Nuevas reacciones multicomponentes para la síntesis de derivados de piridina como agentes antineurodegenerativos potenciales

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Farmacia, Departamento de Química Orgánica y Farmacéutica, leída el 15-06-2015Las principales conclusiones derivadas de esta tesis son las siguientes, 1. La reacción multicomponente catalizada por tricloruro de indio entre compuestos betadicarbonílicos, dimetilhidrazina, acroleínas y etanol proporciona derivados de 6etoxi1,4,5,6tetrahidropiridina. Esta transformación se acopló con un proceso de doble eliminación, sin necesidad de etapas de purificación intermedias, para dar lugar a un método de síntesis de piridinas 2,3disustitutidas que pudo adaptarse también a la preparación de varias familias de piridinas fusionadas. 2. La reacción tricomponente entre compuestos betadicarbonílicos, chalconas y acetato amónico en etanol a reflujo, en presencia de una cantidad catalítica de nitrato cérico amónico, conduce a 4,6diaril1,4dihidropiridinas. Estos compuestos mostraron una selectividad mejorada hacia el canal Cav1.3 neuronal en comparación con otras dihidropiridinas previamente conocidas y se comportan como agentes neuroprotectores frente a procesos de isquemia. 3. Una reacción similar entre betacetoamidas, chalconas y acetato amónico condujo al aislamiento directo de derivados de nicotinamida, a través de una secuencia reacción tricomponente, oxidación. 4. Se ha puesto a punto la síntesis de dihidropiridinas fusionadas y sus análogos oxigenados a través de reacciones tricomponentes de tipo Hantzsch entre malononitrilo, aldehídos aromáticos y pirazoles funcionalizados en C5 con estructura de lactama o amidina. Estos compuestos fueron diseñados por métodos computacionales como inhibidores de la enzima GSK3beta y se están estudiando como agentes anti Alzheimer. 5. Se han diseñado estructuras híbridas que contienen como fragmentos estructurales el nimodipino y un aza análogo de CGP37157 como agentes anti Alzheimer potenciales por estabilización de los niveles de calcio neuronal y mitocondrial a través de una aproximación multidiana. Estos compuestos se sintetizaron a través de una variante de la síntesis de Hantzsch de dihidropiridinas. También se han obtenido compuestos híbridos del mismo análogo de CGP37157 y ácido lipoico, un antioxidante capaz de atravesar la barrera hematoencefálica. Ambas familias de compuestos se están investigando como agentes anti Alzheimer. 6. Se ha desarrollado un método para la alquenilación oxidativa de arilsulfonamidas por medio de una reacción de activación CH catalizada por especies de a RuII.Depto. de Química en Ciencias FarmacéuticasFac. de FarmaciaTRUEunpu

I PROGRAMMI PER LA VISUALIZZAZIONE DI IMMAGINI DELLA TERRA COME AUSILIO DIDATTICO ALL’INSEGNAMENTO DELLA GEOGRAFIA: GOOGLE EARTH E NASA WORLD WIND

Lo sviluppo di nuove tecnologie informatiche in campo cartografico ha portato alla creazione di applicazioni che consentono innovative operazioni utili non solo per iniziative scientifiche, ma anche didattiche. Tra questi prodotti vi sono Google Earth e Nasa World Wind, strumenti gratuiti ideati per la visualizzazione tridimensionale della Terra tramite la composizione di immagini satellitari, foto aeree e dati topografici. Oltre a questa prerogativa le ultime versioni di questi software sono state arricchite da molteplici funzioni che possono essere utilizzate a fini didattici in quanto permettono il collegamento tra le immagini tridimensionali del globo terrestre con dati, carte e informazioni inerenti alcune discipline quali la Cartografia tematica e storica e la Geografia fisica e umana.The development of new data processing technologies in cartographic field took to the creation of applications which not only allow useful scientific and didactic operations Google Earth and Nasa World Wind are two of these products; they are free tools planned for the three-dimensional Earth display through the composition of satellite images, aerial photos and topographical data. Besides this prerogative the last versions of this software have been enriched by many functions which can be used to didactic purposes because they allow the link between the three-dimensional images of terrestrial globe with data, maps and information useful for the thematic and historical cartography and the physical and human geography

MacArthur-Bates Communicative Developmental Inventories (CDI): A Research Synthesis Evaluating Children at 2-36 months,

This synthesis will touch on the current parent-based assessments available while focusing specifically on the MacArthur-Bates Communicative Inventory English and Spanish versions. It will analyze studies that have used this test to predict language delays in infants from 2-36 months and look at its validity and effectiveness. It will use the PRISMA method to narrow search results. The PRISMA method is an evidence-based minimum set of items for reporting in systematic reviews and meta-analyses. Areas of concern were socioeconomic status, level of parent education, race, design, and effects of disability on CDI performance. 26 studies met the criteria to be used in this synthesis. The main aspect targeted was data on vocabulary production. Results showed just under half of the CDI scores were compromised by one or more of the variables analyzed. This study concluded results of the CDI should be reviewed with caution

Women in World War II

Women changed the course of history after World War II. Before World War II, women had briefly helped their country during the Great War but had returned home following the war. After the stock market crash in 1929, many people struggled to provide for their families which led women to take jobs again. When American joined World War II after Pearl Harbor, the large influx of men joining the army led companies in a lurch for employees. American propaganda strongly encouraged women to do their patriotic duty and to leave the household, only temporarily, to help their country. Women in America took to industry, military, and service employment to serve their country. This paper will explore the effect women\u27s employment had on American society after the war ended; it will show the general participation of women across the country and their fight to maintain that employment in the postwar society

A Formal Method for Assessing Architecture Model and Design Maturity Using Domain-independent Patterns

AbstractDesign patterns have been used as a formal or systematic means for extracting and patterning knowledge about good design choices, as well as capturing lessons learned associated with poor design choices (or so-called anti-patterns). Yet little attention is devoted specifically to pattern languages that are based on the fabric of architecture models – the conceptual data model – to capture reusable design knowledge and architecting best practices that can be applied in more than one domain at a high level of abstraction. This paper demonstrates a simple model-based method for identifying and patterning architecture design aspects that are domain-independent, and thus transferable and reusable in any system design with a comparable data model. The use of this method in formally documenting good and poor patterns in an abstract way is demonstrated by example. Discovered patterns such as those presented herein can be distributed, codified in a tool of choice, and sought out in actual architecture models of systems using automation. Since there may not be universal agreement on a common set of “good” and “poor” patterns, individual architects or organizations can use this method to state their particular practices as formal axioms, and structure them to assist in the assessment of model and design maturity against their own specific standards

Synthesis and Characterization of Inorganic Perovskites for Nanophotonics

In questa tesi di dottorato vengono affrontati diversi aspetti riguardanti la fisica delle perovskiti inorganiche alogenate. In particolare mi focalizzerò su: • Proprietà intrinseche del materiale come il disordine strutturale e dinamico, approfondito da uno studio della fotoluminescenza in un grande insieme di campioni CsPbBr3 che si differenziano per morfologia e protocollo di sintesi. Siccome il disordine pregiudica la forma spettrale della linea della fotoluminescenza e gioca un ruolo importante nelle proprietà di trasporto del supporto al bordo della banda, l’indagine presentata in questa tesi è di interesse per l’ampio insieme delle applicazioni optoelettroniche delle perovskiti alogenate. I risultati ottenuti durante l’attività di dottorato contribuiscono a chiarire le principali caratteristiche del disordine in questa classe di semiconduttori. • L’interazione tra i microcristalli di CsPbBr3 e il substrato/metasuperficie su cui sono depositati. Infatti, l’integrazione di perovskiti alogenate su metasuperfici e strutture fotoniche è una ricerca in fase iniziale e un’indagine approfondita è necessaria prima dell’implementazione di dispositivi fotonici innovativi. In particolare presenterò una serie di risultati sperimentali riguardanti effetti non lineari (comportamento superlineare e sublineare) nell’emissione radiativa di film CsPbBr3 depositati da spin-coating su un particolare tipo di metasuperficie realizzata da microrisonatori core-shell (T-Rex) assemblati in pattern esagonali su un substrato di silicio. I risultati sperimentali evidenziano la presenza di Amplified Spontaneous Emission (ASE) che, a seconda della struttura del campione, si presenta e non si presenta con un aumento superlineare dell’emissione. In particolare si distinguono due processi: l’amplificazione della luce da emettitori disposti in modo casuale e l’amplificazione da una distribuzione abbastanza ordinata di nanocristalli intorno a un risonatore. • CsPbBr3 ha caratteristiche ottimali come adsorbitore e catalizzatore nei pro- cessi di assorbimento degli inquinanti dalle acque reflue industriali. Nella parte finale del mio lavoro mostrerò i risultati preliminari riguardanti il rapido assorbimento del Blu di Metilene (MB), una sostanza tipicamente utilizzata nell’industria tessile, disciolta in soluzione acquosa quando le nanopolveri di CsPbBr3 (NPs) sono incapsulate all’interno di sferette di chitosano (CH-BB). Un aumento significativo della percentuale di adsorbimento di MB si ottiene in presenza delle nanopolveri di perovskite rispetto all’uso delle sferette di chitosano vuote.In this PhD thesis several aspects of the physics of halide inorganic perovskites are addressed. In particular I will focus on: • Intrinsic properties of the material such as the structural and dynamical disorder by a deep study of the photoluminescence in a large set of CsPbBr3 samples differing for morphology and synthesis protocol. Being the disorder affecting the spectral line shape of the photoluminescence, and playing a major role in the carrier transport properties at the band edge, the investigation here presented is of interest for the large set of optoelectronic applications of halide perovskites. The results obtained during the PhD activity contribute to clarify the main characteristics of disorder in this class of semiconductors. • The interaction between CsPbBr3 microcrystals and the substrate/metasurface where they are deposited. In fact, the integration of halide perovskites in metasurfaces and photonic structures is a research at the early stage and deep investigation is required before the implementation of innovative photonic devices. In particular I will present a set of experimental results concerning non-linear effects (superlinear and sublinear behavior) in the radiative emission of CsPbBr3 films deposited by spin-coating on a particular type of metasurface realized by core-shell microresonators (T-Rex) assembled in an esagonal pattern on a silicon substrate. The experimental results evidence the presence of Amplified Spontaneous Emission (ASE) which, depending on the sample structure, does or does not show up with a superlinear increase of the emission. In particular we distinguish between two processes: light amplification by randomly arranged emitters and amplification by a quite ordered distribution of nanocrystals around a resonator. • CsPbBr3 has optimal characteristics as adsorber and catalyst in the processes of absorption of pollutants from industrial waste water. In the final part of my work I will show preliminary results concerning the fast adsorption of Methylene Blue (MB), a substance typically used in the textile industry, dissolved in aqueous solution when CsPbBr3 nanopowders (NPs) are encapsulated inside chitosan bubbles (CH-BB). A significant increase of the adsorption percentage of MB is obtained in presence of the perovskite nanopowders respect to the use of empty chitosan bubbles

Female employment and first childbirth in Italy: what news?

AbstractIn the last decades, female participation in the labour market has been found to be increasingly associated with higher fertility levels in high-income countries—albeit to a lesser extent in countries characterised by poor welfare support to working mothers. Among the latter camp, Italy is an intriguing case study, which is marked by lower female labour force participation and fertility rates when compared to most other European countries. Recent macro-level evidence suggests that a reverse in the female employment/fertility relationship is gradually taking place in Italy, driven largely by the Northern regions. However, the evolution of the relationship between female employment and fertility has (to the best of my knowledge) never been addressed at the micro-level. Through the use of individual-level retrospective data, this study analyses the link between female employment and fertility, paying special attention to differences between Northern and Southern Italy, and its evolution over time. The results suggest that female employment began to be positively associated to fertility at the individual level, both in Northern and Southern Italy (although to slightly different extents), from 2010 onwards

Synthesis and Characterization of Multi-Component Enrichment Polymer Layers for Chemical Sensor Applications

This dissertation presents the building and study of a universal enrichment polymer layer system (EPLS). Thin polymer films have been utilized as enrichment layers for evanescent waveguide chemical sensors. The chemical nature of the polymer provides affinity which promotes the analyte to be absorbed. Having one highly sensitive polymer layer is suitable for a single target volatile organic compound (VOC). Here, the development of multi-layered and multi-component thin polymer films has been done to allow for more diverse affinity. Several parameters were identified to make the EPLSs suitable as enrichment layers for chemical sensor devices. The evanescent sensor devices used chalcogenide (ChG) glass, which is an infrared (IR) transparent material, and the principle of attenuated total reflection (ATR). This allowed the use of mid-IR spectroscopy to identify the absorbance of the absorbed VOCs in the polymer films. Changes of the absorbance due to influences of the EPLS were observed. These changes have not been reported before by researchers but can potentially be used to aid in fast and accurate identification of chemical compounds. The thicknesses of the total EPLS were kept to ≤ 30 nm so the evanescent wave would not be completely absorbed by the EPLS and absorbed VOC. Poly(glycidyl methacrylate) (PGMA) was a binding polymer for all EPLSs. As such, a single component PGMA film was tested to understand how the polymer influences the EPLS. Sensitivity to VOC concentration was conducted by mixture analysis and dilution by nitrogen gas in dynamic flow conditions. Comparison of each EPLS is done as well as to determine wavelengths of interest. Polymers were applied to ChG microdisk and amorphous silicon microring resonators and were found to increase sensitivity versus no polymer film at all. Two distinct layered enrichment nanoscale systems were synthesized and characterized - a six layer system and a five layer system. The polymer layered systems were characterized by atomic force microscopy, ellipsometry, and IR spectroscopy. Polymers utilized were PGMA, poly(acrylic acid), 60% epoxidized poly(butadiene), and poly(4-vinyl pyridine). In-situ ellipsometry was done to determine the swelling fraction of the film. In-situ attenuated total reflection (ATR) FT-IR spectroscopy was used to identify absorbance differences. Each EPLS proved to promote unique interactions which brought about differences in VOC absorbance in the mid-IR region