Synthèse et étude de nouvelles molécules potentiellement polymérisables pour la fabrication de matériaux électroluminescents : analogues du 1,3,5 benzènetripyrrole, méthyle 3,5-bipyrrolebenzoate et 6,12-diméthyle-1,5-dipyrrolediazocane

Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.

Decreased 5-F{T1fti Receor Gene Expression and 5-F4T11 Receptor Protein in the Cerebra'' Cortex and Brain Stem during Pancreatic Regenera tion in Rats

The present study was to investigate the rote of central 5-11T and 5-HT,:v receptor Lindin4o and acne expression in it 'at mo(lel of pancreatic regeneration using 60" -, pancreatcutumy. The pancreatic regeneration was evaluated by 5-HT content and 5-HT,,receptor gene expression in the cerebral cortex (CC) and brain stem MS) of Alain opcrate,t, 7 It utd 7 (.lays panereatectomised rats. 5-11T content significantly increased in the CC' (I' 1.1)11 and 13S (P 0.05) of 72 Ii p.ntcreateetomiscd rats. Sympathetic activity was decreased as indicated by the significantly decreased norcpiuephrine (NIi) and epinephrine (FTI) Icvcl (1' < 0.001 and P < 0.05) in the plasma of 72 h panereateetomised rats. 5-111 ,^, receptor density and affinity was decreased in the CC (P < 0.01) and BS (P < 0.01). These rh:)nge; correlated with a diminished 5-IITIA receptor mRNA expression in the brain region. studied. Our resuils suggest that the brain 5-11T through 5-HTin receptor has it funcuon:0 rule iii 11w pi+ncreatic regcner:ttion through the sympathetic regulation.

Compact Planar Multiband Antenna for GPS, DCS, 2.4/5.8 GHz WLAN Applications

A compact single –feed multiband planar antenna configuration Suitable for GPS, DCS. 2.4/5.8 GHz WLAN applications are presented. The antenna has dimensions 38 x 3 x 1.6 mm and offers good radiation and reflection characteristics in the above frequency bands. The antenna has a simple geometry and can be easily fed using a 50 coaxial probe

Compact Planar Multiband Antenna for GPS,DCS 2.4/5.8 GHz WLAN Applications

A compact single - feed muttiband planar antenna configuration suitable for GPS, DCS. 2.4/5.8 GHz WLAN applications is presented. The antenna has dimensions 38 x 3 x 1.6 mm and offers good radiation and reflection characteristics in the above frequency bands. The antenna has a simple geometry and can be easily fed using a 50 coaxial probe.

A Novel Decision Tree Algorithm for Numeric Datasets - C 4.5*Stat

Decision trees are very powerful tools for classification in data mining tasks that involves different types of attributes. When coming to handling numeric data sets, usually they are converted first to categorical types and then classified using information gain concepts. Information gain is a very popular and useful concept which tells you, whether any benefit occurs after splitting with a given attribute as far as information content is concerned. But this process is computationally intensive for large data sets. Also popular decision tree algorithms like ID3 cannot handle numeric data sets. This paper proposes statistical variance as an alternative to information gain as well as statistical mean to split attributes in completely numerical data sets. The new algorithm has been proved to be competent with respect to its information gain counterpart C4.5 and competent with many existing decision tree algorithms against the standard UCI benchmarking datasets using the ANOVA test in statistics. The specific advantages of this proposed new algorithm are that it avoids the computational overhead of information gain computation for large data sets with many attributes, as well as it avoids the conversion to categorical data from huge numeric data sets which also is a time consuming task. So as a summary, huge numeric datasets can be directly submitted to this algorithm without any attribute mappings or information gain computations. It also blends the two closely related fields statistics and data mining

Diagnóstico y tratamiento de las dificultades lectoras (en niñas de 4., 5. y 6. de EGB).

Realizar una investigación aplicada en unos centros escolares, con el fin de aportarles unas orientaciones pedagógicas en la función lectora. Detectar problemas lectores en niñas de 4., 5. y 6. de EGB y ofrecer una orientación para resolverlos. Centro A (colegio nacional de Barcelona): 88 alumnas de cuarto de EGB, 84 alumnas de quinto de EGB, 90 alumnas de sexto de EGB. Centro B (colegio privado de Palma de Mallorca): 35 alumnas de cuarto de EGB, 45 alumnas de quinto de EGB, 50 alumnas de sexto de EGB. Propone una base teórica sobre el tema de la lectura. Plantea las siguientes hipótesis: 1. Medios de que se sirve un departamento de orientación para detectar dificultades lectoras. 2. ¿Es suficiente con que el orientador dé al profesor un diagnóstico de las dificultades lectoras?, ¿es necesario que el diagnóstico vaya acompañado de tratamiento?. Aplica las distintas pruebas y elabora un diagnóstico general. Realiza diagnósticos analíticos para las niñas con dificultades. Aplica al centro B actividades correctivas y tratamiento de la lectura. Hace un estudio comparativo de los dos centros. Verifica las hipótesis. Sociogramas. Prueba de WISC. Prueba de F. Huerta. Prueba de Vistorino Arroyo del Castillo. Índices estadísticos. Investigación aplicada. Comparación de medias. Existe en cada curso un elevado pocentaje de niñas con dificultades lectoras. Comparando los centros A y B, después del tratamiento, se observa un avance en vocabulario y lectura oral a favor del centro A. Es necesaria la creación o adaptación de tests de lectura debido a la escasez existente. Se detecta la importancia de ejercicios de vocabulario en colegios situados en zonas bilingües.

El duende : reconocimiento de las letras mayúsculas y minúsculas : 4-5 años.

Software educativo que trata de enseñar a niños de 4 y 5 años a identificar las letras mayúsculas y minúsculas a través del juego.

Oxford reading tree. Teacher's guide 2 : stages 4-5.

Explicaciones detalladas de cómo sacar el máximo provecho de cada etapa. Las ideas y sugerencias de esta guía mantienen y amplían la filosofía de la lectura, y el programa, según la propuesta de métodos de enseñanza establecidos en la guía del primer nivel, que ayudarán a dar a los niños la confianza, y las habilidades necesarias para hacer frente a historias con textos más extensos y complejos. Contiene actividades de apoyo a una serie de estrategias de lectura, recursos fotocopiables, actividades tranversales de los contenidos curriculares, evaluación con hojas de registro. También incluye material adicional.

Premier English . Ages 4-5 pre-school.

Cuaderno de trabajo diseñado para trabajar las directrices de alfabetización junto con el programa de estudios primarios. Las tarjetas muestran treinta y seis palabras de uso común, asociadas a una imagen, que pueden utilizarse para ayudar en el reconocimiento de palabras y frases. También pueden usarse las tarjetas para practicar la ortografía mirando, escribiendo y comprobando las palabras. Al final de la publicación están las soluciones a los ejercicios propuestos .

Formation of triple helical nanofibers using self-assembling chiral benzene-1,3,5-tricarboxamides and reversal of the nanostructure's handedness using mirror image building blocks

Intertwining triple helical nanofibers with an overall handedness have been formed from self-assembling chiral benzene-1,3,5-tricarboxamides 1, 2 and 3, whereas the achiralbenzene-1,3,5-tricarboxamide 4 upon self-association gives rise to straight nanofibers without any twist and transmission electron microscopy images of chiral compounds clearly demonstrate that the handedness of the triple helical nanofibers can be reversed by using the enantiomeric benzene-1,3,5-tricarboxamide building blocks.

Solvent extraction and lanthanide complexation studies with new terdentate ligands containing two 1,3,5-triazine moieties

The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L-5) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D-Am/D-Eu separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO3. Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO3. In order to investigate the possible nature of the extracted species crystal structures of L-5 and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L-4) were also determined. The structure of L-5 shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L-5 is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L-4. The crystal structure of Yb(L-4)(NO3)(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L-4 and L-5 are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L-1) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L-4 and L-5 is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L-1 evolve from the presence of two adjacent nitrogen atoms in the triazine rings.

Cytenamide-1,4-dioxane (2/1)

In the crystal structure of the title compound [systematic name: 5H-dibenzo[a,d]cycloheptatriene-5-carboxamide-1,4dioxane(2/1)], 2C(16)H(13)NO center dot C4H8O2, the cytenamide molecules form a hydrogen-bonded R-2(2)(8) dimer. The solvent molecule is located between two adjacent cytenamide dimers and forms N-H center dot center dot center dot O hydrogen bonds with one cytenamide molecule from each dimer.