Química General I_Curs 2019_2020_Apunts per a treballar a l'aula

El document forma part dels materials docents programats mitjançant l'ajut del Servei de Política lingüística de la Universitat de València.Apunts utilitzats a l'aula per a fer les exposicions de la part teòrica de l'assignatura de química general segons la guia docent del curs en qüestió. Conta dels temes que es detallen a continuació: Tema 1. INTRODUCCIÓ. Tema 2. ESTRUCTURA ATÒMICA Tema 3. ÀTOMS POLIELECTRÒNICS i PROPIETATS PERIÒDIQUES Tema 4. ENLLAÇ QUÍMIC I Tema 5. ENLLAÇ QUÍMIC II. Formulació química orgànica Tema 6. ESTRUCTURA I ENLLAÇ. COMPORTAMENT QUÍMIC ÀCID-BASE Tema 7. SUBSTÀNCIES MOLECULARS Temes 8 i 9. SÒLIDS NO MOLECULARS Tema 10. Formulacions orgànica i inorgànica bàsiques

Mating disruption to control the striped rice stem borer: Pheromone blend, dispensing technology and number of releasing points

The effect of using low densities of different dispensing technologies on mating disruption of the striped rice stem borer, Chilo suppressalis Walker, was evaluated in the rice-growing area of Valencia (Spain) from 2011 to 2013. The reduction of the current number of release points (30 polymeric dispensers/ha) was investigated by installing 3 aerosol devices per ha (Experiments 1 and 2) or with clusters of hand-applied dispensers (10 or 5 release points/ha; Experiment 3). The influence of pheromone blend on disruption was also studied by loading aerosol devices with the three-component blend or only the main pheromone compound, Z-11-hexadecenal. Results showed that the installation of 3 aerosol devices/ha or clusters of passive dispensers (total dose: 6.6-7.9 g/ha) proved equally effective as the conventional treatment with 30 Selibate (R) CS dispensers/ha (similar to 5 g/ha), reducing damage below 1% of infested plants. Although the treatment with 3 aerosol devices/ha loaded with Z-11-hexadecenal provided control of damage comparable to the conventional mating disruption treatment, the higher captures recorded suggest that mating disruption with the incomplete pheromone blend is only slightly effective in the tested conditions. These changes in the number of point sources and pheromone blend could represent important advantages for the implementation of mating disruption against C. suppressalis. (C) 2016 Korean Society of Applied Entomology, Taiwan Entomological Society and Malaysian Plant Protection Society. Published by Elsevier B.V. All rights reserved.We would like to thank Francisco Girona, Vicente Dalmau and Manuel Lainez (CAPA-Generalitat Valenciana) for their assistance in organizing experiments and providing trial fields. In addition, thanks to Helen Warburton for English editing. This project was funded by Fundacion Agroalimed and Ecologia y Protection Agricola SL (Valencia, Spain).Vacas González, S.; Navarro Fuertes, I.; Primo Millo, J.; Navarro-Llopis, V. (2016). Mating disruption to control the striped rice stem borer: Pheromone blend, dispensing technology and number of releasing points. Journal of Asia-Pacific Entomology. 19(2):253-259. doi:10.1016/j.aspen.2016.02.001S25325919

Sex Pheromone of the Invasive Mealybug Citrus Pest, Delottococcus aberiae (Hemiptera: Pseudococcidae). A New Monoterpenoid with a Necrodane Skeleton

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Agricultural and Food Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://pubs.acs.org/page/policy/articlesonrequest/index.html].[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)Vacas, S.; Navarro Fuertes, I.; Marzo, J.; Navarro-Llopis, V.; Primo Millo, J. (2019). Sex Pheromone of the Invasive Mealybug Citrus Pest, Delottococcus aberiae (Hemiptera: Pseudococcidae). A New Monoterpenoid with a Necrodane Skeleton. Journal of Agricultural and Food Chemistry. 67(34):9441-9449. https://doi.org/10.1021/acs.jafc.9b01443S94419449673

Identification of the Male-Produced Aggregation Pheromone of the Four-Spotted Coconut Weevil, Diocalandra frumenti

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Agricultural and Food Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.jafc6b04829[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).Vacas González, S.; Navarro Fuertes, I.; Seris, E.; Ramos, C.; Hernández Suárez, E.; Navarro-Llopis, V.; Primo Millo, J. (2017). Identification of the Male-Produced Aggregation Pheromone of the Four-Spotted Coconut Weevil, Diocalandra frumenti. Journal of Agricultural and Food Chemistry. 65(2):270-275. doi:10.1021/acs.jafc6b04829S27027565

Airborne Pheromone Quantification in Treated Vineyards with Different Mating Disruption Dispensers against Lobesia botrana

Mating disruption (MD) is widely used against the European grapevine moth (EGVM), Lobesia botrana (Denis and Schi ermüller; 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 di erent 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 e ective in limiting the damage inflicted by EGVM, they performed di erently and provided di erent 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 di erent 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

Sex Pheromone of the Invasive Mealybug Citrus Pest, Delottococcus aberiae (Hemiptera: Pseudococcidae). A New Monoterpenoid with a Necrodane Skeleton

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 β-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

General Diastereoselective Synthetic Approach toward Isospongian Diterpenes. Synthesis of (-)-Marginatafuran, (-)-Marginatone, and (-)-20-Acetoxymarginatone

This work describes a synthetic approach to the carbocyclic skeleton of isospongian diterpenes that uses the commercially available monoterpene (S)-carvone as a C-ring synthon, which is incorporated into the tetracyclic isospongian framework via a C -> ABC -> ABCD ring annulation strategy using intramolecular Diels-Alder and ring-closing metathesis reactions. This approach has been successfully used to prepare both the title natural isospongians and several nonnatural oxygenated analogues. A preliminary evaluation of the inhibitory activity of the small collection of synthesized isospongians on the mammalian mitochondrial respiratory chain revealed that most were able to inhibit the integrated electron transfer chain (NADH oxidase activity) in the micromolar range.We thank the Spanish Ministerio de Ciencia e Innovacion (MICINN) and the company EPA S.L. (Cadet, Spain) for their continuous support of our work (Projects BQU2002-00272 and AGL2009-12940-C02-02). We also thank the S.C.S.I.E. of the University of Valencia for providing access to their NMR facilities and E. Estornell and V. Romero for biological assay support.Gris, A.; Cabedo Escrig, N.; Navarro Fuertes, I.; De Alfonso, I.; Agullo, C.; Abad Somovilla, A. (2012). General Diastereoselective Synthetic Approach toward Isospongian Diterpenes. Synthesis of (-)-Marginatafuran, (-)-Marginatone, and (-)-20-Acetoxymarginatone. Journal of Organic Chemistry. 77(13):5664-5680. doi:10.1021/jo3008034S56645680771

Engineering of a plant isoprenyl diphosphate synthase for development of irregular coupling activity

We performed mutagenesis on a regular isoprenyl diphosphate synthase (IDS), neryl diphosphate synthase from Solanum lycopersicum (SlNPPS), that has a structurally related analogue performing non-head-to-tail coupling of two dimethylallyl diphosphate (DMAPP) units, lavandulyl diphosphate synthase from Lavandula x intermedia (LiLPPS). Wild-type SlNPPS catalyses regular coupling of isopentenyl diphosphate (IPP) and DMAPP in cis-orientation resulting in the formation of neryl diphosphate. However, if the enzyme is fed with DMAPP only, it is able to catalyse the coupling of two DMAPP units and synthesizes two irregular monoterpene diphosphates; their structures were elucidated by the NMR analysis of their dephosphorylation products. One of the alcohols is lavandulol. The second compound is the trans-isomer of planococcol, the first example of an irregular cyclobutane monoterpene with this stereochemical configuration. The irregular activity of SlNPPS constitutes 0.4% of its regular activity and is revealed only if the enzyme is supplied with DMAPP in absence of IPP. The exchange of asparagine 88 for histidine considerably enhanced the non-head-to-tail coupling. While still only observed in the absence of IPP, irregular activity of the mutant reaches 13.1 % of its regular activity. The obtained results prove that regular IDS are promising starting points for protein engineering aiming at the development of irregular activities and leading to novel monoterpene structures

Engineering of a Plant Isoprenyl Diphosphate Synthase for Development of Irregular Coupling Activity

We performed mutagenesis on a regular isoprenyl diphosphate synthase (IDS), neryl diphosphate synthase from Solanum lycopersicum (SlNPPS), that has a structurally related analogue performing non-head-to-tail coupling of two dimethylallyl diphosphate (DMAPP) units, lavandulyl diphosphate synthase from Lavandula x intermedia (LiLPPS). Wild-type SlNPPS catalyses regular coupling of isopentenyl diphosphate (IPP) and DMAPP in cis-orientation resulting in the formation of neryl diphosphate. However, if the enzyme is fed with DMAPP only, it is able to catalyse the coupling of two DMAPP units and synthesizes two irregular monoterpene diphosphates; their structures were elucidated by the NMR analysis of their dephosphorylation products. One of the alcohols is lavandulol. The second compound is the trans-isomer of planococcol, the first example of an irregular cyclobutane monoterpene with this stereochemical configuration. The irregular activity of SlNPPS constitutes 0.4% of its regular activity and is revealed only if the enzyme is supplied with DMAPP in the absence of IPP. The exchange of asparagine 88 for histidine considerably enhanced the non-head-to-tail coupling. While still only observed in the absence of IPP, irregular activity of the mutant reaches 13.1% of its regular activity. The obtained results prove that regular IDS are promising starting points for protein engineering aiming at the development of irregular activities and leading to novel monoterpene structures

Alternative Hapten Design for Zearalenone Immunoreagent Generation

Appropriate hapten design and synthesis have been identified as critical steps to gener-ate high-performance immunoreagents and to develop sensitive and selective immunoanalytical methods. Antibodies and immunoassays for the major mycotoxin zearalenone have been reported and marketed. However, zearalenone haptens have mostly been prepared by the oxime active ester technique, and hapten characterization has generally been poor or non-existent. In the present study, novel haptens of zearalenone with longer linkers and with alternative tethering sites have been designed for immunizing and assay conjugate preparation. All of these molecules were purified and spectroscopically verified, and a structure-activity relationship evaluation was carried out. This approach revealed that the hapten with the linker at the carbonyl group generated antibodies with a higher affinity than the hapten functionalized at the phenyl moiety. Antibodies produced with the latter hapten, on the other hand, showed lower cross-reactivity values to the major zearalenone metabolites. Finally, similar immunoassay sensitivity was achieved with all of the antibodies when heterologous haptens were employed. Furthermore, by altering the structure of the competing antigen, the immunoassay selectivity was modified. These results demonstrate that immunochemical methods for zearalenone rapid analysis can still be improved in terms of sensitivity and selectivity.This research was funded by the SPANISH MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD, grant numbers RTI2018-096121 and AGL2015-64488, and co-financed by EUROPEAN REGIONAL DEVELOPMENT FUNDS. Animal manipulation as well as mass, spectrometric, and proteomic analysis was performed at the SCSIE service of the University of Valencia. The proteomics laboratory is a member of Proteored.Peer reviewe