No presente trabalho descrevemos a preparação dos compostos de adição entre hexafluorofosfatos dos lantanídeos e a DMA. Foram obtidos os compostos de toda a série lantanídica, e através de análises elementares foi possível estabelecer que os mesmos apresentam as fórmulas gerais: Ln(PF6)3.7DMA (Ln= La-Ho) e Ln(PF=La-Ho) e Ln(PF6)3 .6DMA (Ln= Er-Lu, Y). Os produtos são cristalinos, não apresentam higroscopicidade e fundem numa faixa de temperatura entre 115 e 125°C; são solúveis em água, nitrometano, acetonitrila, metanol, nitrobenzeno e acetona. Além da análise química elementar, os compostos foram caracterizados por espectroscopia de absorção na região do infra-vermelho, medidas de condutância molar em nitrometano e acetonitrila, medidas de condutância equivalente de alguns compostos representativos, registros de difratogramas de raios-X (método do pó). Foram obtidos espectros na região do visível dos compostos de praseodímio, neodímio, hôlmio e érbio. Os espectros de absorção na região do infra-vermelho mostraram que a coordenação do ligante se dá através do oxigênio do grupo carbonila e que o ânion PF6- não deve estar coordenado ao íon lantanídeo tripositivo, mantendo sua simetria octaédrica. Os valores obtidos para as medidas de condutância molar evidenciaram que os compostos comportam-se como eletrólitos 1:3 em acetonitrila e nitrometano. As medidas de condutância equivalente de alguns compostos em várias concentrações em acetonitrila, confirmaram a existência deste tipo de eletrólito e indicaram um comportamento de eletrólito fraco neste solvente, sugerindo a existência de pares iônicos, em solugões concentradas. Os difratogramas de raios-X obtidos pelo método do pó, permitiram verificar a existência de três séries isomorfas distintas: a primeira constituída apenas do composto de lantânio, a segunda formada pelos compostos Ln(PF6)3.7DMA e a última com preendendo os compostos de composição Ln(PF6)3.6DMA. Os espectros de absorção eletrônica em acetonitrila e DMA são muito semelhantes, sugerindo que a simetria em torno do íon central é a mesma nesses solventes e diferentes da dos correspondentes hexafluorofosfatos dos lantanídeos em solução aquosa. Os espectros de soluções dos compostos de praseodímio, neodimio, hôlmio e érbio em acetonitrila, em diferentes concentrações não são substancialmente modificados, apresentando absortividades molares praticamente iguais para as diversas bandas observadas na região do visível, mesmo em soluções concentradas, indicando que quando há formação de pares iônicos, a proximidade do ânion não modifica o arranjo ao redor do cátion complexo, volumoso, contendo sete ou seis moléculas de DMA. / The preparation and characterization of adducts between lanthanide hexafluorophosphates and DMA are described. According to elemental analysis the compounds present two general compositions: Ln(PF6)3.7DMA (Ln= La-Ho) and Ln(PF6)3.6DMA (Ln= Er-Lu, Y). The compounds are crystalline, not hygroscopic and melt between 115-125°C. They are soluble in water, nitromethane, acetonitrile, methanol, nitrobenzene and acetone. The adducts were characterized by infrared spectra, molar conductance measurements in nitromethane and acetonitrile, equivalent conductance and X-ray powder patterns. The electronic spectra of the compounds of praseodimium, neodymium, holmium and erbium were also obtained in different conditions. According to infrared spectra, the ligand is coordinated to the lanthanides through the carbonyl oxygen and the PF6- ions are not coordinated, maintaining its octahedral symmetry. Conductance data of millimolar solutions in nitromethane and acetonitrile indicate a behaviour of 1:3 electrolytes. Equivalent conductances of some compounds in acetonitrile showed a behaviour of weak electrolytes, suggesting the existence of ion pairs in concentrated solutions. According to X-ray data three types of patterns were observed, corresponding to: a) the compound of lanthanum; b) compounds from cerium to holmium; c) compounds from erbium to lutetium and yttrium. The electronic spectra of the compounds in acetonitrile and in DMA are practically identical, suggesting that the environment around the lanthanide ion is maintained in these solvents, but are different of the corresponding lanthanide hexafluorophosphates in aqueous solution. The spectra of solutions of the compounds of praseodymium, neodymium, holmium and erbium at different concentrations in acetonitrile are not considerably modified presenting about the same molar absorptivities. This fact may be explained in terms that vicinity of the anion does not modify the environment around the bulky, tripositive lanthanide cation complex.

Os compostos de paládio vêm apresentado uma vasta linha de aplicação, tanto como catalisadores como precursores em reações de síntese orgânica. Dentre esses compostos, os ciclopaladatos, que são compostos cíclicos com uma ligação Pd-heteroátomo, permite a formação de novas estruturas cíclicas contendo algum heteroátomo, como nitrogênio, oxigênio ou enxofre. Neste trabalho foram sintetizadas aminas propargílicas capazes de se coordenar a sais de paládio, formando novos ciclopaladatos através da reação de cloropaladação. Esses compostos se encontram na forma de dímeros e podem apresentar-se como diferentes isômeros. Estudos espectroscópicos, tais como RMN de 1H, 13C e raios-X de monocristais foram realizados para a elucidação estrutural desses novos compostos. Além dos isômeros geométricos clássicos (cisóide e transóide) foram observados pela primeira vez a formação de atropoisômeros. Esses ciclopaladatos, contendo nitrogênio ligado ao paládio, foram testados frente a alenos diferentemente substituídos, mostrando que ocorre a inserção do aleno na ligação Pd-C e, seguido da depaladação, ocorre a formação de novos compostos heterocíclicos a seis membros. Alguns ciclopaladatos, quando em solução, podem apresentar certa instabilidade, ocorrendo a decomposição do ciclopaladato com a regeneração do alcino precursor do respectivo ciclopaladato. Assim, estudou-se a reação de decomposição de diferentes ciclopaladatos, chamada de retrocloropaladação, utilizando a técnica de RMN de 1H em diferentes intervalos de tempo. / Palladium compounds have application in different fields, such as catalysis or as precursors in organic synthesis reactions. Among these compounds, the palladacycles, which are cyclic compounds with a Pdheteroatom bond, allow the formation of new cyclic structures with at least one heteroatom such as nitrogen, oxygen or sulfur. In this work, propargylic amines were synthesized, which are capable to coordinate with palladium salts, affording new palladacycles by chloropalladation reactions. These compounds are dimers and can be present as different isomers. Spectroscopic analyses, such as 1H, 13C NMR and X-Ray of monocrystals were performed in order to elucidate the structure of these new compounds. Besides the classic geometric isomers (cisoid and transoid) for the first time the formation of atropisomers was observed. This palladacycles, with nitrogen bonded to palladium, were tested with different substituted allenes and showed the insertion of allene into the Pd-C bond. Subsequent depalladation resulted in the formation of new six member heterocycles. Some palladacycles are not stable in solution and undergo decomposition reactions yielding the alkyne precursors of palladacycle. We have studied these decomposition reactions of different palladacycles, called retro-chloropalladation, using 1H NMR analysis at different time intervals.

N-acylethanolamines (NAEs) including anandamide are lipid derivative molecules, which play vital roles in physiological and developmental processes in plants and animals and mediate stress responses. In mammals, NAEs are synthesized from hydrolysis of their precursor molecule N-acylphosphatidylethanolamine (NAPE) by NAPE-specific phospholipaseD (NAPE-PLD). All NAEs including anandamide (NAE20:4) are hydrolyzed by fatty acid amide hydrolase (FAAH) into free fatty acid and ethanolamine. To date, different NAEs including anandamide have been identified in Physcomitrella patens but its metabolic pathway remains undiscovered. It is hypothesized that NAE metabolic pathway in P. patens is conserved and is similar to that of other eukaryotic systems. To this extent, putative PpNAPE-PLD and PpFAAH were identified and cloned for heterologous expression and characterization. Expression of PpFAAH was further verified by Western blot analysis. Future studies will involve biochemical characterization of putative PpNAPE-PLD and PpFAAH, to establish the evolutionarily conserved nature of NAE functions in early land plants.

Tesis para optar al grado de Mag?ster en Gesti?n para la Globalizaci?n / Este trabajo presenta el desarrollo de un modelo de negocios para BeautifulLogs , un gestor de logs de aplicaciones (m?viles o web) desarrolladas para una infraestructura conocida como la nube (cloud computing). El desarrollo del modelo de negocio sigue una metodolog?a basada en los m?todos Lean Startup y Customer Development, enfocada en validar con clientes reales los supuestos de un modelo de negocios y reflejando los avances y el estado de dicho modelo en un Canvas de Modelo de Negocios. Cada validaci?n se conforma de un experimento con un resultado esperado en el caso en que el supuesto sea correcto. Durante el desarrollo de este proceso para el modelo de negocios de BeautifulLogs se encontr? un espacio en el mercado (ya existente) de este tipo de herramientas, nicho basado en necesidades avanzadas que no est? siendo cubierto por las soluciones actuales. Entre estas necesidades se cuenta la necesidad de almacenar la informaci?n por m?s tiempo que las soluciones actuales (que promedian dos semanas), incrementar la potencia de las funciones de b?squeda y agregar elementos de m?tricas y anal?ticas inferidas a partir de los mismos logs. En base a estas necesidades se establecieron propuestas de valor empaquetadas en planes con un precio validado por los propios usuarios encuestados. El modelo de negocio sigue el esquema SaaS: Software como servicio por el cual el cliente paga una mensualidad (o anualidad) a cambio de su uso. Si bien los costos variables para poder ofrecer las soluciones ofrecidas en los planes resultaron ser relativamente elevados (para el mercado SaaS), existe un saludable margen entre el ingreso variable promedio por usuario (USD 143,33) y el costo variable por usuario proyectado (USD 68,13). Por otra parte, los costos de adquisici?n, la conversi?n de usuarios y el crecimiento neto de usuarios se presentan como las variables claves que determinar?n la rentabilidad del negocio, que en un escenario moderado proyecta ventas por casi un mill?n de d?lares en el octavo trimestre de vida del negocio. En su forma actual, el modelo requiere una inversi?n inicial de USD 350.000 a ocupar principalmente en desarrollo de la plataforma, as? como tambi?n en capital de trabajo. La recomendaci?n a seguir es levantar una fracci?n de esa inversi?n para efectuar una validaci?n de clientes mediante un producto m?nimo viable, que permita bajar el riesgo presentado por la variaci?n de las variables claves mencionadas anteriormente.

El turismo rosa est�� formado por el segmento l��sbico gay, el cual es un grupo con altos / beneficios econ��micos para el turismo, ya que est�� acostumbrado a darse lujos y viajar / constantemente. La oferta tur��stica para el segmento l��sbico gay es poca, por lo que se / desean saber las expectativas que tiene el segmento sobre lugares como hoteles, / restaurantes, centros nocturnos, entre otros. A partir de la investigaci��n, se pudo conocer los or��genes del segmento, el / crecimiento del turismo l��sbico gay, al igual que la amplitud de la oferta existente. Saber la / importancia de las expectativas del consumidor para proveer una oferta interesante e / innovadora para dicho segmento. Se menciona el impacto que tienen las experiencias en / los consumidores, y en consecuencia, su comportamiento. Fue importante saber acerca de / la discriminaci��n y la aceptaci��n del segmento l��sbico gay. A trav��s de entrevistas profundas, se pudo conocer las caracter��sticas que busca el / segmento l��sbico gay en la oferta tur��stica. / (cont.) Se muestran las caracter��sticas que buscan para / lugares como hoteles y restaurantes, al igual que sus preferencias y gustos para algunos / establecimientos. Se exponen las incomodidades y molestias en varios lugares visitados. Y por ��ltimo, se mencionan los destinos gay friendly m��s importantes y frecuentados a / nivel mundial..

Reproduction de : Thèse de doctorat : Physique nucléaire : Lyon 1 : 2002. / Titre provenant de l'écran-titre. 50 réf. bibliogr.

Thesis (Ph. D.)--University of Chicago, Department of Neurobiology, Pharmacology, and Physiology, 2001. / Includes bibliographical references. Also available on the Internet.

[Alpha]-Amino ketones can serve as important intermediates for the synthesis of biologically active molecules, and making these precursors in a practical manner has long been a challenge for organic chemists. The oxygen-carbon-carbon-nitrogen (O-C-C-N) sequence is common in natural and synthetic compounds of biological interest, due in part to their relatedness to peptides. Because of the many known carbonyl transformations, [alpha]-amino ketones have the potential to form various amine derivatives. Herein we present our research endeavors which led to several novel methods of forming this type of functionality. These endeavors culminated with the development of a two-step hydrazidation/N-N bond cleavage technique for forming [alpha]-amino ketals--which can be readily hydrolyzed to [alpha]-amino ketones. / text

The loop bandwidth of a fractional-N PLL is a desirable parameter for many applications. A wide bandwidth allows a significant attenuation of phase noise arising from the VCO. A good VCO typically requires a high Q LC oscillator. It is difficult to build an on-chip inductor with a high Q factor. In addition, a good VCO also requires a lot of power. Both these design challenges are relaxed with a wide loop bandwidth PLL. However a wide loop bandwidth reduces the effective oversampling ratio (OSR) between the update rate and loop bandwidth and makes quantization noise from the ΔΣ modulator a much bigger noise contributor. A wide band loop also makes the noise and linearity performance of the phase detector more significant. The key to successful implementation of a wideband fractional-N synthesizer is in managing jitter and spurious performance. In this dissertation we present a new PLL architecture for bandwidth extension or phase noise reduction. By using clock squaring buffers with built-in offsets, multiple clock edges are extracted from a single cycle of a sinusoidal reference and used for phase updates, effectively forming a reference frequency multiplier. A higher update rate enables a higher OSR which allows for better quantization noise shaping and makes a wideband fractional-N PLL possible. However since the proposed reference multiplier utilizes the magnitude information from a sinusoidal reference to obtain phases, the derived new edges tend to cluster around the zero-crossings and form an irregular clock. This presents a challenge in lock acquisition. We have demonstrated for the first time that an irregular clock can be used to lock a PLL. The irregularity of the reference clock is taken into account in the divider by adding a cyclic divide pattern along with the ΔΣ control bits, this forces the loop to locally match the incoming patterns and achieve lock. Theoretically this new architecture allows for a 6x increase in loop BW or a 24dB improvement in phase noise. One potential issue associated with the proposed approach is the degraded spurious performance due to PVT variations, which lead to unintended mismatches between the irregular period and the divider pattern. A calibration scheme was invented to overcome this issue. In simulation, the calibration scheme was shown to lower the spurs down to inherent spurs level, of which the total energy is much less than the integrated phase noise. A test chip for proof of concept is presented and measurements are carefully analyzed. / text

N-alkenyl aziridines are a unique class of molecules that do not behave as typical enamines as a result of the inability of the nitrogen atom lone-pair of electrons to delocalize. The attenuated nucleophilicity of these enamines presents opportunities for selective functionalization and reactivity not available to classical enamines. An operationally simple and mild copper-mediated coupling has been developed that facilitates the preparation of a broad range of N-alkenyl aziridines not available through existing methods. The preparation and reactivity of highly functionalized N-alkenyl aziridines are reported. Also reported is the application of the chemoselective amine/aldehyde/alkyne (A3) multicomponent coupling involving amphoteric aziridine aldehydes as the aldehyde component. This coupling allows access to propargyl amines with pendent aziridine functionality.