and 10:1 ratios, regardless the infestation level of the plot. These results suggest that MK 5 is a good behavioral antagonist of the pheromone to be considered as a putative agent to control the pest in new future integrated pest management (IPM) strategies.

Aggressive mimicry coexists with mutualism in an aphid.

Understanding the evolutionary transition from interspecific exploitation to cooperation is a major challenge in evolutionary biology. Ant-aphid relationships represent an ideal system to this end because they encompass a coevolutionary continuum of interactions ranging from mutualism to antagonism. In this study, we report an unprecedented interaction along this continuum: aggressive mimicry in aphids. We show that two morphs clonally produced by the aphid Paracletus cimiciformis during its root-dwelling phase establish relationships with ants at opposite sides of the mutualism-antagonism continuum. Although one of these morphs exhibits the conventional trophobiotic (mutualistic) relationship with ants of the genus Tetramorium, aphids of the alternative morph are transported by the ants to their brood chamber and cared for as if they were true ant larvae. Gas chromatography-mass spectrometry analyses reveal that the innate cuticular hydrocarbon profile of the mimic morph resembles the profile of ant larvae more than that of the alternative, genetically identical nonmimic morph. Furthermore, we show that, once in the brood chamber, mimic aphids suck on ant larva hemolymph. These results not only add aphids to the limited list of arthropods known to biosynthesize the cuticular chemicals of their deceived hosts to exploit their resources but describe a remarkable case of plastic aggressive mimicry. The present work adds a previously unidentified dimension to the classical textbook paradigm of aphid-ant relationships by showcasing a complex system at the evolutionary interface between cooperation and exploitation.

Field trapping of the flathead oak borer Coroebus undatus (Coleoptera: Buprestidae) with different traps and volatile lures.

The flathead oak borer Coroebus undatus F. (Coleoptera: Buprestidae) is one of the primary pests of cork oak Quercus suber L. in the Mediterranean region causing great economic losses to the cork industry. Very little is known about its biology and behavior and, so far, no control measures have been established. We present the results of a pilot study aimed to develop an efficient trapping method for monitoring this harmful pest. In a 3-year field study, purple-colored prism traps baited with a mixture of green leaf volatiles (GLVs) from the host have been shown the most effective combination to catch C. undatus adults (solely females) compared to other trap and lure types tested. Wavelength and reflectance measurements revealed that purple traps exhibit reflectance peak values similar to those found in the abdominal and elytral cuticle of both sexes, suggesting the involvement of visual cues for mate location in this species. The data presented are the first to demonstrate captures of adults of the genus Coroebus by an attractant-based trapping method.

EAG responses increase of Spodoptera littoralis antennae after a single pheromone pulse.

Increased behavioral sensitivity to the pheromone after brief exposure of the whole insect to the sex pheromone has been documented in antennal lobe neurons of Spodoptera littoralis. We investigated whether a brief stimulus of the major component of the pheromone on naïve antenna separated from the head increased the electroantennographic responses after successive stimulations at different times. The response increase was clear 30 min after the first stimulation, and this effect lasted at least 60 min, the average life time of the antenna. Our results suggest that the olfactory receptor neurons, and not only the neurons in the antennal lobe, may be involved in the increased antennal response after a single pheromone pulse.

Phytal: a candidate sex pheromone component of the moroccan locust dociostaurus maroccanus.

Outbreaks of locusts cause enormous economic losses to agriculture in many countries. To develop environmentally friendly strategies for their control, much research has been focused on the factors that influence locust biology, particularly infochemical-mediated interactions. We present herein the identification and synthesis of both Z and E isomers of phytal (3,7,11,15-tetramethylhexadec-2-enal, 1), which are involved in chemical communication and behaviour of the Moroccan locust, Dociostaurus maroccanus, a serious agricultural pest. The compound was identified by comparison of its chromatographic and spectrometric features and microchemical reactions with those of a synthetic sample. The natural compound was shown to have the R,R configuration by chiral HPLC analysis, and its structure is unique as an insect pheromone component. Both isomers of phytal are produced by sexually mature adult males and elicit electroantennographic responses in antennae of both sexes. In two-choice olfactometer bioassays, males and females significantly preferred the stream enriched with racemic phytal to the control. In contrast, hydrogenated phytal was behaviourally inert. Both isomers of phytal are specific to D. maroccanus as they are absent in the closely related, habitat-sharing species Dociostaurus jagoi and Calliptamus wattenwylianus. Legs and wings are the main release sites of the compound: approximately 90 % of that emitted by living individuals. In biosynthetic studies, phytal appears to proceed from oxidation of phytol (2) after injection of deuterated phytol into the abdomen of the insect or after administration in the diet. Our results demonstrate that phytal is a candidate sex pheromone component of the Moroccan locust; it is produced by mature males, and might be eavesdropped upon by conspecific males.

Electrophysiological and behavioural responses of Pityophthorus pubescens (Coleoptera: Scolytinae) to (E,E)-α-farnesene, (R)-(+)-limonene and (S)-(-)-verbenone in Pinus radiata (Pinaceae) stands in northern Spain.

BACKGROUND: Some twig beetles in the genus Pityophthorus (Coleoptera: Scolytinae) may vector pitch canker disease Fusarium circinatum (Niremberg & O'Donnell) of Pinus spp. (Pinaceae). Because Pityophthorus pubescens (Marsh.) has been found to be associated with F. circinatum in the Basque Country (northern Spain), various experiments were conducted to assess the beetle's behavioural responses to (E, E)-α-farnesene, (R)-(+)-limonene and (S)-(-)-verbenone to develop a potential inhibitor to host attraction. These experiments comprise electroantennographic and double-choice olfactometer tests, as well as field assays in Pinus radiata D. Don stands. RESULTS: Both sexes of P. pubescens showed similar electroantennographic responses to different doses (from 1 ng to 1 µg in decadic steps) of each individual compound, with depolarisations to (S)-(-)-verbenone (100 ng) being similar to those of the aggregation pheromone (+)-trans-pityol. In olfactometer assays, both sexes were significantly attracted to (+)-trans-pityol, but the attraction was reduced when increasing amounts of the chemicals were added to the pheromone. Particularly relevant was the repellent effect induced by (S)-(-)-verbenone at 1 ng dose and higher. In the field, (E, E)-α-farnesene, (R)-(+)-limonene and (S)-(-)-verbenone reduced significantly the number of beetles attracted to (+)-trans-pityol and racemic trans-pityol, with (S)-(-)-verbenone being the most effective. CONCLUSIONS: (S)-(-)-Verbenone showed an interesting potential for use in the protection of P. radiata stands. A potentially effective strategy, which could be implemented in further, more in-depth studies, could involve the use of this semiochemical as repellent and (+)-trans-pityol-baited traps as attractant in a 'push-pull' strategy.

Electrophysiological and behavioral responses of the black-banded oak borer, Coroebus florentinus, to conspecific and host-plant volatiles.

Aspects of the chemical ecology of the black-banded oak borer, (BBOB) Coroebus florentinus (Coleoptera: Buprestidae), were studied. Odors produced by males and females were similar, both qualitatively and quantitatively. Nonanal, decanal, and geranylacetone, identified in the headspace of both sexes, elicited strong electroantennographic responses from male antennae, but not from female antennae. In dual-choice olfactometer experiments, a blend of these three compounds was attractive to both sexes; males responded to decanal alone, while females responded to geranylacetone alone, suggesting that these compounds are responsible for activity of the blend to the respective sexes. Antennae of both sexes responded electroantennographically to the green leaf volatiles (E)-2-hexenal, (E)-2-hexenol, 1-hexanol, (Z)-3-hexenyl acetate, and n-hexyl acetate, all identified from the host plant Quercus suber. In behavioral experiments, only females were attracted to host-plant odors, and in tests with synthetic compounds, females were attracted to (E)-2-hexenol, 1-hexanol, and (Z)-3-hexenyl acetate. It is likely that these compounds play a role in foraging and/or oviposition behavior of BBOB females.

Moths behaving like butterflies. Evolutionary loss of long range attractant pheromones in castniid moths: a Paysandisia archon model.

BACKGROUND: In the course of evolution butterflies and moths developed two different reproductive behaviors. Whereas butterflies rely on visual stimuli for mate location, moths use the 'female calling plus male seduction' system, in which females release long-range sex pheromones to attract conspecific males. There are few exceptions from this pattern but in all cases known female moths possess sex pheromone glands which apparently have been lost in female butterflies. In the day-flying moth family Castniidae ("butterfly-moths"), which includes some important crop pests, no pheromones have been found so far. METHODOLOGY/PRINCIPAL FINDINGS: Using a multidisciplinary approach we described the steps involved in the courtship of P. archon, showing that visual cues are the only ones used for mate location; showed that the morphology and fine structure of the antennae of this moth are strikingly similar to those of butterflies, with male sensilla apparently not suited to detect female-released long range pheromones; showed that its females lack pheromone-producing glands, and identified three compounds as putative male sex pheromone (MSP) components of P. archon, released from the proximal halves of male forewings and hindwings. CONCLUSIONS/SIGNIFICANCE: This study provides evidence for the first time in Lepidoptera that females of a moth do not produce any pheromone to attract males, and that mate location is achieved only visually by patrolling males, which may release a pheromone at short distance, putatively a mixture of Z,E-farnesal, E,E-farnesal, and (E,Z)-2,13-octadecadienol. The outlined behavior, long thought to be unique to butterflies, is likely to be widespread in Castniidae implying a novel, unparalleled butterfly-like reproductive behavior in moths. This will also have practical implications in applied entomology since it signifies that the monitoring/control of castniid pests should not be based on the use of female-produced pheromones, as it is usually done in many moths.

New identification of proanthocyanidins in cinnamon (Cinnamomum zeylanicum L.) using MALDI-TOF/TOF mass spectrometry.

The inner bark of Ceylon cinnamon (Cinnamomum zeylanicum L.) is commonly used as a spice and has also been widely employed in the treatment and prevention of disease. The positive health effects associated with the consumption of cinnamon could in part be due to its phenolic composition; proanthocyanidins (PA) are the major polyphenolic component in commercial cinnamon. We present a thorough study of the PA profile of cinnamon obtained using matrix-assisted laser desorption/ionization tandem time-of-flight (MALDI-TOF/TOF) mass spectrometry. In addition to the advantages of MALDI-TOF as a sensitive technique for the analysis of high-molecular-weight compounds, the tandem arrangement allows the identification of the compounds through their fragmentation patterns from MS/MS experiments. This is the first time that this technique has been used to analyze polymeric PA. The results show that cinnamon PA are more complex than was previously thought. We show here for the first time that they contain (epi)gallocatechin and (epi)catechingallate units. As gallates (galloyl moieties) and the pyrogallol group in gallocatechins have been related to the biological activity of grape and tea polyphenols, the presence of these substructures may explain some of the properties of cinnamon extracts. MALDI-TOF/TOF reveals that cinnamon bark PA include combinations of (epi)catechin, (epi)catechingallate, (epi)gallocatechin, and (epi)afzelechin, which results in a highly heterogeneous mixture of procyanidins, prodelphinidins, and propelargonidins.

Proteomics of toxic oil syndrome in humans: Phenotype distribution in a population of patients.

OBJECTIVES: Toxic oil syndrome (TOS) is a disease that appeared in Spain in 1981. Epidemiological work traced the origin to the ingestion of aniline-adulterated rapeseed oil, fraudulently marketed and sold as edible oil. It affected more than 20,000 people with over 400 deaths in the first 2 years. In 2001 evidence was presented that genetic factors could play a role in the susceptibility of individuals to the disease. Thus, a prospective study on the differences in gene expression in sera between control versus TOS-affected populations, both originally exposed to the toxic oil, was undertaken in our laboratory. METHODS: Differential protein expression was analyzed by two-dimensional electrophoresis (2-DE). Problems related with serum analysis by 2-DE were addressed to improve protein detection in the gel images. Three new commercial systems for albumin depletion were tested to optimize the detection of minor proteins. The use of nonionic reductants or the presence of thiourea in the gels, were also tested. RESULTS: From the resulting optimized images, a group of 329 major gel spots was located, matched and compared with serum samples. Thirty-five of these protein spots were found to be under- or over-expressed in TOS patients (threefold increase or decrease). Proteins in these spots were identified by matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) peptide map fingerprinting and database search. Several haptoglobin (Hp) isoforms were found to be differentially expressed, showing expression phenotypes that could be related with TOS. Resolution of the homologous α-1s and α-1f chains, with a mass difference of only 0.043Da, was obtained after guanidation of the protein with O-methylisourea. We applied this procedure to the study of the distribution of the Hp alleles HP(2), HP(1s) and HP(1f) in control versus TOS-affected populations. The MALDI-TOF proteotyping method was validated by a parallel analysis of the serum samples by 2-DE. CONCLUSIONS: Data obtained from 54 TOS cases and 48 controls indicate significant differences in the distribution of Hp phenotypes in the two populations. Haptoglobin phenotypes have been reported to have biological and clinical consequences and have been described as risk factors for several diseases. Consequently, it was concluded that haptoglobin polymorphism could play a role in TOS.

Sex pheromone of the Spanish population of the beet armyworm Spodoptera exigua.

The pheromone composition of the Spanish population of the beet armyworm (BAW), Spodoptera exigua (Lepidoptera: Noctuidae), was identified. Analysis of female gland extracts showed the presence of compounds Z9,E12-14:Ac (1), Z9-14:Ac (2), Z11-16:Ac (3), Z9,E12-14:OH (4), Z9-14:OH (5), and Z11-16:OH (6) in a ratio of 26:11:1:22:31:9. The amount of compound per gland ranged from 2.08 ng for 5 to 0.09 ng for 3. However, analysis of female volatiles by SPME revealed only the presence of compounds, 1, 2, 3, and 5 in a 34:40:4:22 ratio. In electroantennogram assays, compound 1 elicited the highest response, and the C14 acetates evoked higher electrophysiological responses than the corresponding alcohols or C16 isomers. In a wind tunnel, no behavioral difference was observed between formulations based on the gland extracts and female volatiles. In both cases, males responded as when virgin females were used as the attractant source. Compound 1 alone elicited upwind flight by males, but required the presence of compound 5 in a 80:20 to 40:60 ratio for full activity. Ternary mixtures of 1, 5 and the minor components did not improve the performance of the 1+5 blend in a 60:40 ratio. In the field, the mixture 1+5+3 in a 56:37:7 ratio was the most attractive formulation, and is expected to be useful in future pest control strategies.