Progress towards a concise total synthesis of subincanadine E is reported. This natural product was first isolated from the Picralima nitida cell suspension culture line in 1982 under the name pericine and later in 2002 from Aspidosperma subincanum as subincanadine E. It is the most potent compound of its class with in vitro cytotoxicity against both murine lymphoma L1210 and human epidermoid carcinoma KB cells (LD50, 0.3 ug/mL and 4.4 ug/mL, respectively) and was found to be six times more potent than codeine as an opiate agonist in a 3H-naloxone binding study (IC50, 0.6 umol/L). The first-generation synthesis produced an undesired internal olefin that, upon attempted isomerization, catalyzed an unusual intermolecular Diels-Alder reaction. A revised second-generation synthesis employed (±)-harmicine and showcased an intramolecular Pd-catalyzed cross-coupling reaction that furnished an unanticipated 5-membered ring instead of the predicted 6-membered ring via methylene linker activation. Further studies utilizing an amide intermediate and organocuprate chemistry produced no desired carbon-carbon bond formation. A third-generation synthesis was carried out from enantiopure (S)-carvone. This route explored regioselective oxime formation and protecting group manipulations for a subsequent Beckmann rearrangement, which provided the first access to 5-amino derivatives of carvone. An intramolecular Pd-catalyzed cross-coupling reaction was performed to construct the aza-bicycle prior to indole installation. Contingent on its success, indole introduction and a double alkylation would provide an akuammicine-like scaffold that can ring-open upon hydride exposure to afford (15S)-subincanadine E in 16 overall steps. This work accomplished 10 steps toward the first total asymmetric synthesis of (15S)-subincanadine E.

Empirical studies have shown that algal- and detrital-based food web components are coupled in many pelagic systems as algal carbon enhances bacterioplankton production and growth efficiencies. Such phyto-bacterioplankton coupling impacts carbon flow through plankton food webs, yet the extent of coupling is poorly understood in systems receiving large amounts of allochthonous carbon. To investigate this issue, bacterioplankton abundance (BA) and community composition were compared to chlorophyll a concentrations and phytoplankton production in the tidal-freshwater James River (VA). BA averaged 107 cells mL-1 and was significantly related to chlorophyll a, phytoplankton production, and DOC concentrations. Analysis of DOC quality using fluorescence spectroscopy revealed that the fulvic DOC fraction was dominated by allochthonous compounds. However, estimates of DOC C:N and DOC turnover rates indicated that DOC was more labile in the lower part of the study reach where BA was highest. T-RFLP analysis of 16s rDNA showed that bacterioplankton community composition significantly varied between the upper and lower portions of the sampling reach. These findings suggest that coupling of food web components is an important pathway affecting carbon cycling within the tidal-fresh water James River.

Name of the thesis Effect of nitric oxide on cerebral blood flow during neuronal activity Aim of the thesis The aim of this thesis is to determine whether the application of 7-nitroindazole, relatively specific inhibitor of neuronal nitric oxide synthase, affects the baseline blood pressure. Furthermore, to determine whether the application of the substance affects the baseline cerebral blood flow and whether it influences blood flow in brain during transcallosal stimulation with increasing frequency. Research method The research took place at the premises of the Institute of Physiology, Academy of Sciences of the Czech Republic. Experiments were carried out on laboratory albino Wistar rats. The group contained both experimental and control sample. General anesthesia was performed to rats, stimulating and sensing electrodes were implanted in epidural area of sensorimotor cortex and Laser Doppler flow probe was implanted into the contralateral hemisphere. A plastic catheter was applied in the carotid artery for measuring systemic blood pressure. In the first part of the experiment, we tested the effects of 7-nitroindazole on the systemic blood pressure. In the second part of the experiment, we investigated the effects of 7-nitroindazole on baseline cerebral blood flow. The third part of the...

In the thesis we study a method for determining resonance energies - gen- eralization of the method of analytical continuation in the coupling constant, which is based on continuation of the coupling constant λ as a function of the momentum k. A formula for λ(k) is derived for spherically symmetric potential consisting of finite number of δ-functions and its Taylor series is studied. Taylor series of λ(k) and its asymptotic behavior is studied for sep- arable potential. Proper choice of added potential parameters is studied on examples. A method for determining λ(k) poles is described for spherically symmetric potential with added δ-function. It is tested whether the knowl- edge of λ(k) poles can be useful to improve the accuracy of the determination of the resonance parameters of the original potential.

This thesis studies the quantum reflection factor of the sinh-Gordon model under boundary conditions consistent with integrability. First, we review the affine Toda field theory in Chapter One. In particular, the classical and quantum integrability of the theory are reviewed on the whole line and on the half-line as well, that is, in the presence of a boundary. We next consider the sinh-Gordon model which is restricted to a half-line by boundary conditions maintaining integrability in Chapter Two. A perturbative calculation of the reflection factor is given to one loop order in the bulk coupling and to first order in the difference of the two parameters introduced at the boundary. The result provides a further verification of Ghoshal's formula. The calculation is consistent with a conjecture for the general dependence of the reflection factor on the boundary parameters and the bulk coupling. In Chapter Three, quantum corrections to the classical reflection factor of the sinh-Gordon model are studied up to second order in the difference of boundary data and to one loop order in the bulk coupling. Chapter Four deals with the quantum reflection factor for the sinh-Gordon model with general boundary conditions. The model is studied under boundary conditions which are compatible with integrability and in the framework of the conventional perturbation theory generalised to the affine Toda field theory. It is found that the general form of a subset of the related quantum corrections are hypergeometric functions. Finally, we sum up this thesis in Chapter Five along with some conclusions and suggestions for further future studies.

The Hypothalamic-Pituitary-Adrenal (HPA) and –Gonadal (HPG) axes have been considered mutually inhibitory; however, emerging evidence supports the proposition that this might not necessarily be the case. This idea is termed “coupling,” in which the HPA-HPG axis are mutually activated or deactivated. Coupling is examined across three data sets with different time-courses of stress exposure, and results demonstrate HPA-HPG co-activation occurs. Furthermore, stress exposure influences this relationship. The discussion shows how it is physiologically possible to have positive coupling or co-activation between these axes according to complex regulatory feedback systems and overlapping neural structures. Findings are interpreted developmentally, because adolescence may be a critical time for this co-activation to occur. Finally, the discussion emphasizes an individual difference perspective because each individual differs in the duration and type of stress they experience, and these exerted individualized effects on HPA-HPG coupling.

Thesis advisor: James P. Morken / The first highly enantioselective diboration of unfunctionalized terminal alkenes has been developed using a platinum-phosphonite complex. This transformation produces versatile 1,2-bis(boronate)esters that can manipulated chemoselectively to generate a pletheroa of enantioenriched structural motifs. When combined with an appropriate palladium catalyst, the diboration product undergoes an efficient alkyl boron cross-coupling with aryl and vinyl electrophiles producing a wide range of enantioenriched homobenzylic and homoallylic boronates. Alternatively, when the 1,2-bis(boronate)ester diboration product contains an adjacent Z-olefin (derived from diboration of cis-1,3-dienes), allylation to aldehydes can be achieved delivering the syndiastereomer of product exclusively with excellent chirality transfer. Notably, the products obtained from the two described reactions contain an additional boronate moiety, which can be further functionalized through known carbon-boron bond transformations. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The objective of this thesis is to present a theoretical and experimental investigation of the dynamics of micro and nano-electromechanical systems electrothermally tuned and electrostatically actuated, and explore their potential for practical applications. The first part of the dissertation presents the tuning of the frequency of clamped-clamped micro and nano-resonators, straight and curved. These resonators are electrothermally or electrostatically tuned. The effect of geometric parameters on the frequency variation is investigated experimentally and theoretically using a reduced order model based on the Euler-Bernoulli beam theory. High tunability is demonstrated for micro and nano beams, straight and initially curved. The second part discusses the dynamical behavior of a curved (arch) beam electrothermally tuned and electrostatically actuated. We show that the first resonance frequency increases up to twice its fundamental value and the third resonance frequency decreases until getting very close to the first resonance frequency triggering the veering phenomenon. We study experimentally and analytic ally, using the Galerkin procedure, the dynamic behavior of the arch beam. Next, upon changing the electrothermal voltage, the second symmetric natural frequency of the arch is adjusted to near twice, three times, and four times the fundamental natural frequency. This gives rise to a potential two-to-one, three-to-one, and four-to-one autoparametric resonances between the two modes. These resonances are demonstrated experimentally and theoretically. The third part of the dissertation is concerned with the incorporation of the electrothermally tuned and electrostatically actuated microresonators into potential applications: filtering and sensing. First, we experimentally prove an exploitation of the nonlinear softening, hardening, and veering phenomena of an arch beam, to demonstrate a flat, wide, and tunable bandwidth and center frequency by controlling the electrothermal actuation voltage. Second, a pressure sensor based on the convective cooling of the air surrounding an electrothermally heated resonant bridge is demonstrated experimentally. The concept is demonstrated using both straight and arch microbeam resonators driven and sensed electrostatically. The change in the surrounding pressure is shown to be accurately tracked by monitoring the change in the resonance frequency of the structure.

Les pérovskites hybrides organiques-inorganiques ont attiré l'attention en raison de leurs applications potentielles dans des dispositifs optiques et plus récemment dans les dispositifs photovoltaïques. L'arrangement cristallin des pérovskites forme une structure en multi-puits quantiques dans laquelle les états excitoniques présentent une grande force d'oscillateur et une énergie de liaison importante, ce qui rend la réalisation de microcavités dans le régime de couplage fort possible à la température ambiante. Etant un matériau relativement nouveau, les pérovskites ont encore beaucoup de comportements qui ne sont pas bien compris et beaucoup de travail de recherche est nécessaire. Ce manuscrit est divisé en deux parties. Dans la première partie, la dynamique des excitons sur une pérovskite particulière (C6H5-C2H4-NH3)2PbI4 (PEPI) est étudiée à température ambiante par mesure de type pompe-sonde sous faible et fort régime d'excitation. Sous forte densité d'excitation, un processus de recombinaison Auger des excitons est présent. Une relaxation intrabande ultra-rapide a été observée. La deuxième partie du manuscrit est consacrée à l'étude de la microphotoluminescence à temperature ambiante de microcavités à base de PEPI à haut facteur de qualité. Des nouvelles pérovskites avec des propriétés optimisées (propriétés optiques d'émission, rugosité de surface et photostabilité) ont également été synthétisées. / The reason for choosing this thesis comes from the fact that in the near future,I would like to gain more knowledge and experience in scientific research and especially in the study of non linear effects in optical microcavities where new opportunities are opened and high efficient light sources could be exploited.In last ten years, an increasing number of studies are dedicated on hybrid organic-inorganic materials, due to the possibility of combining the properties both of inorganic(high mobility, electrical pumping, band engineering ) and of organic materials (low cost technology, high luminescence quantum yield at room temperature).In this context , organic-inorganic perovskites having a chemical formula (R-NH3)2MX4 where M is a metal, X halogen and R an organic chains presents a natural hybrid system . When deposited by spin coating, the molecules self-organize to form a multiple quantum wells structure. Because of the strong binding energy, optical features can be seen at room temperature. Moreover, such pervoskite presents great flexibility in their optical properties such that the spectral position of the excitonic transitions can be tailored by substituting different halides X, and the photoluminescence efficiency can be tailored by changing the organic part R. This kind of perovskites has been studied both for fundamental studies and for applications in optoelectronics. In order to increase the coupling between light and matter (exciton), perovskite has been inserted in planar microcavity and strong coupling regime has been achieved at room temperature. The strong coupling of light with exciton give rise to polariton quasi-particles, which have new properties not seen in either photons or excitons. In order to go further and have better study in stimulated scattering of polaritons in these microcavities ,a better understanding of the electronic structure as well as the excitonic interactions in these quantum wells are necessary due to the lack of information on the dynamic and on the carrier interaction of these structures. In order to study the hybrid polaritons, it will be first necessary to improve the knowledge about the relaxation in the perovskite layers. So, ultrafast pump-probe experiments will be performed on hybrid microcavities, and also on perovskite layers.

Thesis advisor: James P. Morken / (+)-Discodermolide is a marine natural product and is one of the most potent microtubule stabilizers in human cell lines. Because of its unique linear structure and important properties, a number of total syntheses of (+)-discodermolide and its derivatives have been reported. Herein, an efficient, highly convergent, and stereocontrolled total synthesis is presented (Chapter 2). The synthesis relied on the development of three catalytic and stereoselective processes: platinum-catalyzed asymmetric diene diboration, nickel-catalyzed diastereoselective hydroboration of chiral dienes (Chapter 1), and nickel-catalyzed borylative diene-aldehyde coupling (see Chapter 4). Combination of these reactions allows preparation of the target in a short sequence. Moreover, the development of rhodium-catalyzed asymmetric hydroformylation (Chapter 3) makes this approach the first Roche ester free (+)-discodermolide synthesis. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.