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A total synthesis of the oleander scale [ Aspidiotus nerii (Bouche)] sex pheromone, the unique sesquiterpenoid containing a cyclobutane moiety of this class of compounds, has been developed. In order to implement this sex pheromone as a new environmentally friendly tool to manage this pest, a more cost-effective, multigram synthesis was required. This new synthetic route, having a Blaise reaction, iron-catalyzed carbon-carbon coupling, and [2 + 2] photocycloaddition reactions as key steps, provides a general access to 4-alkyl lactones as well as a robust access to the target sex pheromone. Starting from readily available compounds as 3-hydroxypropanenitrile, ethyl bromoacetate, and 2-acetyl butyrolactone, the synthetic sequence afforded the A. nerii sex pheromone with minimum intermediate purification and good overall yield in nine linear steps.

Plant-based bioproduction of insect sex pheromones has been proposed as an innovative strategy to increase the sustainability of pest control in agriculture. Here, we describe the engineering of transgenic plants producing (Z) -11-hexadecenol (Z11-16OH) and (Z) -11-hexadecenyl acetate (Z11-16OAc), two main volatile components in many Lepidoptera sex pheromone blends. We assembled multigene DNA constructs encoding the pheromone biosynthetic pathway and stably transformed them into Nicotiana benthamiana plants. The constructs contained the Amyelois transitella AtrΔ11 desaturase gene, the Helicoverpa armigera fatty acyl reductase HarFAR gene, and the Euonymus alatus diacylglycerol acetyltransferase EaDAct gene in different configurations. All the pheromone-producing plants showed dwarf phenotypes, the severity of which correlated with pheromone levels. All but one of the recovered lines produced high levels of Z11-16OH, but very low levels of Z11-16OAc, probably as a result of recurrent truncations at the level of the EaDAct gene. Only one plant line (SxPv1.2) was recovered that harboured an intact pheromone pathway and which produced moderate levels of Z11-16OAc (11.8 μ g g -1 FW) and high levels of Z11-16OH (111.4 μ g g -1 ). Z11-16OAc production was accompanied in SxPv1.2 by a partial recovery of the dwarf phenotype. SxPv1.2 was used to estimate the rates of volatile pheromone release, which resulted in 8.48 ng g -1 FW per day for Z11-16OH and 9.44 ng g -1 FW per day for Z11-16OAc. Our results suggest that pheromone release acts as a limiting factor in pheromone biodispenser strategies and establish a roadmap for biotechnological improvements.

[EN] The monoculture situation of truffle cultivation is favoring the appearance of pests that would not be economically important in naturally balanced forest ecosystems. The most prominent of them is the European truffle beetle Leiodes cinnamomeus (Panzer) (Coleoptera: Leiodidae), for which there are no effective control methods capable of reducing its populations. The potential of the mass trapping technique against this beetle, based on adapted pitfall traps and the semiochemical methyl disulfide as an attractant, is explored in the present work. Two trap densities (40 and 80 traps/ha) were tested in 2-yr field trials carried out in the region of Teruel (Spain) with black truffle cultivation tradition. Kairomone dispensers were placed in the field immediately before adult outbreak and remained active there throughout the season. The efficacy of each treatment was measured according to the reduction in beetle populations and the damaged truffles in the center of the treated areas. The results showed that both trapping densities reduced adult populations (mean 57% catch reduction), but 80 traps/ha were needed to significantly lower damage parameters (>40% reduction), percentage of attacked truffles and number of galleries/g truffle. The cost effectiveness of these treatments and possible improvements are discussed., This work has been supported by the project `A2. Efectos de Leiodes sobre la produccion de trufa negra de Teruel: evaluacion de la incidencia y posibilidades de control' from Gobierno de Aragon (FITE 2016). We would like to thank the owners of the fields (Jose Igual, Hnos Salvador Redon (Eugenio y Eladio) and Daniel and Maria from Trufas Bertolin SL) for allowing us to use their orchards and their trust to manage truffles. Finally, we also want to thank Pablo Lopez for his support in the field work, Helen Warburton for English editing and Prof. Gonzalo Garcia-Donato for the statistical support.

Mating disruption (MD) is widely used against the European grapevine moth (EGVM), Lobesia botrana (Denis and Schifferm&uuml, ller, Lepidoptera: Tortricidae), by installing passive dispensers or aerosol devices. The present work reports a new sampling and quantification methodology to obtain absolute data about field airborne pheromone concentration based on air samplings and sensitive chromatographic-spectroscopic methods. Samplings were performed in fields treated with passive dispensers or aerosol devices at different moments throughout the crop cycle to study how they act and how the disruption is triggered. Moreover, pheromone adsorption and releasing capacity of vine leaves were studied to elucidate their role in the disruption. Although both types of dispensers were effective in limiting the damage inflicted by EGVM, they performed differently and provided different airborne pheromone concentration profiles. Results also proved that leaves were able to adsorb and release part of the airborne pheromone acting as subsequent and additional pheromone sources. This fact could explain the different concentration profiles. Moreover, our results suggest that lower pheromone emission than that of the current passive dispensers still could provide an adequate performance in the field. Competitive mechanisms involved in MD using both dispensers, the dynamics of the airborne pheromone throughout the time and the importance of the canopy are discussed.

[EN] Native to sub-Saharan Africa, Delottococcus aberiae De Lotto (Hemiptera: Pseudoccidae) is an invasive mealybug that has been recently reported in Europe, seriously damaging citrus production in eastern Spain. In this study, we isolated and determined the structure of the sex pheromone of D. aberiae, to provide a highly specific and effective lure for detecting, monitoring, and potentially controlling this pest. The volatile profile of D. aberiae virgin and mated females was studied by aeration and collection of effluvia in Porapak-Q The resulting extracts were analyzed by gas chromatography coupled to mass spectrometry (GC-MS), revealing a candidate compound specific of virgin females. GC-MS and nuclear magnetic resonance spectroscopy data evidenced a new compound, (4,5,5-trimethyl-3-methylenecyclopent-1-en-1-yl)methyl acetate, with an unusual beta-necrodol skeleton. This compound was synthesized and shown to be attractive to male D. aberiae in both laboratory and field experiments. A GC analysis using an enantioselective stationary phase and polarimetry analyses of the synthetic enantiomers showed the natural compound emitted by virgin females to be the - enantiomer., This work received funding from Universitat Politecnica de Valencia (postdoctoral contract for SV) and Conselleria de Agricultura, Medio Ambiente, Cambio Climaico y Desarrollo Rural (Generalitat Valenciana) under grant agreement (S8456000)

Spotted wing drosophila, Drosophila suzukii Matsumura (Diptera: Drosophilidae), has become a key pest for soft fruits and cherries in Europe in less than a decade since the first outbreak in 2007. Although this pest&rsquo, s passive dispersal ability has been observed over more than 1400 km in 1 year, active spread has not yet been extensively studied. A mark&minus, release&minus, recapture (MRR) method based on protein-marked flies was employed to determine the flight capacity of D. suzukii. Sterile marked flies were released and recaptured in a trap grid at increasing distances from 10 to 250 m from the releasing point to study flight distance during periods ranging from 3 h to 1 week. MRR experiments were replicated in the presence and absence of host fruits to study how they could affect dispersal behavior. The dispersal capacity of the Mediterranean fruit fly, Ceratitis capitata Wiedemann (Diptera: Tephritidae) was also studied under the same conditions. The results showed a low dispersal ability for D. suzukii, with a daily flight distance below 100 m with no predominant wind. The implications on natural dispersion and control methods based on attractants are discussed.

Background The optimisation of the lure is essential for the implementation of trapping systems to control insect pests. In this work, the response of the red palm weevil (RPW), Rhynchophorus ferrugineus Olivier, to increasing emission rates of its aggregation pheromone (ferrugineol) and the efficacy of a convenient synthetic kairomone based on fermentation odours (ethyl acetate and ethanol) have been evaluated in different years and locations along the Mediterranean basin. Results In general, although capture data and emission had noticeable variability among locations, significantly fewer RPW were captured in pyramidal Picusan® traps with the lowest ferrugineol emission rates tested (0.6-3.8 mg day-1 ). Captures increased rapidly with ferrugineol emission up to 4-5 mg day-1 ; then, higher emission rates did not improve or reduce captures, up to the highest emission rate tested of 50.9 mg day-1 . Thus, there is no evidence of an optimum release rate corresponding to a maximum of RPW catches. Traps baited with the synthetic kairomone (1:3 ethyl acetate/ethanol) captured 1.4-2.2 times more total weevils than traps baited only with ferrugineol. Moreover, in most of the locations, the synthetic blend was at least as effective as the local coattractants used (plant material + molasses). Conclusions Ferrugineol emission rate can vary in a wide range without significantly affecting RPW response. Coattractants based on fermenting compounds, ethyl acetate and ethanol, are able to improve the attractant level of ferrugineol and could be employed to replace non-standardised natural kairomones in RPW trapping systems after further optimisation of their proportions and doses. © 2016 Society of Chemical Industry.

[EN] Improved trap efficacy is crucial for implementing control methods for red palm weevil, Rhynchophorus ferrugineus (Olivier; Coleoptera: Dryophthoridae), based on trapping systems, such as mass trapping, attract and infect or attract and sterilize techniques. Although new trap designs have been proposed and aggregation pheromone dispensers have been optimized, aspects such as the use of co-attractants (molasses) and trap placement are still not well defined and standardized. The efficacy of three concentrations of molasses and different formulations to reduce water evaporation in traps was studied in different field trials to improve trapping systems and to prolong trap servicing periods. In addition, the performance of installing groups of traps or single traps was also evaluated with the aim of improving the attracted/captured weevils ratio. Our results showed that captures increased when molasses were added at 15% to the water contained in the trap and that a thin layer of oil, created by adding 2-3% of paraffinic oil to water, was able to effectively reduce evaporation and prolong trap servicing periods. Moreover, 3.5-fold more weevils were captured when placing five traps instead of one at the same trapping point. Results obtained allow improved efficacy and may have an impact in the economic viability of trapping systems and, therefore, in integrated pest management programs., We want to thank Vicente Dalmau from Conselleria de Agricultura, Peixca i Alimentacio (GVA) and Jose Juan Lopez from TRAGSA for their help and technical assistance in field trials. Also, we want to thank Helen Warburton for English editing. The research leading to these results has received funding from the 7th European Union Framework Programme under grant agreement FP7 KBBE 2011-5-289566 (PALM PROTECT).

The influence of a-copaene as a fruit volatile in the susceptibility of Olea europaea L. to the olive fruit fly Bactrocera oleae (Rossi) has been investigated. By studies on the relative area of volatile components from different cultivars, a positive correlation was found between the abundance of a-copaene in the samples and the corresponding degree of fruit infestation. SPME-GC-MS analysis of volatiles from uninfested fruits of O. europaea L. cv. Serrana were performed over two years to determine the variation of a-copaene throughout the different phenological stages. The results suggested that this sesquiterpene has a significant effect on cultivar susceptibility and may act as an oviposition promoter. Further analysis by chiral GC showed that olive fruits release both a-copaene enantiomers. Bioassays on each enantiomer revealed that fruits with increased amounts of (+)-alpha-copaene favor oviposition of B. oleae females, whereas the increase of (-)-alpha-copaene affords no statistically significant differences in host preference.

[EN] The four-spotted coconut weevil, Diocalandra frumenti Fabricius (Coleoptera: Dryophthoridae), is a small weevil found attacking economically important palm species, such as coconut, date,, oil, and Canary palms. Given the scarcity of detection and management tools for this pest, the availability of a pheromone to be included in trapping protocols would be a crucial advantage. Previous laboratory experiments showed evidence for aggregation behavior; thus, our main goal was to identify the aggregation pheromone in this species. The volatile profile of D. frumenti individuals was studied by aeration and collection of effluvia in Porapak-Q and also by solid phase microextraction (SPME) techniques. Moreover, solvent extraction of previously frozen crushed individuals was also performed. All resulting extracts and SPME fibers were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). The comparison of male and female samples provided the candidate compound, 5ethyl-2,4-dimethy1-6,8-dioxabicyclo [3.2.1]octane (multistriatin), whose biological activity was evaluated in olfactometer and field assays., This work received funding from Direccion General de Agricultura del Gobierno de Canarias (Spain).

[EN] Attraction of California red scale males, Aonidiella aurantii (Maskell), to different release rates of the sex pheromone compound 3-methyl-6-isopropenyl-9-decen-1-yl acetate was evaluated in field trials. This study was aimed to study pheromone emission-response correlations and the existence of an optimum release rate that maximizes trapping efficacy. Release profiles of the pheromone dispensers deployed were determined by gas chromatography to estimate the various emission rates tested. The results reveal that the mean number of A. aurantii males caught correlates with the daily pheromone release rates by means of a quadratic model. The obtained model indicates the existence of a relative maximum of the captures corresponding to an optimum release rate of ca. 300 mu g/day. Higher emission rates (up to 1 g/day) resulted in lower captures. Implications for the mating disruption technique are discussed., The research leading to these results received funding from the Spanish Ministry of Science and Innovation [project number AGL2009-10725].

Araujia sericifera is a native perennial, climbing laticiferous shrub from South America that is currently naturalized in many other countries. Previous data describe promising properties for A. sericifera, but no systematic study of its bioactive compounds and possible medicinal applications has been conducted to date. In the present study, aerial parts of A. sericifera (leaves, stems, and fruits) were explored by combining GC-MS and NMR spectroscopy analysis for both nonpolar (hexane) and polar (methanol) extracts. The hexanic extracts contained high amounts of pentacyclic triterpenes including two new metabolites, 3-tigloyl germanicol (18) and 3-tigloyl lupeol (19). The methanolic extracts revealed the presence of luteolin-7-glucoside (24), trigonelline (22), and conduritol F (23) as the main constituents. A multivariate study of a meaningful number of extracts allowed us to determine the distribution of compounds inside the plant. A cytotoxic evaluation in vitro showed that both leaf and fruit hexanic extracts presented a moderate activity against human breast carcinoma cell lines (MDA-MB-453 and MCF-7) and human colon carcinoma cell line (HCT-116) by the MTS [3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium] assay.

The authors would like to thank 'Coop. San Bernardo de Carlet', Carlos Monzo and Vicente Morato for providing trial orchards. This research was funded by the Atomic International Energy Agency through research contract No. 15726. Thanks also to Suterra Europe Biocontrol SL for providing Magnet (R) MED devices.

Given the social importance related to the red palm weevil, Rhynchophorus ferrugineus Olivier (Coleoptera: Curculionidae), efforts are being made to develop new control methods, such as the deployment of trapping systems. In this work, the efficacy of a new black pyramidal trap design (Picusan) has been verified in comparison with white and black buckets. In addition, the attractant and synergistic effect of ethyl acetate (EtAc) at different release levels has been evaluated under field conditions. The results show that Picusan traps captured 45% more weevils than bucket-type traps, offering significantly better trapping efficacy. The addition of water to traps baited with palm tissues was found to be essential, with catches increasing more than threefold compared with dry traps. EtAc alone does not offer attractant power under field conditions, and the release levels from 57 mg/d to 1 g/d have no synergistic effect with ferrugineol. Furthermore, significantly fewer females were captured when EtAc was released at 2 g/d. The implications of using EtAc dispensers in trapping systems are discussed.

Communication., A new family of stable layered organic–inorganic materials has been prepared, in one-step solvothermal process. They are based on an ordered nickel cluster-type nanoribbons separated from each other by specific alkyl (heptyl- or dodecyl-) arylic mono-carboxylate moieties acting as molecular spacers, perpendicular to the 1D inorganic chains. These organic spacers contain hydrocarbon tails with different length which control the separation level between inorganic 1D sub-units, inhibiting the 3D growth of conventional DUT-8-type metal–organic frameworks (MOFs). The lamellar nature of the materials formed was studied and confirmed by different characterization techniques, showing the structural location of individual organic and inorganic building units. They have been successfully used as a long-lasting biodegradable and water-proof materials for controlled release of chemicals, such as pheromones for sustainable treatment of insect plagues., The support of the European Union (ERC‐AdG‐2014‐671093—SynCatMatch) and the Spanish Government (MAT2014‐52085‐C2‐1‐P and Severo Ochoa program SEV‐2012‐0267) is acknowledged.

Highlight Over 100 fruit volatile QTLs were identified in a RIL population derived from the red-fruited wild species Solanum pimpinellifolium and a fresh market tomato variety ‘Moneymaker’ and subsequently confirmed in introgression lines., Volatile organic compounds (VOCs) are major determinants of fruit flavor, a primary objective in tomato breeding. A recombinant inbred line (RIL) population consisting of 169 lines derived from a cross between Solanum lycopersicum and a red-fruited wild tomato species Solanum pimpinellifolium accession (SP) was characterized for VOCs in three different seasons. Correlation and hierarchical cluster analyses were performed on the 52 VOCs identified, providing a tool for the putative assignation of individual compounds to metabolic pathways. Quantitative trait locus (QTL) analysis, based on a genetic linkage map comprising 297 single nucleotide polymorphisms (SNPs), revealed 102 QTLs (75% not described previously) corresponding to 39 different VOCs. The SP alleles exerted a positive effect on most of the underlying apocarotenoid volatile QTLs—regarded as desirable for liking tomato—indicating that alleles inherited from SP are a valuable resource for flavor breeding. An introgression line (IL) population developed from the same parental genotypes provided 12 ILs carrying a single SP introgression and covering 85 VOC QTLs, which were characterized at three locations. The results showed that almost half of the QTLs previously identified in the RILs maintained their effect in an IL form, reinforcing the value of these QTLs for flavor/aroma breeding in cultivated tomato.

BACKGROUND: The control of Ceratitis capitata Wiedemann traditionally has relied on chemical control with organophosphate insecticides. The use of many of these substances has been banned by new European directives; therefore, the development of new control methods is essential to manage this pest. Bait sprays with spinosad, mass trapping and lure-and-kill techniques have been the base for new integrated pest management programmes. In this study, a 2 year field trial was conducted in two citrus areas to test the efficacy of attract-and-kill devices against mass trapping and spinosad-plus-bait treatments. RESULTS: The Magnet® MED attract-and-kill device, Spintor® treatments and mass trapping achieved good control of C. capitata populations, as confirmed by low percentages of damaged fruit in the assessments performed during the harvest period. On the other hand, fly population levels on plots treated with other attract-and-kill prototype devices increased more than threefold by comparison with the populations recorded in the rest of the treated plots. The same effect was observed for fruit damage, with 6–8 times less damage with Magnet® MED and spinosad treatments, respectively, than with the attract-and-kill prototype devices. CONCLUSION: By using an effective attractant, conventional trapping systems can be replaced with cheaper and easier-to-handle attract-and-kill devices. The efficacy of these devices and their advantages over conventional mass trapping systems are discussed. © 2012 Society of Chemical Industry

BACKGROUND: In recent years, environmentally safe measures to control the California red scale (CRS), Aonidiella aurantii (Maskell), have been successfully implemented. These measures include mating disruption (MD) and biological control. The goal of this study was to examine the effect of high concentrations of the CRS sex pheromone on its life history parameters and scale-cover surface area under controlled laboratory conditions. RESULTS: The developmental time of bothmales and females of CRS increased with exposure to airborne pheromone.MD had an effect on both the total number of progeny and on the crawler production period for females. Accordingly, demographic parameters such as net fecundity (R0) and intrinsic rate of increase (rm) were significantly lower in the pheromone-treated populations. The largest scale-cover surface areas were observed in the CRS reared in the pheromone environment. CONCLUSION:Aclear influence of airborne pheromone on the biology of CRS has been demonstrated. In addition to the classical mating disruption benefits of this technique, additional benefits, such as increase in the duration of exposure to natural enemies and increase in size, which benefits some species of parasitoids, have been confirmed., The authors thank H Monton, C Vidal and D Martinez for technical assistance with experiments. This work was partially funded by the Spanish Ministry of Science and Innovation (projects AGL2008-05287-C04/AGR and AGL2009-10725) and the Conselleria d'Agricultura, Pesca i Alimentacio de la Generalitat Valenciana. PV was the recipient of a grant from IVIA. Thanks also to the Ecologia y Proteccion Agricola S.L. for supplying the pheromone.

[EN] Volatile compounds are together with sugars and organic acids the main determinants of tomato fruit flavour and are therefore important for consumer acceptance. Consequently, in the last years many studies have been performed using different volatile analytical techniques on a large diversity of tomato fruits, aimed mainly at detecting the compounds affecting flavour or at the identification of QTLs and key genes involved in fruit volatile contents. The comparison of three of the analytical methods most commonly applied (headspace, solid phase microextraction, adsorption on Tenax followed by thermal desorption) revealed not only differences in sensitivity, but also dramatic variations in the volatile profile obtained by each of these techniques. The volatile profile was also largely influenced by the way samples were processed before analysis. Four widely used sample processing methods were compared (whole tomato, sliced fruit and two different types of fruit paste), each one producing a characteristic volatile pattern. Therefore, great care should be taken when comparing results available from the literature obtained by means of different methods, or when using the volatile levels obtained in an experiment to predict their influence on tomato flavor or consumer preference, or to assess the success of breeding programs., We thank Rafael Fernandez for providing excellent tomato fruits for this study. Funding to AG was provided through CALITOM and ESPSOL from FECYT and EUSOL (EU FP7 program) and Quality Fruit FA 1106.

BACKGROUND: New directives on sustainable use of pesticides have encouraged research on efficient alternative pest control methods. In the case of the California red scale (CRS), Aonidiella aurantii (Maskell), this imperative, along with the many difficulties in controlling this pest, have led to the investigation of new approaches. Previously developed mating disruption (MD) dispensers, together with the augmentative releases of the parasitoid Aphytis melinus DeBach, are here considered as a combined strategy for use against A. aurantii. RESULTS: Efficacy of MD was demonstrated by a mean reduction of 80% in CRS male catches and a mean fruit damage reduction of 83% compared with the control. A delay in the development of A. aurantii instars was observed in the MD plot. This delay increased the period of exposure of the susceptible instars to natural enemies, which resulted in higher predation and parasitism levels in the MD plot. Under laboratory conditions, A. melinus mating behaviour and effects on A. aurantii were not significantly altered in a CRS-pheromone-saturated environment. CONCLUSION: Mating disruption pheromone did not affect the behaviour or level of parasitism by A. melinus or the incidence of other generalist predators. Therefore, A. aurantii pheromone appears to be compatible with augmentative releases and biological control, making its use a good strategy for CRS management. Copyright © 2011 Society of Chemical Industry

BACKGROUND: The tomato leafminer (Tuta absoluta Povolny) has rapidly colonised the whole Mediterranean and South-Atlantic coasts of Spain, and it has become a key problem in both outdoor and greenhouse crops. New control methods compatible with biological control are required, and mating disruption appears to be a perfect method in current agriculture, as it is an environmentally friendly and residue-free technique. IPM packages tested have included the use of pheromones to detect populations, but there has not been much previous research on mating disruption of T. absoluta. In this work, pheromone doses varying from 10 to 40 g ha−1, emitted at a constant rate over 4 months, were tested in greenhouses with different levels of containment in order to evaluate the efficacy of mating disruption on T. absoluta. RESULTS: Trials on containment level revealed that the flight of T. absoluta was satisfactorily disrupted with an initial pheromone dose of 30 g ha−1, and levels of damage did not significantly differ from those in reference plots with insecticide treatments. Later efficacy trials confirmed previous experiences, and release studies showed that control of damage and flight disruption were taking place when releasing at least 85 mg pheromone per ha per day. CONCLUSION: Effective control using pheromone application against T. absoluta can be achieved, in greenhouses with high containment levels, for 4 months, with initial doses of 30 g ha−1. Further research must be conducted in order to evaluate the prospect of outdoor application of mating disruption systems. Copyright © 2011 Society of Chemical Industry

Since the discovery of Lobesia botrana Denis & Schiffermuller (Lepidoptera: Tortricidae) sex pheromone, it has played an important role in the control and detection of this pest, for example, through the use of pheromone-baited traps and mating disruption techniques. Rubber septa are the most common pheromone dispensers used in monitoring traps, but often dispenser performance is not optimized. The key to improve methods based on pheromones as attractants (monitoring, mass trapping, or ‘attract and kill’) is to know the optimum emission interval, because release rates can strongly affect the attraction. In this work, five levels of pheromone load with different release rates were compared in traps using mesoporous pheromone dispensers to investigate the optimum release rate maximizing L. botrana catches. Residual pheromone loads of the dispensers were extracted and quantified by gas chromatography, to study release profiles and to estimate the various emission levels. The efficacy of pheromone emission was measured in field trials as number of moths caught. A quadratic model was fitted to relate the numbers caught vs. the daily emission rates. The resulting quadratic term was statistically significant, confirming the existence of a relative maximum for L. botrana catches. Taking into account that the trial was carried out only in one location, an optimum emission value of ca. 400 μg per day could be considered to enhance the attraction of L. botrana under West-Mediterranean weather conditions.

Reaction of five benzylic alcohols in solution at 78°C has been performed in the presence of a series of HY zeolites at three different levels of Na+ -to-NH4+ exchange (HY-21, HY-50 and HY-100) and framework Si-to-Al ratio (HY-100, HY-200 and HY-400). Dehydration to form a CC double bond is the main primary process for 1-phenyl- and 1,1-diphenylethanol. Nevertheless, the initial alkenes are unstable, giving rise to the corresponding phenylethanes and, in the case of styrene, also to dimers. In contrast, benzyl alcohol and diphenylmethanol gave equimolar amounts of phenylmethanes and phenyl ketones, by an intermolecular hydride transfer not observed under conventional homogeneous acid catalysis. This process was found to be highly demanding from the point of view of the acid strength of the sites involved. Finally, triphenylmethanol showed a remarkable reluctance to undergo any change, although small amounts of triphenylmethane, benzophenone and 9-phenyl-9-hydroxyfluorene were detected after long reaction times.

BACKGROUND: The control of California red scale, Aonidiella aurantii (Maskell), has encountered many difficulties, which has raised interest in alternative control methods. Up to now, the A. aurantii sex pheromone has been used only for monitoring. In a previous work the authors described a biodegradable mesoporous pheromone dispenser for mating disruption. To verify the efficacy of these dispensers, three field trials were conducted, and the results are shown in this paper. RESULTS: The study of the release profile of these dispensers revealed a mean pheromone emission value of 269 µg day−1 and levels of residual pheromone of 10% at the end of 250 days. During the second flight, an A. aurantii male catch reduction of 98% was achieved in the mating disruption plot of trial 1, 93.5% in trial 2 and 76.7% in trial 3. During the third flight, reductions were 94.1, 82.9 and 68.1% in trials 1, 2 and 3 respectively. Considering damaged fruit with more than five scales, reductions of about 80 and 60% were obtained in the mating disruption plots of trials 2 and 3, respectively, compared with an untreated plot, and a reduction of about 70% in trial 1 compared with an oil-treated plot. CONCLUSION: Mating disruption has been found to be an efficient technique to control this pest, working equally well to a correctly sprayed oil treatment. Further studies are needed to improve the determination of the time of dispenser application and evaluate the effects of the pheromone on natural enemies. Copyright © 2010 Society of Chemical Industry

BACKGROUND: Chemosterilisation with lufenuron bait stations is a recently developed technique that is being implemented for Ceratitis capitata Wiedemann control. The aim of this work was to evaluate the chemosterilising effect of lufenuron against four economically important Latin American fruit flies species: Anastrepha ludens (Loew.), A. obliqua Macquart, A. serpentina Wiedemann and A. striata Schiner (Diptera: Tephritidae) in order to design a similar strategy for their control. RESULTS: Sexually mature adults were treated by ingestion with concentrations ranging from 0.1 to 30.0 mg g−1 of lufenuron in the diet. In addition, conspecific crosses with only one of the sexes being treated (30.0 mg g−1) were performed in order to appraise the contribution of each sex to the sterilising effect. In all cases, fecundity was not affected by the treatments, as opposed to fertility where all Anastrepha species studied were significantly affected, although to different extents. The conspecific crosses showed that treated males of A. ludens, A. obliqua and A. serpentina were not able to transmit the sterility to their respective untreated females. Only in the case of A. striata did crossing treated males with untreated females significantly reduced egg hatch. CONCLUSION: Although further investigations are required, the present results demonstrate that the use of lufenuron for controlling A. striata could be potentially viable. Copyright © 2010 Society of Chemical Industry

BACKGROUND: The chemosterilisation technique has been demonstrated to reduce the population and fruit damage of the Mediterranean fruit fly, Ceratitis capitata (Wiedemann), in citrus orchards. Field trials showed efficacy by reducing the fruit fly population, which was progressively achieved by continuous application of lufenuron to several generations. Different authors have suggested that field trials should be carried out in isolated or wide areas in order to reduce fruit fly intrusion and obtain best results. To this end, a wide-area trial over 3600 hectares has been under investigation in Valencia (Spain) since 2002 to validate the chemosterilisation technique against the fruit fly. The whole area was treated with 24 traps ha−1, using more than 86 000 traps in the field trial. RESULTS: A continuous decrease in fruit fly population was observed over the 4 years under trial. Moreover, results showed a significant reduction in persimmon damage in the chemosterilant treatment area compared with a malathion aerial treatment area. In the case of citrus damage, no significant differences were obtained between malathion and chemosterilant treatments. CONCLUSION: The chemosterilant method reduces Mediterranean fruit fly populations, and therefore it is a candidate treatment to replace aerial treatments with insecticides in order to suppress this pest. In addition, the efficacy of chemosterilant treatment is increasing year after year. The possibility of using this technique combined with other control methods is discussed. Copyright © 2010 Society of Chemical Industry

Traditional chemical control against Chilo suppressalis Walker is currently being replaced in Spain by new methods based on pheromones. A key step to improve the efficacy of these methods is the determination of the optimum pheromone release rate, which is still uncertain for this pest. In this work, the pheromone release profile and the field performance of a new mesoporous dispenser was compared with a standard commercial dispenser. For this purpose, pheromone loads were extracted from field-aged dispensers and quantified by gas chromatography with flame ionization detector. In addition, a field trial was carried out with traps baited with one, two, or three mesoporous dispensers per trap, as well as with traps containing one standard dispenser. We found that the highest number of field catches did not correspond to the highest pheromone emission rate, which suggests a repellent effect of the insect if the emission is excessive. The results suggest that the attractant activity was maximized by emitting approximately 34 microg/d. The efficacy of the mesoporous dispenser and its possible improvements are discussed.

[EN] Knowledge about the behaviour of trimedlure (TML) dispensers is essential to ensure the efficacy of monitoring and control methods based on TML as attractant. There are several commercially available TML dispensers, and each of them has a different useful life and TML release profile. Their emission is also affected differently by environmental factors. Even the same type of dispenser sometimes shows an important variability in the TML release rate. Because of the importance of methods based on TML lures in the control of the Mediterranean fruit fly and the influence of the TML dispenser on the efficacy of these control methods, we developed a non-destructive flow-through system to measure the TML release rate. This volatile collection method (VCM) adsorbs TML vapour on a Tenax TA desorption tube, and TML is quantified by Thermal desorption coupled with gas chromatography/mass spectrometry. Two types of TML dispensers, a polymeric (Aralure) and a mesoporous (Epalure), were field aged during 3 months. The TML release rates of these dispensers were determined by both, VCM and solvent extraction method. In this study, the correlation between both measurement methods is shown. A field trial has also been carried out to correlate trap catches and TML emission of each type of tested dispenser. The VCM allows a quick and accurate evaluation of the current behaviour of commercial dispensers along their useful life. It also allows comparing the TML release rate between different dispensers. We believe that the VCM can be useful for dispenser manufacturers to determine seasonal dispenser performance before a new product is introduced in the market, and to rapidly verify TML dispenser release when field-aged dispenser efficacy is in question. Thus, it can be employed as a quality control of commercial dispensers., We want to thank financial support from 'Fundacion Jose y Ana Royo' and 'Conselleria de Agricultura Pesca y Alimentacion de la Generalitat Valenciana', and Juan Sanchis for his support in the field trial.

[EN] New agricultural techniques are attempting to reduce the application of synthesized pesticides and replace them with new environmentally friendly methods such as mass trapping, mating disruption, or chemosterilization techniques. All these methods are based oil the release of a lure for insect attraction or confusion. The Success of the chosen method depends on the quality of the attractant emission from the dispenser. Currently, used dispensers with a polymeric matrix and new dispensers with mesoporous inorganic materials were evaluated to obtain more efficient emission kinetics. In this Study, the selected pest was the Mediterranean fruit fly, Ceratitis capitata (Wiedemann) and the lure used vas trimedlure (TML). The dispensers were validated by means of a field study comparing insect catches with attractant release values. As a result, we have demonstrated that mesoporous dispensers have it clearly longer lifetime than the polymeric Plug. Furthermore, the attractant release rate is less dependent oil temperature in mesoporous than in polymeric dispensers.

[EN] Lufenuron is a chitin synthesis inhibitor, which is able to impede Mediterranean fruit fly, Ceratitis capitata (Wiedemann), reproduction. In laboratory trials, following ingestion of lufenuron, the eggs laid by female Ceratitis capitata were prevented from hatching. In field trials in Valencia, Spain, lufenuron showed its effectiveness by reducing C. capitata wild populations and its continuous application to several generations of fruit fly resulted in increased pest control. This field trial was conducted in an isolated valley some 80ha in size, over a continuous four-year period. In order to maintain the sterilizing effect in the field throughout the whole year, a new lufenuron bait gel was developed. This bait gel was introduced in to delta traps suspended in trees at a density of 24 traps ha 1, and these traps were replaced once a year during the field trial. Monitoring of the adult C. capitata population was conducted to assess the effects of the chemosterilant treatment. In the first year of treatment with sterilizing traps, a reduction of the C. capitata population was observed, indicating that the traps reduce the population right from the first generation. In the second, third and fourth years, a continuous and progressive reduction of the adult Mediterranean fruit fly population was observed. Therefore, the successive application of chemosterilization treatment has a cumulative effect on reducing the fly population year after year. Aerial treatment using malathion does not produce this cumulative effect, and consequently every year it is necessary to start again with the same number of flies as the year before. The possibility of using the chemosterilant method alone or combined with the sterile insect technique is discussed., The authors thank Stephen Skillman for helpful suggestions on the first version of the manuscript, Syngenta for supplying technical grade lufenuron, and the R&D+i Linguistic Assistance Office at the Universidad Politécnica de Valencia for their help in revising and correcting this paper. This research has been supported by ‘Fundación José y Ana Royo’, ‘Conselleria d’Agricultura Peixca i Alimentacio-GVA’ and INIA project number RTA03-103-C6.

[EN] Biological control of Ceratitis capitata (Wiedemann) (Diptera: Tephritidae) using entomopathogenic fungi is being studied as a viable control strategy. The efficacy of a Metarhizium anisopliae (Metschnikoff) Sorokin (Hypocreales: Clavicipitaceae)-based attractant contaminant device (ACD) to control C. capitata was evaluated in a medium-scale (40 ha) 2-yr field trial using a density of 24 ACD per ha. Results showed that this density was adequate to efficiently reduce fruitfly populations and that the inoculation dishes (IDs) needed replacing mid-season to provide protection for the entire season. In this study, fungal treatment was even more effective than conventional chemical treatment. Population dynamics in fungus-treated fields along with the infectivity study of field-aged IDs in the laboratory found that the ACD remained effective for at least 3 mo. The results suggest M. anisopliae-based ACD can be used to control C. capitata in the field. The implications of its use, especially as a tool in an integrated pest management program, are discussed., We thank Hellen Warbunton for editing the manuscript. This work was partially supported by the Instituto Nacional de Investigaciones Agrarias (INIA; Proyect: RTA03-103-C6-4) and the Comision Espanola Interministerial de Ciencia y Tecnologia (CICYT; Proyect: AGL2006-13346-C02-02).

Mating disruption has proved successful against California red scale (CRS), Aonidiella aurantii Maskell (Hemiptera: Diaspididae) in Mediterranean citrus. Although mating disruption does not affect negatively the parasitism by Aphytis melinus DeBach (Hymenoptera: Aphelinidae), a CRS parasitoid introduced to the Mediterranean, there is no information regarding its potential effect on the native Aphytis species. In the present study, the effect of CRS mating disruption on the field parasitism inflicted by Aphytis spp. has been assessed and compared to a mineral oil and a control treatment. In order to confirm the effectiveness of the mating disruption we also evaluated its effect on the captures of the CRS males and on fruit infestation. Moreover, the potential role of the CRS sex pheromone as kairomone for the Aphytis species was also evaluated by comparing captures of parasitoids on sticky traps with or without pheromone. Significantly lower CRS male captures and fruit damage were registered in the mating disruption respect to the control or oil treatments indicating that mating disruption was effective. In September, when compared to the control, parasitism by Aphytis spp. was significantly lower in the mating disruption and mineral oil treatments and crucially no Aphytis chrysomphali Mercet were registered in the mating disruption treatment. Finally, while the captures of both A. melinus and Aphytis lepidosaphes (Mercet) were not significantly different between traps with or without pheromone, A. chrysomphali captures were significantly higher in traps baited with CRS pheromone. These results suggest a possible kairomonal effect of the CRS pheromone on A. chrysomphali .

[EN] The capacity of inhibition of the mammalian mitochondrial respiratory chain of brevioxime 5a, a natural insecticide compound isolated from Penicillium brevicompactum culture broth, and another 15 analogue compounds, other oximes 5b and 5c; two diastereomeric pyrrolidines 1c' and 1c"; five pyrrolines 3c', 3c" (diastereomers between them), 3a, 3b, and 6; two oxazines 4c' and 4c" (also diastereomers between them); and four pyrrol derivatives 7-10, are analyzed in this paper. Compounds 3b, 3c', 3c", 4c', 4c", 5b, 5c, 6, and 10 were found to be inhibitors of the integrated electron transfer chain (NADH oxidase activity) in beef heart submitochondrial particles (SMP), establishing that all of them except compound 3b and 6 only affected to complex I of the mitochondrial respiratory chain. The most potent product was 5b, with an IC50 of 0.27 mu M, similar to the IC50 values of other known complex I inhibitors. The diastereomeric pairs 1 c'/1c", 3c'/3c", 4c'/4c", and 5c have not been previously described. Chemical characterization, on the basis of spectral data, is also shown., We acknowledge the Fundacio¿n Jose¿ y Ana Royo for a postdoctoral grant to M.C.G., and the Conserjerı¿a de Educacio¿n y Ciencia de la C. Valenciana for the doctoral grant to M.P.L. This work has been supported by Oficina de Ciencia y Tecnologı¿a. I+D projects of the Generalitat Valenciana (Project GV01- 293), the Conselleria d Agricultura, Pesca i Alimentacio¿ (Project GVCAPA00-0529), and Fondos Europeos de Desarrollo Regional (FEDERFSE) of the European Union through the Fondo de Investigacio¿n Sanitaria (FIS 01/0406).

The activity of the titanium mesoporous molecular sieve Ti-MCM-41 and amorphous Ti-silicate materials for carbon–carbon bond formation in the Mukaiyama aldol-type reaction between benzaldehyde and methyl trimethylsilyl dimethylketene acetal was studied and the reaction network established. Only tetrahedral Ti IV is catalytically active, where Ti VI and highly dispersed TiO 2 are not active or only slightly active for the Mukaiyama reaction and have no effect on selectivity. Whereas in Ti-zeolites only a some of the active sites are accessible to reactants, all of them are accessible in Ti-MCM-41. The structured Ti-MCM-41 offers a clear catalytic advantage over amorphous Ti-silicalites. Water has a negative effect on catalytic activity and selectivity, and catalyst preactivation and hydrophobicity play an important role in the final catalytic behavior. The influence of different solvents on conversion was explored.

The essential oils of the aerial parts of four populations of Sideritis linearifolia collected in two different years were investigated by GC-FID and GC-MS. The qualitative composition was similar in all populations but their quantitative composition was quite different. A major difference occurs in the monoterpene hydrocarbons and diterpene fractions among the examined populations. Diterpene compounds were detected and identified for the first time in the essential oil of Sideritis linearifolia and have been found to include higher percentages of sesquiterpene compounds. The relationship between variability of essential oil compounds and climatic enviromental conditions is reported. Copyright © 2004 John Wiley & Sons, Ltd.

Penitrem G (7), a new indole-diterpenoid compound, has been isolated together with the already known mycotoxins penitrems A-D (1-4) and F (6) from the mycelium of Penicillium crustosum Thom. The structure of penitrem G was established on the basis of spectroscopic data. In addition, paspaline (8), another indole-diterpenoid mycotoxin that has not been previously described in this fungus, was also isolated. These compounds were tested for insecticidal activity against the hemipteran Oncopeltus fasciatus Dallas and the dipteran Ceratitis capitata Wiedemann. Penitrems A-D and F showed convulsive and insecticidal activities against both insect species. In addition, important reductions in the fecundity and fertility of the surviving C. capitata females were observed. In contrast, penitrem G and paspaline did not show any kind of activity. Mortality data and sublethal effects of the treatments have allowed preliminary structure-activity relationships to be proposed.

[EN] Trapping systems for the red palm weevil, Rhynchophorus ferrugineus Olivier, rely on the use of natural plant odor sources to boost the attractiveness of the aggregation pheromone. The identification of the key odorants involved in attraction is essential in the development of a synthetic pheromone synergist to replace the nonstandardized use of plant material in traps. Canary Islands date palms (Phoenix canariensis) have become preferred hosts for R. ferrugineus in Europe; thus, the volatile profile of different P. canariensis plant materials, including healthy and infested tissues, is investigated in the present work by means of solid phase microextraction (SPME-GC-MS), aimed to identify pheromone synergists. The electroantennography (EAG) response of the compounds identified was recorded, as well as the preliminary field response of several EAG-active compounds. The so-called palm esters (ethyl acetate, ethyl propionate, ethyl butyrate, and propyl butyrate) elicit the strongest EAG responses but performed poorly in the field. Mixtures of esters and alcohols give evidence of better performance, but release rates need further optimization., The research leading to these results has received funding from the 7th European Union Framework Programme under Grant Agreement FP7 KBBE 2011-5-289566 (PALM PROTECT).

The use of traps and other attract-and-kill devices in pest management strategies to reduce Mediterranean fruit fly populations has proved to be efficient. Nevertheless, many farmers are concerned about the effect of these devices on the trees where they are hung. Direct field observations have revealed that fruit damage is higher in trees with traps than in trees without them. This work evaluates the efficacy of different types of attract-and-kill device to protect fruit of the single tree on which the device is placed.Results suggested that trees with traps had at least the same fruit damage than trees without them. When traps were baited with protein hydrolysate, fruit damage was even higher than in trees without traps. However, fruit damage was significantly diminished when efficient bait station devices were used.Although mass trapping is able to control fruit fly populations as a control method, trees with some types of trap and bait are more susceptible to fly puncture. However, bait station devices reduce fruit damage in the single trees where they are hung. Bait stations are more efficient in fruit protection because fruit flies are affected as soon as they contact the device. Some recommendations for the use of the different attract-and-kill devices are discussed.

Bait stations are widely used to control Ceratitis capitata, even though the effect of intrusion from untreated areas decreases the efficacy of the technique. In this work, the edge effect of outer fruit fly populations from untreated areas and backyard orchards has been studied. For this purpose, a field trial was carried out during four years in a wide area of 10 000 ha located in Valencia (Spain). The main growing species were Prunus persica, Prunus domestica, Citrus sinensis, Citrus reticulata and Diospyros kaki. An area of 3,600 ha was treated with chemosterilant bait stations. Fruit fly populations were monitored during the 4 years of study inside and outside the treated area using Tephri-traps baited with trimedlure. A grid of 180 traps was placed in the field with an intertrap distance of 450 m. Multiple linear regression was applied to model population levels as a function of distance to untreated areas and backyards. The distance at which outer medfly populations influenced the treated wide-area population was about 1.3 km. This value reflects the distance at which a given fruit fly population is influenced by outer populations and suggests that C. capitata is able to move more than 1 km seeking for hosts. Thus, buffer areas in area-wide integrated pest management of Mediterranean fruit fly should be at least 1.3 km wide.

[EN] Laboratory experiments were conducted to evaluate the compatibility of using the entomopathogenic fungus Metarhizium anisopliae, to be dispensed in a new attractant contaminant device (ACD), jointly with sterilized Ceratitis capitata males, as an integrated approach to control this major pest. The exposure of sterile Vienna 8 (V8) strain and wild type (WT) males to the contaminating part (infective dish) of the ACD showed similar susceptibility levels to the fungal strain (LT50 value of 4.52 and 4.72 days, respectively). Sterile V8 males were significantly less attracted to the infective dish (18.4%) than WT males (28.5%). As the success of Sterile Insect Technique (SIT) heavily relies on the mating success of sterile males in the field, mating performance of infected males was assessed. Around 85% of the females were mated, independently of the male strain and treatment (fungus-treated or untreated males) indicating that mating performance was unaffected by the fungus under laboratory conditions. Females showed a greater tendency to remate if previously mated to fungus-treated males, either V8 or WT. Our data suggest that this M. anisopliae based-ACD does not impair the performance of C. capitata sterile males and, therefore, it could be used combined with area wide SIT-based programs, providing that these results are validated in field conditions. The implications of this combined strategy to control C. capitata are discussed. (C) 2014 Elsevier Inc. All rights reserved., This work was partially supported by the "Comision Interministerial de Ciencia y Tecnologia" (CICYT, Spain) (Grant: AGL2006-13346-C02-02).

Seventy-nine volatile compounds chosen from those emitted by Mediterranean fruit fly males, fruits and food baits, were tested for their attractiveness to females of Ceratitis capitata (Wiedemann) in field trials with a wild population. To correct for density fluctuations, the results were presented as a percentage of males caught in the same type of traps baited with trimedlure, a known male attractant. The mixtures of corn steep liquor with ammonia compounds and amines were the most effective attractants for females. Other compounds exhibiting C. capitata attraction were a mixture ethyl acetate+acetic acid+ethanol for both sexes, and p-cymene, 1,3-diethylbenzene and borneol for females.

New analogues of the bioactive enamides isolated from P. brevicompactum (2 and 3) have been synthesized to improve the biological activities. Two different structural modifications have been introduced: substitution of the aliphatic side chain present in the natural products (1−4) by other groups frequently found in other active compounds and use of other nitrogen-containing five-membered rings with different degrees of oxidation. In this way, the insecticidal and fungicidal activities have been improved. Thus, compound 9, which posseses a 3-pyrroline ring, exhibited important insecticidal activity against third-instar nymphs of Oncopeltus fasciatus Dallas (100% mortality at 7.5 μg/cm2). Remarkable fungicidal activity was also found, and preliminary structure−activity relationships could be established. Keywords: Penicillium brevicompactum; fungal metabolites; β-ketoamide; analogues; insecticide; fungicide