Relative basicities of free base porphyrins : understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond.

Angular momentum of S0 galaxies

The aim of this thesis is to study the angular momentum of a sample of S0 galaxies. In the quest to understand whether the formation of S0 galaxies is more closely linked to that of ellipticals or that of spirals, our goal is to compare the amount of their specific angular momentum as a function of stellar mass with respect to spirals. Through kinematic comparison between these different classes of galaxies we aim to understand if a scenario of passive evolution, in which the galaxy’s gas is consumed and the star formation is quenched, can be considered as plausible mechanism to explain the transformation from spirals to S0s. In order to derive the structural and photometric parameters of galaxy sub-components we performed a bulge-disc decomposition of optical images using GALFIT. The stellar kinematic of the galaxies was measured using integral field spectroscopic data from CALIFA survey. The development of new original software, based on a Monte Carlo Markov Chain algorithm, allowed us to obtain the values of the line of sight velocity and velocity dispersion of disc and bulge components. The result that we obtained is that S0 discs have a distribution of stellar specific angular momentum that is in full agreement with that of spiral discs, so the mechanism of simple fading can be considered as one of the most important for transformation from spirals to S0s.

Suppression of nonlinear distortion in few-mode fibres using strong mode coupling

In this paper, we investigate the impact of linear mode coupling on the efficiency of intermodal four-wave mixing and on the group delay statistics in few-mode fibres. The investigation will include not only the weak or strong linear coupling regimes, but also the transition region between them, the intermediate coupling regime. This analysis will allow to assess the level of coupling strength require to suppress the nonlinear distortion in a few-mode fibre below the level of distortion for single-mode propagation without mode coupling.

Nonlinear distortion in mode delay compensated few-mode fibre spans with intermediate coupling

Nonlinear distortion in delay-compensated spans for intermediate coupling is studied for the first time. Coupling strengths under -30dB/100m allow distortion reduction using shorter compensation lengths and higher delays. For higher coupling strengths no significant penalty results from shorter compensation lengths.

A Decade-Bandwidth Low-Noise Mixer RFIC with a Distortion-Canceling Output Amplifier

This paper presents a 1-10 GHz low-noise downconvert mixer RFIC suitable for wideband receivers. A switched transconductor mixing core is adopted to reduce noise at high frequencies. By adding a series inductor to the RF transconductor, a flat 4-5 dB noise figure (NF) and a high gain of 26.5 dB can be achieved over a broad bandwidth out to 10 GHz. A CMOS output amplifier is also integrated on-chip, employing derivative superposition (DS) for high linearity and an OIP3 of 16.5 dBm. The circuit consumes less than 20 mW of dc power and occupies an active chip area of less than 0.2 mm2.

React vs Angular : Slaget om användarupplevelsen

Lately, various programming frameworks has been developed for developing web applications. These frameworks focus on increasing the user experience by performance improvements such as faster render times and response times. One of these frameworks are React, which has introduced a completely new architectural pattern for both managing the state and data flow of an application. React also offers support for native application development and makes server-side rendering possible. Something that is difficult to accomplish with an application developed with Angular 1.5, which is used by the company Dewire today. The aim of this thesis was to compare React with an existing Angular project, in order to determine whether React could be a potential replacement for Angular. To gain knowledge about the subject, a theoretical study of web- based sources has been made. While the practical part has been to rebuild a web application with React together with the architecture Flux, which is based on a view from the Angular project. The implementation process was repeated until the view was completed and a desired data flow, as in the Angular application, was reached. The resulting React application was later compared with the Angular application developed by the company, where the outcome of the comparison showed that the React performed better than Angular in all tests. In conclusion, due to the timeframe of the project, only the most important parts of the Angular project were implemented in order to carry out the measurements that were of interest to the company. By recreating most of the functionality, or the entire Angular application, more interesting comparisons could have been done.

Design and modeling of optical fibers for spatial division multiplexing using the orbital angular momentum of light

Les besoins toujours croissants en terme de transfert de données numériques poussent au développement de nouvelles technologies pour accroître la capacité des réseaux, notamment en ce qui concerne les réseaux de fibre optique. Parmi ces nouvelles technologies, le multiplexage spatial permet de multiplier la capacité des liens optiques actuels. Nous nous intéressons particulièrement à une forme de multiplexage spatial utilisant le moment cinétique orbital de la lumière comme base orthogonale pour séparer un certain nombre de canaux. Nous présentons d’abord les notions d’électromagnétisme et de physique nécessaires à la compréhension des développements ultérieurs. Les équations de Maxwell sont dérivées afin d’expliquer les modes scalaires et vectoriels de la fibre optique. Nous présentons également d’autres propriétés modales, soit la coupure des modes, et les indices de groupe et de dispersion. La notion de moment cinétique orbital est ensuite introduite, avec plus particulièrement ses applications dans le domaine des télécommunications. Dans une seconde partie, nous proposons la carte modale comme un outil pour aider au design des fibres optiques à quelques modes. Nous développons la solution vectorielle des équations de coupure des modes pour les fibres en anneau, puis nous généralisons ces équations pour tous les profils de fibres à trois couches. Enfin, nous donnons quelques exemples d’application de la carte modale. Dans la troisième partie, nous présentons des designs de fibres pour la transmission des modes avec un moment cinétique orbital. Les outils développés dans la seconde partie sont utilisés pour effectuer ces designs. Un premier design de fibre, caractérisé par un centre creux, est étudié et démontré. Puis un second design, une famille de fibres avec un profil en anneau, est étudié. Des mesures d’indice effectif et d’indice de groupe sont effectuées sur ces fibres. Les outils et les fibres développés auront permis une meilleure compréhension de la transmission dans la fibre optique des modes ayant un moment cinétique orbital. Nous espérons que ces avancements aideront à développer prochainement des systèmes de communications performants utilisant le multiplexage spatial.

Nonlinear distortion generation mechanisms in Doherty amplifiers

Nowadays, wireless communications systems demand for greater mobility and higher data rates. Moreover, the need for spectral efficiency requires the use of non-constant envelope modulation schemes. Hence, power amplifier designers have to build highly efficient, broadband and linear amplifiers. In order to fulfil these strict requirements, the practical Doherty amplifier seems to be the most promising technique. However, due to its complex operation, its nonlinear distortion generation mechanisms are not yet fully understood. Currently, only heuristic interpretations are being used to justify the observed phenomena. Therefore, the main objective of this work is to provide a model capable of describing the Doherty power amplifier nonlinear distortion generation mechanisms, allowing the optimization of its design according to linearity and efficiency criteria. Besides that, this approach will allow a bridge between two different worlds: power amplifier design and digital pre-distortion since the knowledge gathered from the Doherty operation will serve to select the most suitable pre-distortion models.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

The tetrahexahedric angular Calogero model

The spherical reduction of the rational Calogero model (of type A n−1 and after removing the center of mass) is considered as a maximally superintegrable quantum system, which describes a particle on the (n−2)-sphere subject to a very particular potential. We present a detailed analysis of the simplest non-separable case, n=4, whose potential is singular at the edges of a spherical tetrahexahedron. A complete set of independent conserved charges and of Hamiltonian intertwiners is constructed, and their algebra is elucidated. They arise from the ring of polynomials in Dunkl-deformed angular momenta, by classifying the subspaces invariant and antiinvariant under all Weyl reflections, respectively.