Stereoselective synthesis of substituted hexahydro-3a,4a-diazacyclopentaphenanthren-4-ones and aminoferrocenes

This thesis explored the development of several methodologies for the stereoselective construction of ligand frameworks and some of their applications. The first segment concerns the application of an enantioselective lithiation at an Sp3_ hybridized position adjacent to nitrogen by means of the widely used and typically highly effective enantioselective lithiation with ( -)-sparteine. This investigation was intended to develop a method to install chirality into a system that would be converted into a family of diaminoylidenes for use as phosphine mimics in transition metal catalysis or as nucleophilic reagents. Molecular modeling of the system revealed some key interactions between the substrate and (-)-sparteine that provided general insight into the diamine's mode of action and should lend some predictive value to its future applications. The second portion focuses on the development of methods to access 1,2- disubstituted aminoferrocenes, an underexplored class of metallocenes possessing planar chirality. Two routes were examined involving a diastereoselective and an enantioselective pathway, where the latter method made use of the first BF3-mediated lithiation-substitution to install planar chirality. Key derivatives such as 1,2- aminophosphines, made readily accessible by the new route, were evaluated as ligands for Pd(II), Pt(II) and Ir(I). These complexes show activity in a number of transformations with both achiral and prochiral substrates. Optimization experiments were conducted to prepare enantiomerically enriched 2-substituted-I-aminoferrocenes by direct asymmetric lithiation of BF3-coordinated tertiary aminoferrocenes. A predictive computational model describing the transition state of this reaction was developed in collaboration with Professor Travis Dudding's group (Department of Chemistry, Brock University). The predicted stereochemistry of the process was confirmed by single-crystal X-ray analysis of a 2-phosphino-l-dimethylaminoferrocene derivative. Enantiomerically pure samples of the aminophosphine ligands derived from this new process have given promising preliminary results in the enantioselective hydrogenation of prochiral alkenes and warrant further stUdy in metal-mediated catalysis.

Diastereoselective Lithiation-Substitution of N-Silyl-Protected-(S)-Tetrahydro-1H-pyrrolo[1,2-c]imidazole-3(2H)-ones and Applications of Their Derivatives

This thesis describes a method involving the preparation of an L-proline-derived imidazolone protected with an N-triethylsilyl group that undergoes diastereoselective lithiation followed by electrophile quench to give C5-substituted products with syn stereochemistry. The N-silylated derivatives may be more easily N-deprotected as compared to previous N-t-Bu analogues to give secondary ureas. These may serve as precursors to N-phenyl chiral bicyclic guanidines or as NHC precursors for synthesis of corresponding complexes.

Diastereoselective Lithiation-Substitution of N-Silyl-Protected-(S)-Tetrahydro-1H-pyrrolo[1,2-c]imidazole-3(2H)-ones and Applications of Their Derivatives

This thesis describes a method involving the preparation of an L-proline-derived imidazolone protected with an N-triethylsilyl group that undergoes diastereoselective lithiation followed by electrophile quench to give C5-substituted products with syn stereochemistry. The N-silylated derivatives may be more easily N-deprotected as compared to previous N-t-Bu analogues to give secondary ureas. These may serve as precursors to N-phenyl chiral bicyclic guanidines or as NHC precursors for synthesis of corresponding complexes.

Charter and Context: The Facts for Which We Need Evidence and The Mysterious Other Ones

Cet article a précédemment été publié par la Supreme Court Law Review (Second Series).

Synthesis, Antifungal and Antitumor Activity of Novel (Z)-5-Hetarylmethylidene-1,3-thiazol-4-ones and (Z)-5-Ethylidene-1,3-thiazol-4-ones

New hetaryl- and alkylidenerhodanine derivatives 3a-d, 3e, and 4a-d were prepared from heterocyclic aldehydes 1a-d or acetaldehyde 1e. The treatment of several rhodanine derivatives 3a-d and 3e with piperidine or morpholine in THF under reflux, afforded (Z)-5-(hetarylmethylidene)-2-(piperidin-1-yl) thiazol-4(5H)-ones and 2-morpholinothiazol-4(5H)-ones 5a-d, 6a-d, and (Z)-5-ethylidene-2-morpholinothiazol-4(5H)-one (5e), respectively, in good yields. Structures of all compounds were determined by IR, 1D and 2D NMR and mass spectrometry. Several of these compounds were screened by the U.S. National Cancer Institute (NCI) to assess their antitumor activity against 60 different human tumor cell lines. Compound 3c showed high activity against HOP-92 (Non-Small Cell Lung Cancer), which was the most sensitive cell line, with GI(50) = 0.62 mu M and LC50 > 100 mu M from the in vitro assays. In vitro antifungal activity of these compounds was also determined against 10 fungal strains. Compound 3e showed activity against all fungal strains tested, but showed high activity against Saccharomyces cerevisiae (MIC 3.9 mu g/mL).

Objective quality of life, optimism, and social-juridical variables, as predictive ones of the subjective quality of life in disarmed Colombian persons

The goal of this research was to identify predic- tive psychosocial factors of the subjective quality of life in a group of 60 people, with ages between 19 and 57, from both sexes, included in the program of demobilization and social inclusion of the Pro- grama de la Alta Consejería para la Reintegración Social y Económica de Personas y Grupos Alzados en Armas en Colombia. this research was a predic- tive correlational descriptive study. the Question- naire of optimism/Pessimism was used to assess the optimist or pessimist trend, and, for assess the quality of life, these strategies were combined: a home visit to value the objective quality of life, the Analogous scale of subjective Quality of Life to value satisfaction and well-being, and a general format to collect socio-demographic and juridical information. Results show that some variables as perceived health, optimism, educational level, re- ligious believes, objective quality of life, type of demobilization and years spent in the armed group operating outside the law, are associated to better levels of perceived quality of life. The findings and limitations of the study are discussed.  

La Lij a les ones hertzianes. 'Lij a las ondas hertzianas'.

Resumen en catalán

Sons, ones, veus i partitures. 'Sonidos, ondas, voces y partituras'.

Crédito variable para enseñanza secundaria (12-16) para ciencias experimentales-música. Con este crédito se pretende hacer una aportación técnica a la enseñanza musical: la intervención del ordenador y del osciloscopio para establecer la interelación entre los sonidos, las ondas, las voces y las partituras. Los hechos, conceptos y sistemas que se trabajan son: el movimiento ondulatorio, el sonido como fenómeno físico y biológico, la producción de sonidos, la música y la acústica. Se incluyen cuestionarios, ejercicios y problemas, visita a una parte del Museo de la Ciencia, construcción y lectura de gráficos, uso de programas de ordenador (entre ellos framework), uso de un osciloscopio. El crédito incluye objetivos, valores, actividades y normas, actividades de aprendizaje, actividades de evaluación, orientaciones didácticas para el/la profesor/a, bibliografía y un anexo de los ficheros incluídos en el disquet que acompaña el crédito.

Ones i vibracions. 'Ondas y vibraciones'.

Crédito común para el área de Física del Bachillerato Científico e Industrial. Se centra en el tema de las ondas mecánicas y la luz. Tiene como característica que no se usan funciones trigonométricas y se utiliza un método cualitativo en el análisis de las funciones. Se insiste en los fenómenos de interferencia y difracción. Además del diseño del crédito, se incluye todo el material de soporte de las actividades de aprendizaje propuestas. Éstas tienen una presencia constante y exhaustiva y están muy ligadas a las exposiciones teóricas y a las aplicaciones numéricas.

In situ (enciclopèdia audiovisual de les ciències i les tècniques) : ones i vibracions. 'In situ (enciclopedia audiovisual de las ciencias y las técnicas) : ondas y vibraciones'.

Este vídeo forma parte de la Enciclopedia Audiovisual de las Ciencias y las Técnicas, y se estructura en capítulos de cuatro minutos. Cada capítulo expone el estudio de un objeto o fenómeno científico y propone: recordatorios, definiciones, exploraciones para entender mejor un funcionamiento, animaciones para representar fenómenos complejos, descubrimientos y aplicaciones y puntos que remiten a otros capítulos de la enciclopedia directamente relacionados con el tema que se trata. Los capítulos incluidos en este volumen son: la cámara fotográfica; la luz de colores; la propagación de la luz; el láser; las ondas electromagnéticas; los rayos X y los rayos gamma; el sónar; el radar; las ondas sonoras; la guitarra; el micrófono; el altavoz; la modulación y la frecuencia, y, las antenas.

Anàlisi del camp d'ones internes en sistemes limnològics petits. Simulacions amb el POM

Aquí hem aplicat el Princeton Ocean Model als embassaments de Sau i Boadella, situats a Catalunya, Espanya. Les simulacions s'han realitzat a l'estació d'estiu, quan la columna d'aigua està estratificada de forma contínua, i sota un règim de brisa amb velocitats de fins a 4 m/s. Basant-nos en aquestes simulacions hem analitzat el camp d'ones internes i comparat els resultats numèrics amb dades experimentals disponibles. El model reprodueix adequadament tots els modes observats en l'espectre de la velocitat i temperatura mesurades i ajuda a identificar els diferents modes. Les simulacions mostren la importància dels modes rotacionals en el camp d'ones internes dels embassaments estratificats. En el període estudiat, el radi de Rossby per l'embassament de Sau és de l'ordre de 100 m, que és varies vegades més petit que la amplitud de l'àrea lacustre de l'embassament, i el número de Rossby és de l'ordre de 0.1, corroborant la importancia de l'efecte de Coriolis.

Incubation success of released hand-reared pheasants Phasianus colchicus compared with wild ones

We investigated previously observed but unexplained differences in incubation success between wild and hand-reared common pheasants Phasianus colchicus. Hand-reared birds are widely released in late summer in Britain and elsewhere to supplement wild stocks for shooting purposes. We radio-tracked 53 wild and 35 previously released reared female pheasants occupying simultaneously the same areas on a game-keepered estate in eastern England between February and mid July 1999 and 2000. Predation of adult birds was comparatively low for both wild and reared birds, and overall survival did not differ between years or between groups. However, of 52 nests incubated by wild females 49% hatched, whereas of 30 nests incubated by reared pheasants only 22% hatched. Mayfield estimates of daily nest survival probability thus differed significantly between groups. However, predation of eggs was similar for both wild and reared birds. Instead the observed difference in hatch rates was due to nest abandonment, with more reared females (41%) deserting apparently unmolested nest sites than wild females (6%).

Synthesis and photoreactivity of aryl substituted 4,5-dithienyl[1,3]dithiol-2-ones

UV irradiation of hitherto unknown 4,5-bis-benzol[b]thiophen-3-yl-[1,3]dithiol-2-one gave 3-(3-benzo[b]thienyl)-thieno[3,4-c]benzo[ e][1,2]dithine by loss of carbon monoxide and rearrangement, whereas 4,5-bis-(2-bromo-phenyl)-[1,3]dithiol-2-one gave a polymeric material containing S-S bridges. The Structures of both photoproducts were demonstrated on the basis of chemical behaviour and/or X-ray diffraction. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of chiral 3,4,5,6-tetrahydro-1,4-thiazin-2-ones (thiamorpholin-2-ones)-novel heterocycles possessing enhanced carbonyl electrophilicity over their oxygen counterparts

We report herein the first synthesis of chiral derivatives possessing the 1,4-thiazinone core. As predicted, the thiolactone is more susceptible to nucleophilic attack than the equivalent lactone system.

One’s own soundtrack: affective music synthesis

Computer music usually sounds mechanical; hence, if musicality and music expression of virtual actors could be enhanced according to the user’s mood, the quality of experience would be amplified. We present a solution that is based on improvisation using cognitive models, case based reasoning (CBR) and fuzzy values acting on close-to-affect-target musical notes as retrieved from CBR per context. It modifies music pieces according to the interpretation of the user’s emotive state as computed by the emotive input acquisition componential of the CALLAS framework. The CALLAS framework incorporates the Pleasure-Arousal-Dominance (PAD) model that reflects emotive state of the user and represents the criteria for the music affectivisation process. Using combinations of positive and negative states for affective dynamics, the octants of temperament space as specified by this model are stored as base reference emotive states in the case repository, each case including a configurable mapping of affectivisation parameters. Suitable previous cases are selected and retrieved by the CBR subsystem to compute solutions for new cases, affect values from which control the music synthesis process allowing for a level of interactivity that makes way for an interesting environment to experiment and learn about expression in music.