Estudo eletroquímico e químico-quântico da oxidação do antidepressivo tricíclico amitriptilina

This work presents the electrochemical and quantum chemical studies of the oxidation of the tricyclic antidepressant amitriptyline (AM) employing a carbon-polyurethane composite electrode (GPU) in a 0.1 mol L-1 BR buffer. The electrochemical results showed that the oxidation of AM occurs irreversibly at potentials close to 830 mV with the loss of one electron and one proton and is controlled by reagent and product adsorption. According to the PM3 results, the atom C16 is the region of highest probability for the oxidation of AM since it has the largest charge variation.

Excitation modes of vortices in submicron magnetic disks

Classical and quantum theory of spin waves in the vortex state of a mesoscopic submicron magnetic disk have been developed with account of the finite mass density of the vortex. Oscillations of the vortex core resemble oscillations of a charged string in a potential well in the presence of the magnetic field. A conventional gyrotropic frequency appears as a gap in the spectrum of spin waves of the vortex. The mass of the vortex has been computed, and the result agrees with experimental findings. The finite vortex mass generates a high-frequency branch of spin waves. The effects of an external magnetic field and dissipation have been addressed.

Uma introdução à espectroscopia atômica: II - o espectro do sódio

The present article is devoted to Chemistry or Physics undergraduate students, given their difficulty to understand fundamental concepts and technical language used in atomic spectroscopy and quantum mechanics. An easy approach is shown in the treatment of the emission spectrum of the sodium atom without any involved calculations. In a previous article, the hydrogen spectrum was considered and the energy degeneracy of the angular momentum quantum number was observed. For the sodium spectrum, due to the valence electron penetration into internal shells, a breakdown of this degeneracy occurs and a dependence of this penetration on the angular momentum quantum number is observed. The eigenvalues are determined introducing the quantum defect correction (Rydberg correction) in the denominator of the Balmer equation, and the energy diagram is obtained. The intensity ratio for the observed doublets is explained by introducing new wave functions, containing the magnetic quantum number of the total angular momentum.

The Detector Control Systems for the CMS Resistive Plate Chamber at LHC

The RPC Detector Control System (RCS) is the main subject of this PhD work. The project, involving the Lappeenranta University of Technology, the Warsaw University and INFN of Naples, is aimed to integrate the different subsystems for the RPC detector and its trigger chain in order to develop a common framework to control and monitoring the different parts. In this project, I have been strongly involved during the last three years on the hardware and software development, construction and commissioning as main responsible and coordinator. The CMS Resistive Plate Chambers (RPC) system consists of 912 double-gap chambers at its start-up in middle of 2008. A continuous control and monitoring of the detector, the trigger and all the ancillary sub-systems (high voltages, low voltages, environmental, gas, and cooling), is required to achieve the operational stability and reliability of a so large and complex detector and trigger system. Role of the RPC Detector Control System is to monitor the detector conditions and performance, control and monitor all subsystems related to RPC and their electronics and store all the information in a dedicated database, called Condition DB. Therefore the RPC DCS system has to assure the safe and correct operation of the sub-detectors during all CMS life time (more than 10 year), detect abnormal and harmful situations and take protective and automatic actions to minimize consequential damages. The analysis of the requirements and project challenges, the architecture design and its development as well as the calibration and commissioning phases represent themain tasks of the work developed for this PhD thesis. Different technologies, middleware and solutions has been studied and adopted in the design and development of the different components and a big challenging consisted in the integration of these different parts each other and in the general CMS control system and data acquisition framework. Therefore, the RCS installation and commissioning phase as well as its performance and the first results, obtained during the last three years CMS cosmic runs, will be

Técnica de bombeio e prova para medidas de absorção de estado excitado e de emissão estimulada, em materiais sólidos dopados com íons terras raras

Rare earth ion doped solid state materials are the most important active media of near-infrared and visible lasers and other photonic devices. In these ions, the occurrence of Excited State Absorptions (ESA), from long lived electronic levels, is commonplace. Since ESA can deeply affect the efficiencies of the rare earth emissions, evaluation of these transitions cross sections is of greatest importance in predicting the potential applications of a given material. In this paper a detailed description of the pump-probe technique for ESA measurements is presented, with a review of several examples of applications in Nd3+, Tm3+ and Er3+ doped materials.

Estudos fotoluminescentes em compostos de íons terras raras coordenados por um derivado carbazólico

[RE(czb)3(H2O)2] complexes (where RE = Eu3+, Tb3+, Gd3+; and czb = 4-(9H-carbazol-9-yl)benzoato) have been synthesized and characterized. The Gd3+ complex was used to determine the triplet state energy of the czb ligand. Photoluminescence measurements of the complexes have been carried out under UV excitation. The Tb3+ complex exhibited a strong green luminescence indicating an efficient antenna effect, whereas the Eu3+ complex showed low red luminescence and the Gd3+ complex a blue-green luminescence from the ligand. The luminescence lifetimes and quantum yields have also been measured for the evaluation of the spectroscopic behavior of the complexes.

Resolvendo a equação de Schrödinger utilizando procedimentos numéricos fundamentais

A combination of the variational principle, expectation value and Quantum Monte Carlo method is used to solve the Schrödinger equation for some simple systems. The results are accurate and the simplicity of this version of the Variational Quantum Monte Carlo method provides a powerful tool to teach alternative procedures and fundamental concepts in quantum chemistry courses. Some numerical procedures are described in order to control accuracy and computational efficiency. The method was applied to the ground state energies and a first attempt to obtain excited states is described.

Síntese de cristais líquidos derivados do nitroazobenzeno: uma proposta de síntese multi-etapas aplicada às aulas de química orgânica experimental

We describe a synthetic route consisting of five steps from aniline to obtain liquid crystal compounds derived from nitroazobenzene. Syntheses were performed during the second half of the semester in organic chemistry laboratory classes. Students characterized the liquid crystal phase by the standard melting point techniques, differential scanning calorimetry and polarized optical microscopy. These experiments allow undergraduate students to explore fundamentally important reactions in Organic Chemistry, as well as modern concepts in Chemistry such as self-assembly and self-organization, nanostructured materials and molecular electronics.

TRIHALOMETANOS EM ÁGUA POTÁVEL E RISCOS DE CÂNCER: SIMULAÇÃO USANDO POTENCIAL DE INTERAÇÃO E TRANSFORMAÇÕES DE BÄCKLUND

We briefly investigated the well-known correlation of trihalomethanes, present in fresh water, with cancer hazard in humans. A transient alternative method of chemical simulation using Bäcklund Transformations and Quantum Mechanics is presented. Finally, the method was applied to simulate the interaction between Trichloridemethane and Alanine - as well as its amino and carboxyl groups.

Unusual bismuth-containing surface layers of III-V compound semiconductors

The understanding and engineering of bismuth (Bi) containing semiconductor surfaces are signi cant in the development of novel semiconductor materials for electronic and optoelectronic devices such as high-e ciency solar cells, lasers and light emitting diodes. For example, a Bi surface layer can be used as a surfactant which oats on a III-V compound-semiconductor surface during the epitaxial growth of IIIV lms. This Bi surfactant layer improves the lm-growth conditions if compared to the growth without the Bi layer. Therefore, detailed knowledge of the properties of the Bi/III-V surfaces is needed. In this thesis, well-de ned surface layers containing Bi have been produced on various III-V semiconductor substrates. The properties of these Bi-induced surfaces have been measured by low-energy electron di raction (LEED), scanning-tunneling microscopy and spectroscopy (STM), and synchrotron-radiation photoelectron spectroscopy. The experimental results have been compared with theoretically calculated results to resolve the atomic structures of the studied surfaces. The main ndings of this research concern the determination of the properties of an unusual Bi-containing (2×1) surface structure, the discovery and characterization of a uniform pattern of Bi nanolines, and the optimization of the preparation conditions for this Bi-nanoline pattern.

Characterization Of Process Efficiency Improvement In Laser Additive Manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, has gained a lot of interest in past recent years within various industries, such as medical and aerospace industries. LAM enables fabrication of complex 3D geometries by melting metal powder layer by layer with laser beam. Research in laser additive manufacturing has been focused in development of new materials and new applications in past 10 years. Since this technology is on cutting edge, efficiency of manufacturing process is in center role of research of this industry. Aim of this thesis is to characterize methods for process efficiency improvements in laser additive manufacturing. The aim is also to clarify the effect of process parameters to the stability of the process and in microstructure of manufactured pieces. Experimental tests of this thesis were made with various process parameters and their effect on build pieces has been studied, when additive manufacturing was performed with a modified research machine representing EOSINT M-series and with EOS EOSINT M280. Material used was stainless steel 17-4 PH. Also, some of the methods for process efficiency improvements were tested. Literature review of this thesis presents basics of laser additive manufacturing, methods for improve the process efficiency and laser beam – material- interaction. It was observed that there are only few public studies about process efficiency of laser additive manufacturing of stainless steel. According to literature, it is possible to improve process efficiency with higher power lasers and thicker layer thicknesses. The process efficiency improvement is possible if the effect of process parameter changes in manufactured pieces is known. According to experiments carried out in this thesis, it was concluded that process parameters have major role in single track formation in laser additive manufacturing. Rough estimation equations were created to describe the effect of input parameters to output parameters. The experimental results showed that the WDA (width-depth-area of cross-sections of single track) is correlating exponentially with energy density input. The energy density input is combination of the input parameters of laser power, laser beam spot diameter and scan speed. The use of skin-core technique enables improvement of process efficiency as the core of the part is manufactured with higher laser power and thicker layer thickness and the skin with lower laser power and thinner layer thickness in order to maintain high resolution. In this technique the interface between skin and core must have overlapping in order to achieve full dense parts. It was also noticed in this thesis that keyhole can be formed in LAM process. It was noticed that the threshold intensity value of 106 W/cm2 was exceeded during the tests. This means that in these tests the keyhole formation was possible.

Aktiivisten magneettilaakereiden ohjauslaitteiston vaatimusmäärittely ja toteutus

Aktiivinen magneettilaakeri on järjestelmä joka mahdollistaa pyörivän kappaleen, esimerkiksi sähkökoneen roottorin, leijuttamisen magneettikentässä ilman fyysistä kontaktia vastakappaleiden välillä. Tekniikalla on joitain merkittäviä etuja muihin laakerointijärjestelmiin verrattuna erityisesti suurnopeuksisissa tai puhdastiloissa käytettävissä sähkökäytöissä. Magneettilaakereiden yleistymistä nopeuttaisi ja niiden hintaa laskisi mikäli laakereiden säätöön ja tehonsyöttöön voitaisiin käyttää standardeja teollisuusautomaatiolaitteita erityisesti tätä käyttötarkoitusta varten kehitettyjen laitteiden sijaan. Tässä työssä luodaan menetelmä määrittää vähimmäisvaatimukset aktiivisen magneettilaakerin säätöalgoritmien suorittamiseen käytetylle säätöjärjestelmälle ja anturoinnille sekä laakerin toimintaan tarvittavalle tehoelektroniikalle. Näiden vaatimusten perusteella luodaan katsaus soveltuviin laitteisiin ja kootaan esimerkkikokoonpanot kahdelle erilaiselle magneettilaakeroitavalle kohteelle. Lisäksi työssä esitellään LUT:ssa vuosina 2014-2015 kehitetty magneettilaakerin teholähdeprototyyppi ja selvitetään edellytykset käyttää laitetta laakerijärjestelmän osana.

Preuves interactives quantiques

Cette thèse est consacrée à la complexité basée sur le paradigme des preuves interactives. Les classes ainsi définies ont toutes en commun qu’un ou plusieurs prouveurs, infiniment puissants, tentent de convaincre un vérificateur, de puissance bornée, de l’appartenance d’un mot à un langage. Nous abordons ici le modèle classique, où les participants sont des machines de Turing, et le modèle quantique, où ceux-ci sont des circuits quantiques. La revue de littérature que comprend cette thèse s’adresse à un lecteur déjà familier avec la complexité et l’informatique quantique. Cette thèse présente comme résultat la caractérisation de la classe NP par une classe de preuves interactives quantiques de taille logarithmique. Les différentes classes sont présentées dans un ordre permettant d’aborder aussi facilement que possible les classes interactives. Le premier chapitre est consacré aux classes de base de la complexité ; celles-ci seront utiles pour situer les classes subséquemment présentées. Les chapitres deux et trois présentent respectivement les classes à un et à plusieurs prouveurs. La présentation du résultat ci-haut mentionné est l’objet du chapitre quatre.

Photophysical Investigations of Thiophene Azomethine Derivatives

Une série de dimères composés de thiophène-aniline encombrée stériquement a été synthétisée. Les différents processus de désactivation de l’état singulet excité ont été étudiés par UV-visible, fluorescence, phosphorescence, photolyse par impulsion laser et calculs théoriques. Les graphiques de Stern-Volmer obtenus à partir des expériences de désactivation des états singulet et triplet ont démontré l’efficacité de l’azométhine à désactiver les fluorophores. Les calculs semi-empiriques AM1 examinant l’effet des substituants encombrés ont démontrés que les groupements tert-butyls sur l’aniline ont moins d’influence sur la barrière de rotation N-aryl que les substitutions alkyles en ont sur la rotation de thiophène-C. Les calculs Rehm-Weller basés sur les potentiels d’oxydation et de réduction ont montré que l’autodésactivation de l’état excité des azométhines se fait par transfert d’électron photoinduit menant à une éradication complète de la fluorescence. Des complexes métalliques contenant des ligands azométhines ont aussi été préparés. Le ligand est composé d’une unité hydroxyquinoline lié à un cycle thiophène. Les données photophysiques de ces complexes indiquent un déplacement bathochromique aussi bien en absorbance qu’en fluorescence. Des dispositifs de détection d’ion métallique ont été préparés et un exemple à partir d’une solution de cuivre a montré un déplacement bathochromique.

Superintégrabilité avec séparation de variables en coordonnées polaires et intégrales du mouvement d’ordre supérieur à deux

Dans cette thèse, nous proposons de nouveaux résultats de systèmes superintégrables séparables en coordonnées polaires. Dans un premier temps, nous présentons une classification complète de tous les systèmes superintégrables séparables en coordonnées polaires qui admettent une intégrale du mouvement d'ordre trois. Des potentiels s'exprimant en terme de la sixième transcendante de Painlevé et de la fonction elliptique de Weierstrass sont présentés. Ensuite, nous introduisons une famille infinie de systèmes classiques et quantiques intégrables et exactement résolubles en coordonnées polaires. Cette famille s'exprime en terme d'un paramètre k. Le spectre d'énergie et les fonctions d'onde des systèmes quantiques sont présentés. Une conjecture postulant la superintégrabilité de ces systèmes est formulée et est vérifiée pour k=1,2,3,4. L'ordre des intégrales du mouvement proposées est 2k où k ∈ ℕ. La structure algébrique de la famille de systèmes quantiques est formulée en terme d'une algèbre cachée où le nombre de générateurs dépend du paramètre k. Une généralisation quasi-exactement résoluble et intégrable de la famille de potentiels est proposée. Finalement, les trajectoires classiques de la famille de systèmes sont calculées pour tous les cas rationnels k ∈ ℚ. Celles-ci s'expriment en terme des polynômes de Chebyshev. Les courbes associées aux trajectoires sont présentées pour les premiers cas k=1, 2, 3, 4, 1/2, 1/3 et 3/2 et les trajectoires bornées sont fermées et périodiques dans l'espace des phases. Ainsi, les résultats obtenus viennent renforcer la possible véracité de la conjecture.