44 research outputs found

    Distribution, pest status and agro-dimatic preferences of lepidopteran stem borers of maize in Kenya

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    Lepidopterous stem borers are the main field insect pests that attack maize, Zea mays L. in tropical Africa. A survey was carried during the long and short rain cropping seasons of 2002/2003 across six main agro-climatic zones (ACZs) to determine the spatial distribution of important stem borer species in Kenya. A total of 474 visits were made in the seventy-eight localities conveniently chosen to represent each of the six ACZs. 189,600 stems were checked for infestation, of which 27,799 infested stems were destructively cut and dissected for stem borer larvae identification. An average of 1.4 stem borer larvae were recovered per infested plant. 54.5% of the recovered larvae were identified as Chilo partellus (Swinhoe) (Crambidae), 39.7% as Busseola fusca (Fuller) (Noctuidae), 4.5% as Sesamia calamistis Hampson (Noctuidae) and 0.8% as Chilo orichalcociliellus (Strand) (Crambidae). Minor species present included Eldana saccharina Walker (Pyralidae), Sesamia nonagrioides (Lefebvre) (Noctuidae), Sesamia cretica Lederer (Noctuidae), Sesamia sp. (Noctuidae), Sciomesa piscator Fletcher (Noctuidae), Busseola sp near phaia (Noctuidae), Chilo sp, Ematheudes sp 1 (Pyralidae) and Ematheudes sp 2 (Pyralidae). Farms were grouped into respective ACZs for statistical analysis and subsequent comparison of dominant species: Results indicated that B. fusca was the dominant stem borer species in high potential zones (highland tropics, moist transitional zone and moist mid-altitude) while the exotic C. partellus dominated smallholder farms in low potential zones (dry mid-altitude, dry transional and lowland tropical zone). Within each ACZs, there was evidence of variation in species proportions between seasons. These spatio-temporal differences in community structure are discussed in terms of agro-climatic biological adaptations

    Nouveaux développements en organocatalyse (du dédoublement d'alcools à la protonation énantioselective organocatalysée)

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    Le projet présenté dans ce manuscrit concerne l étude de nouveaux développements en organocatalyse. Dans un premier temps, nous avons développé la fonctionnalisation du squelette 4-(diméthylamino)pyridine. Cette denière a permis de synthétiser 3 nouveaux organocatalyseurs chiraux dont l efficacité a été démontrée dans le dédoublement d alcools secondaires et le réarrangement de Steglich. Cette étude, nous a permis de développer une nouvelle méthode de transprotection O-silyl O-benzoyl. Cette méthode de transprotection nous a conduit à la mise au point de la première réaction de protonation asymétrique organocatalysée d éthers d enols silylés. Tout d abord par l utilisation de fluorure d ammonium chiraux, puis par l emploi d acide carboxylique en présence d amine chirale. Ces deux méthodes ont conduit à l obtention de cétones a-substituées énantioenrichies avec des ee maximum de 92%. Ces méthodologies ont été appliquées à la synthèse énantiosélective d homoisoflavones et d isoflavone.This work deals with the development of new organocatalysis tools for organic synthesis. First, we have performed the functionalization of the 4-(dimethylamino)pyridine scaffold. This functionalization has furnished three original organocatalysts which were evaluated in two reactions : the secondary alcohol resolution and the Steglich rearrangement. During the course of this study we have discovered a new transprotection procedure of O-silyl compounds into O-benzoyl compounds. In addition, we have performed the first organocatalytic enantioselective protonation of silyl enolates mediated by cinchona alkaloids and a latent source of HF. This process was simplified by the use of carboxylic acid and cinchona alkaloids. This two approaches leads to enantioselective proton transfer with enantioselectivities up to 92% ee. Finally this methodologies was applied to the enantioselective synthesis of homoisoflavones and isoflavones with enantioselectivities up to 81%.ROUEN-BU Sciences (764512102) / SudocROUEN-BU Sciences Madrillet (765752101) / SudocSudocFranceF

    Valorisation du groupement sulfoximine en synthèse asymétrique (application à la réaction d'ortho-métallation, synthèse de nouveaux modèles du NADH)

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    Dans une première partie, nous avons développé une voie de synthèse conduisant à la S-phényl-S-tert-butylsulfoximine énantiopure. Différentes S-phényl-S-tert-butylsulfoximine N-substituées ont été préparées et ortho-métallées. Nous avons ainsi montré la capacité du groupe sulfoximine à diriger la réaction d'ortho-métallation et mis au point les conditions de métallation. Ceci nous a permis d'accéder à de nouvelles sulfoximines ortho-substituées. L'utilisation d'électrophiles prochiraux a permis l'obtention des produits ortho-substitués correspondants avec des excès diastéréoisomériques variant de modestes à très bons. Nous avons mis en évidence dans certains cas une réaction secondaire de déterbutylation conduisant au dérivé sulfinamide correspondant. Cette réaction a été étudiée et des conditions de déterbutylation optimisées ont été mises au point. Enfin, il a été montré que cette réaction de déterbutylation est stéréospécifique et qu'elle a lieu avec rétention de configuration. Dans une seconde partie, nous avons développé de nouveaux modèles du NADH en série quinoléine possédant des dérivés soufrés comme inducteur chiral. Une première voie de synthèse a été envisagée à partir de la réaction de condensation de Friedländer. Cette voie n'a pas aboutie en raison de l'effet électroattracteur des groupes soufrés et de l'encombrement stérique en position C2 de la quinoléine. En conséquence, une approche via une réaction de quaternarisation intramoléculaire a été développée, mais celle-ci n'a pu aboutir. Une seconde approche concernant la synthèse de quinoléines moins encombrées à partir de 3-bromoquinoléines a été mise au point. Plusieurs modèles ont été synthétisés en série quinoléine et 6,7-diméthoxyquinoléine comportant un groupement sulfoximine, sulfoxyde ou sulfilimine comme inducteur de chiralité. Parmi ces modèles, seules ceux comportant un sulfoxyde ont permis la réduction du benzoyle formiate de méthyle en mandélate de méthyle. Enfin, cette réduction a eu lieu avec un excellent excès énantiomérique.The first project deals with the use of the sulfoximine as an ortho-directing group in metalation reactions. After optimization of the metalation conditions, the sulfoximine group proved to be an excellent ortho-directing group. Several electrophiles were tested to afford the corresponding ortho-fonctionalized aryl sulfoximines in good yields. The use of prochiral electrophiles allowed us to obtain modest to good diasteroselectivities up to 95%. During this study we observed a side reaction due to a S-deterbutylation. This deterbutylation provided new sulfinamides with high stereoselectivities. After optimization of the S-deterbutylation reaction, the corresponding enantiopures sulfinamides were obtained in good yields. The second project deals with the synthesis of new chiral NADH models in sulphur series. The sulphur allows to install the chirality close to the active site of the NADH model. We chose to develop models in quinoline series. The first relies on a Friedlander type reaction. This strategy allows to introduce the chirality with the commercially available enantiopure S-phenyl-S-methylsulfoximine. All attempts to quaternize the quinoline nitrogen failed probably due to a steric hindrance and the withdrawing effect of the sulfoximine group. To circumvent this problem, we turned our attention to a less hindered structure. This strategy is based on C-S stereospecific bond formation. The key reaction is a halogen metal exchange on the 3-bromoquinoline. Various 1,4-dihydroquinolines substituted at C-3 by a chiral sulfoxide, sulfoximine and racemic sulfilimine derivatives were prepared in few steps. The mimics bearing the sulfoxide auxiliary showed to be highly enantioselective affording the methyl mandelate in 98% e.e.ROUEN-BU Sciences (764512102) / SudocSudocFranceF

    Ligand controlled orthogonal base-assisted direct C-H bond arylation in oxa(thia)zole-4-carboxylate series. New insights in nCMD mechanism

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    International audienceAlkyl- and arylphosphines have been screened in competitive C2–H/C5–H direct phenylation of oxa(thia)zole-4-carboxylates using Cs2CO3 and Rb2CO3 carbonate bases. nCMD-based C2–H selective direct phenylation was highly kinetically reduced (or enhanced) in favor (or to the detriment) of CMD-based direct C5–H phenylation with bromo- and chlorobenzene, respectively, using highly electron-rich ligands. These results gave novel experimental proof in favor of the electrophilic substitution-type mechanism for nCMD process based upon a prior nitrogen-arylpalladium complex interaction that preludes the deprotonation step

    serrano gene and NaCl perception

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    Gustatory information is considered to be important for animals to control behavior when they seek for food or partners. 60 members of gustatory receptor (Gr) genes have been identified in Drosophila.. However little is now about mechanisms of taste perception and transduction in response to stimuli. In order to identify new genes involved in gustation, we performed a genetic screen using Gal4-UAS system based on expression of the reporter gene in chemosensory organs and gustatory defects in larvae and adults. We identified the serrano (sano) gene, which encodes a 778 aa protein with a leucine zipper domain, a putative transmembrane domain, and putative bipartite nuclear localization signals. sano expresssion using the P-Gal4 line can be detected in several neurons of the larval terminal organs. RT-PCR analysis revealed that four transcripts sano expressed at different levels in the peripheral nervous system and the brain of larvae. Loss of aversive response towards high NaCl concentration is observed when sano function is reduced (sanoGal4 homozygous or elav-Gal4-sanodsRNA). A similar taste defect results from the blocking of neuronal transmission in sano expressing neurons (sanoGal4-UAS-TNTE). However, attractive or aversive responses towards low NaCl concentration, sweet or bitter compounds are not affected in elav-Gal4-sanodsRNA larvae. These results strongly suggest that Serrano function is specifically required in sensory neurons of the larval terminal organs for aversive response to high NaCl concentration taste

    serrano gene and NaCl perception in Drosophila

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    Résumé de poster présenté au congrès Neurofly à Manchester en Septembre 2010.International audienc
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