201 |
Dynamic nuclear polarisation of diamondHigh, Grant Lysle 08 1900 (has links)
This study is presented in nine chapters as follows:
Chapter one reviews the reported literature on the NMR of natural diamond. The NMR
signal of diamond consists on a single line at 39 ppm from TMS and two hyperfine lines
due to 13C interactions. The reported relaxation times, measured in natural diamond,
synthetic diamonds and 13C enriched diamonds, are discussed.
The second chapter introduces the apparatus used, which included a Bruker Avance
NMR spectrometer, a Bruker ESP380E pulsed EPR spectrometer and a high powersband
DNP system. The availability of this excellently equiped laboratory presented a
unique opportunity to perform this investigation.
Chapter three outlines the experimental techniques used as well as the manner in which
the acquired data was processed.
The fourth chapter presents an overview of the most common defects found in diamond.
Proposed models of these defects are presented and the resulting EPR spectra displayed.
The methods developed to determine the paramagnetic impurity concentration from the
EPR line width and the spin-spin relaxation times are presented in the fifth chapter. The
line width gives the total paramagnetic impurity concentration to about 10 ppm. The spin-spin
relaxation time allows the determination of Pl and P2 paramagnetic impurity
concentrations individually, to much lower levels from measurements on the central and
hyperfine lines. This information was used in the explanation of the relaxation behaviour
for the various diamonds investigated.
The temperature dependence of the paramagnetic electron relaxation times is reported in the sixth chapter. The results obtained are consistent with the findings in prior work that
Pl impurities are typical Jahn Teller centres. Two diamonds, however, display trends that
depart from this theory. These diamonds contain N3 defect centres, which appear to be
responsible for this behaviour. It was found in these experiments that, bar thermal
expansion effects, the spin-spin relaxation time is essentially independent of temperature.
The seventh chapter deals with the solid state and thermal mixing effects. The relevant
theory, results obtained and a discussion of these results, are presented. The effect of
impurity concentration, defect types, microwave power, the exposure time and the offset
from resonance on the polarisation rates and the 13C polarisation are investigated in depth. Finally the effect of applying the DNP treatment on the central and hyperfine lines
is discussed.
The pulsed DNP process is presented in the eighth chapter. The relevant theory, the
effects of matching of the Hartmann-Hahn condition, impurity concentrations and types,
on the polarisation rate and signal enhancement of JJC nuclei is given. A comparison to
the continuous wave techniques is then made.
The ninth chapter summarises the achievements and recommendations for further work. / Physics / D. Phil. (Physics)
|
202 |
The Impact of Hydrocarbon and Carbon Oxide Impuritiesin the Hydrogen Feed of a PEM Fuel CellKortsdottir, Katrin January 2016 (has links)
The proton exchange membrane fuel cell generates electricity from hydrogen and oxygen (from air) through electrocatalytic reactions in an electrochemical cell. The Pt/C catalyst, commonly used in PEM fuel cells, is very sensitive to impurities that can interact with the active catalyst sites and limit fuel cell performance. Unfortunately, most hydrogen is currently produced from fossil sources, and inevitably contains impurities. The subject of this thesis is the effect of hydrogen impurities on the operation of a PEM fuel cell using a Pt/C anode. The impurities studied are carbon monoxide (CO), carbon dioxide (CO2), and selected hydrocarbons. Particular focus is given to the interaction between the impurities studied and the anode catalyst. The main method used in the study involved performing cyclic voltammetry and mass spectrometry, simultaneously. Other electrochemical techniques are also employed. The results show that all the impurities studied adsorb to some extent on the Pt/C catalyst surface, and require potentials comparable to that of CO oxidation, i.e., about 0.6V, or higher to be removed by oxidation to CO2. For complete oxidation of propene, and toluene, potentials of above 0.8, and 1.0V, respectively, are required. The unsaturated hydrocarbons can be desorbed to some extent by reduction, but oxidation is required for complete removal. Adsorption of ethene, propene, and CO2 is dependent on the presence of adsorbed or gaseous hydrogen. Hydrogen inhibits ethene and propene adsorption, but facilitates CO2 adsorption. Adsorption of methane and propane is very limited and high concentrations of methane cause dilution effects only. The adlayer formed on the Pt/C anode catalyst in the presence of CO2, or moderate amounts of hydrocarbons, is found to be insffuciently complete to notably interfere with the hydrogen oxidation reaction. Higher concentrations of toluene do, however, limit the reaction. / Polymerelektrolytbränslecellen genererar elektricitet fran vätgas och syrgas (fran luft) genom elektrokatalytiska reaktioner i en elektrokemisk cell. Den platina-baserade katalysator som oftast används i dessa bränsleceller är känslig mot föroreningar, då dessa kan interagera med katalysatorns aktiva yta, och därmed begränsna bränslecellens prestanda. Tyvärr produceras dagens vätgas huvudsakligen fran fossila källor och innehåller därför oundvikligen föroreningar. Denna avhandling behandlar hur olika vätgasföroreningar påverkar katalysatorns aktivitet och bränslecellens drift. De föroreningar som studeras är kolmonoxid (CO) och koldioxid (CO2), samt ett antal mindre kolväten. Störst fokus ligger på hur dessa föroreningar interagerar med anodens Pt/C katalysator. Den metod som huvudsakligen används är cyklisk voltammetri kombinerat med masspektrometri, men flera elektrokemiska metoder har använts. Resultaten visar att alla undersökta föroreningar adsorberar på Pt/C katalysatorns yta i större eller mindre utstreckning. For att avlägsna det adsoberade skiktet genom oxidation till CO2 krävs potentialer jämförbara med CO oxidation, dvs ca 0,6V, eller högre. Fullständig oxidation av propen eller toluen kräver potentialer högre än 0,8V respektive 1,0V. De omättade kolvätena kan delvis avlägsnas genom reduktion, men fullständig avlägsning kräver oxidation. Närvaron av väte, i gasform eller adsorberat pa katalysatorn, hämmar adsorptionen av eten och propen, men främjar CO2 adsorption. Metan och propan adsorberar i mycket begränsad utstreckning på Pt/C katalysatorns yta. De prestandaförluster som uppstår av höga koncentrationer av metan förklaras av utspädning av vätgasen. Det adsorberade skiktet som bildas när Pt/C katalysatorn exponeras för CO2 eller måttliga koncentrationer av studerade kolväten, är inte tillräckligt heltäckande for att märkbart påverka vätgasreduktionen. Däremot kan höga koncentrationer av toluen begränsa reaktionen. / <p>QC 20161010</p>
|
203 |
Modélisation des phénomènes de transport solutal et étude d’un dispositif de brassage pour la purification du silicium photovoltaïque / Solute segregation and mechanical stirring modelling for photovoltaic silicon purificationChatelain, Marc 28 October 2016 (has links)
Cette étude s’intéresse à la modélisation de la ségrégation des impuretés lors des procédés de solidification dirigée du silicium pour l’industrie photovoltaïque. Il s’agit d’un problème multi-physiques et multi-échelles qui nécessite des modèles efficaces pour pouvoir traiter des configurations industrielles en 3D. La première partie de l’étude porte sur le développement de fonctions de paroi solutales dans le but d’estimer la ségrégation sans résoudre numériquement la couche limite solutale. Un modèle analytique est alors utilisé pour estimer le paramètre convecto-diffusif à partir de la contrainte de frottement à l’interface solide/liquide. L’approche proposée consiste à coupler une simulation hydrodynamique de la convection dans la phase liquide et un calcul analytique de la ségrégation. Cette démarche est validée sur un cas de référence en 2D. Le modèle développé fournit une estimation pertinente de la concentration dans un lingot solidifié avec une vitesse imposée, y compris sur un maillage ne résolvant pas la couche limite solutale. La deuxième partie de l’étude concerne l’utilisation d’un système de brassage mécanique dans le but de favoriser la ségrégation des impuretés. Des simulations transitoires de brassage sont réalisées avec le logiciel FLUENT. Les résultats sont comparés à des mesures de champ de vitesse par PIV effectuées sur une maquette en eau, afin de valider le modèle hydrodynamique. La simulation de brassage est ensuite couplée à un calcul de ségrégation en régime quasi-permanent qui permet d’analyser l’influence de l’écoulement sur la couche limite solutale. Dans la dernière partie de l’étude, une simulation de solidification dirigée 3D instationnaire en régime de convection forcée, intégrant la thermique du four, est réalisée. Un modèle empirique de forces volumiques est alors proposé pour décrire l’écoulement lié au brassage dans le silicium liquide. Une première tentative d’estimation des ségrégations par l’approche analytique est ensuite mise en œuvre. / The present study focuses on solute segregation during photovoltaic silicon directional solidification. This multi-physics problem involves various spatial and temporal scales. The numerical simulation of this process requires efficient models, especially for 3D industrial configurations. In the first part of the study, solute wall functions are derived from a scaling analysis in order to estimate the segregations without numerical resolution of the solute boundary layer. The method is based on the coupling of an hydrodynamic simulation of convection in the liquid phase and an analytical segregation computation. The developed analytical model provides an estimation of the convecto-diffusive parameter from the wall shear-stress at the solid/liquid interface. A reference case in 2D with imposed solidification rate is used for validation purposes. The developed model provides a meaningful estimation of concentration fields in the ingots. In a second part, we focus on segregation optimization by a mechanical stirrer. Transient stirring simulations, using a sliding mesh technique, are achieved with FLUENT commercial software. Results are compared to PIV velocity field measurements performed on an experimental setup using water. A segregation computation in a quasi-steady regime is then implemented in the stirring simulation. The effect of the stirring parameters are directly observed on the solute boundary layer at the solid/liquid interface. In a third part, a transient solidification simulation, including furnace thermal conditions, is performed in a 3D configuration with forced convection. The flow generated by the impeller is described thanks to an empirical model based on body forces. A first attempt is finally made to retrieve segregations in the ingot with the developed analytical method.
|
204 |
In situ characterization by X-ray synchrotron imaging of the solidification of silicon for the photovoltaic applications : control of the grain structure and interaction with the defects and the impurities / Caractérisation in situ par imagerie X synchrotron de la solidification du silicium pour les applications photovoltaïques : contôle de la structure de grains et interactions avec les défauts et les impuretésRiberi-Béridot, Thècle 22 November 2017 (has links)
Au cours de cette thèse, nous avons étudié in situ la solidification du silicium à l’aide de l'imagerie X-synchrotron. Les deux techniques utilisées lors de la solidification sont la radiographie et la diffraction de Bragg, elles permettent de caractériser: la dynamique des mécanismes de croissance, la cinétique de croissance, la nucléation et la compétition de grains, la déformation du réseau cristallin et les champs de contraintes liés aux dislocations. Ces observations sont combinées avec des caractérisations ex situ pour étudier l'orientation cristallographique, les déformations du réseau cristallin ainsi que les concentrations d'impuretés légères telles que le carbone et l'oxygène.La complémentarité de ces techniques permet d'étudier et de mieux comprendre : les phénomènes physiques liés à la formation de la structure de grain finale. Les résultats concernant la cinétique de croissance de l'interface solide-liquide et des facettes {111}, l'établissement de la structure de grain, l'importance du maclage, l'effet des impuretés légères, le champ de contrainte lié à la croissance et la compétition de grains et les dislocations sont discutés dans le manuscrit. / During this thesis, we studied in situ the solidification of silicon with X-synchrotron imaging. The two techniques used during solidification are radiography and Bragg diffraction and they allow characterizing: dynamic growth mechanisms, growth kinetics, grain nucleation and competition, lattice deformation and dislocation related strain fields. These observations are combined with ex situ characterizations to study the crystallographic orientation, the deformations of the crystal lattice as well as the concentrations of light impurities such as carbon and oxygen. The complementarity of these techniques makes it possible to study and to better understand: the physical phenomena related to the formation of the final grain structure. Results concerning the growth kinetics of the solid-liquid interface and of the {111} facets, the establishment of the grain structure, the importance of twinning, the effect of light impurities, the strain field related to growth and grain competition and dislocations are discussed in the manuscript.
|
205 |
Étude de la cinétique de croissance du graphène en conditions purifiéesCharpin, Carl-Bernard 08 1900 (has links)
No description available.
|
206 |
Elementspurenbestimmung in SolarsiliciumBalski, Matthias Michael 17 June 2014 (has links)
Verunreinigungen von Fremdelementen können den Wirkungsgrad von Solarzellen schon im Spurenbereich beeinträchtigen. Die Kenntnis der Verunreinigungen in Si ist entscheidend für die Produkt- und Produktionskontrolle neuer Solarzellenmaterialien. In dieser Arbeit wurden Analysenmethoden mit unterschiedlichen Messverfahren unter besonderer Berücksichtigung der Ansprüche der Solarindustrie entwickelt, verbessert, charakterisiert und verglichen. Mit der Sektorfeld-Massenspektrometrie (SFMS) mit induktiv gekoppeltem Plasma (ICP) nach Matrixabtrennung konnten 22 Elemente mit Bestimmungsgrenzen bis zu 120 pg g−1, quantifiziert werden. Das neue Verfahren erlaubte die Bestimmung aller Elemente in einem Analysengang ohne Analytverlust. Dabei wurde ein bisher in der Literatur nicht beschriebener Mechanismus aufgeklärt, welcher die Retention von Bor im Matrixverdampfungsschritt ohne Zusatz von Komplexbildnern erlaubt. Mit der Glimmentladungs-(GD )MS wurden 32 Elemente bis in den sub ng g−1-Bereich bestimmt. Es gelang, relative Empfindlichkeitsfaktoren zur Quantifizierung von B, P, As, Ga, Ge und Fe zu errechnen. Methoden basierend auf der elektrothermischen Verdampfung (ETV), gekoppelt an ICP-MS und ICP-Emissionsspektroskopie (OES) sowie Gleichstrombogen-OES wurden zur Charakterisierung von metallurgischem Si-Pulver mit Gehalten im µg g−1-Bereich verwendet. Die Totalreflexion-Röntgenfluoreszenz wurde als Volumenmessmethode für die Si-Analytik eingesetzt. Komplettiert wird das Methodenspektrum durch Oberflächenanalytik von Wafern mittels Laserablation-(LA)-ICP-MS. Es wurden erstmalig für Silicium Konzepte zur quantitativen Bestimmung der Verunreinigungen auf Si-Wafern über eine Kalibrierung der LA mit eingetrockneten flüssigen Standards erarbeitet und gezeigt, dass sich das Verfahren zum Nachweis typischer metallischer Ausscheidungen eignet. Die Neutronenaktivierungsanalyse wurde als anerkannte Referenzmethode der Halbleiterindustrie zur Validierung der Methoden eingesetzt. / Element impurities can affect the efficiency of solar cells already on the trace level. The knowledge of the impurities in Si is thus crucial for the product and production control of new solar cell materials. In this work, analysis methods based on different measurement principles have been developed, improved, characterized and compared with special consideration of the requirements of the solar industry. Sector field mass spectrometry (SFMS) with inductively coupled plasma (ICP) subsequent to matrix separation has been used to determine 22 elements with limits of determination down to 120 pg g−1 on sample basis. The new, optimized procedure allowed the determination of all analytes in one sweep without analyte loss during the evaporation step. A so-far unexplained mechanism for the retention of boron without use of additional complexing agents was elucidated. Glow discharge (GD)MS was used to measure 32 elements down to the sub-ng g−1 range. Relative sensitivity factors for the quantification of B, P, As, Ga, Ge and Fe have been calculated. Methods based on electrothermal vaporization (ETV) coupled to ICP-MS and ICP emission spectroscopy (OES) as well as direct current arc OES were used for the characterization of metallurgical grade Si powder with concentrations in the µg g−1 range. Total reflection X-ray fluorescence was used as a method for bulk impurity concentration analysis. The spectrum of methods is complemented by surface analysis of silicon wafers by laser ablation (LA)-ICP-MS. New concepts for quantitative analysis of silicon surfaces by the calibration of LA with dried liquid standards were elaborated. It has been demonstrated that this method is suitable for the detection of typical metallic precipitations in silicon like copper silicide. For validation of the methods, instrumental neutron activation analysis was used as the generally accepted reference method in the semiconductor industry.
|
207 |
Impact des biocarburants sur le système d’oxydation catalytique des véhicules diesel / Impact of biofuels on the catalytic oxidation system of diesel vehiclesAnguita, Paola 08 October 2018 (has links)
Les normes plus restrictives visent à réduire les émissions de polluants, en particulier le CO2, favorisant l'usage des biocarburants. Cependant, le biodiesel contient des éléments inorganiques (Na, K, Ca et P) qui réduisent la durabilité des systèmes de post-traitement. Dans ce travail sont évalués les performances des catalyseurs d'oxydation diesel (DOCs, catalyseur de référence PtPd/CeZrO2/La-Al2O3). Les résultats de caractérisation ont montré l’influence de ces impuretés sur les propriétés physico-chimiques et catalytiques. Bien que la structure cristalline du catalyseur de référence ne change pas après l'incorporation des impuretés, la surface spécifique diminue. La capacité redox a diminué lorsque les impuretés Na, K et Ca sont présents du à leur faible électronégativité, ce qui augmente l'interaction avec l'oxygène. Cette interaction semble être responsable de l’augmentation de la vitesse de réaction de C3H6. Les résultats NO-TPD ont montré que la forte basicité ces impuretés entraînait une plus forte adsorption du NO. Par DRIFT il a été aussi montré que l’adsorption des intermédiaires du NO, associée au champ électrostatique créé par ces cations, empêche l'oxydation de NO. L'adsorption de CO a été favorisée, améliorant la conversion du CO. La formation de phosphate de cérium observée pourrait stabiliser l'état d'oxydation de Ce3+ (vérifié par XPS), en diminuant l'oxydation de NO due au blocage des sites catalytiques. Néanmoins, les co-oxydations de CO et de C3H6 ont été améliorées en évitant l'auto-empoisonnement. Après vieillissement hydrothermal, l'effet des impuretés a été masqué par le frittage de Pt/Pd, ce qui diminue les performances catalytiques / The more restrictive regulations to reduce pollutants emissions, especially CO2, promote the use of biofuels. However, biodiesel contains inorganic elements (Na, K, Ca and P) that reduce the durability of the after-treatment catalysts. This work aims to evaluate the performance of Diesel Oxidation Catalysts (DOCs, PtPd/CeZrO2/La-Al2O3 reference catalyst). The characterization results have shown that the above-mentioned impurities affect the physico-chemical, redox, surface and catalytic properties. Although the catalyst crystalline structure of reference catalyst did not change after impurities incorporation, the specific surface area decreased. The redox ability was also decreased when Na, K and Ca impurities are present due to their low electronegativity, which increased the oxygen interaction. This high interaction seems to be responsible of the enhanced C3H6 reaction rate. NO-TPD results evidenced that the high basicity of Na, K and Ca impurities resulted in an increase of NO adsorption strength. Accordingly, DRIFT results showed the presence of NO intermediates adsorption associated to the electrostatic field created by these cations, hindering NO oxidation. CO adsorption was also promoted, enhancing CO reaction rate. The formation of cerium phosphate was also observed, which could stabilize the Ce3+ oxidation state (checked by XPS), decreasing NO oxidation due to the blockage of catalytic sites. Nevertheless, CO and C3H6 co-oxidations were enhanced by avoiding self-poisoning. After catalyst hydrothermal aging, the effect of impurities was masked by the sintering of Pt/Pd active sites, which decreases the DOC catalytic performances
|
208 |
Níveis profundos associados a vacância e nitrogênio em diamante / Deep levels associated with vacancy and nitrogen in diamondAlves, Horacio Wagner Leite 05 July 1985 (has links)
Neste trabalho estudamos a estrutura eletrônica de defeitos pontuais em diamante , os quais introduzem níveis profundos na faixa proibida deste material. Utilizamos o modelo de aglomerado molecular dentro de dois formalismos: o Método do Espalhamento Múltiplo X (MS- X), que é um método de primeiros princípios e o método \"Complete Neglect of Differential Overlap\" (CNDO/ BW), que é semi-empírico. Foi empregado um tratamento adequado para os orbitais de superfície em cada um dos dois formalismos . Foram estudados dois sistemas: o Nitrogênio substitucional e a vacância simples. Para o Nitrogênio, analisamos as possíveis distorções associadas a este centro, procurando interpretar os resultados experimentais. A vacância simples mostrou-se ser um sistema bastante semelhante à vacância simples em Silício: em ambos os casos observa - se uma distorção Jahn-Teller. O modelo adotado mostrou- se capaz de descrever satisfatoriamente as estruturas eletrônicas dos dois centros estudados, fornecendo resultados quantitativos que são comparados com a experiência . / In this work we studied the electronic structure of point defects in diamond. To do this we used the molecular cluster model within two formalisms: the first-principles X Scattered wave method MS-X ) and the semiempirical Complete Neglect of Differential Overlap (CNOO/BW) method. In each case, an adequate surface orbitals treatment was utilized. We studied the following systems: the substitutional Nitrogen and the simple neutral vacancy. For the substitutional Nitrogen. We analyzed the possible distortion related to this center trying to interprete the experimental results. For the simple neutral vacancy in diamond. The results showed to be similar to the simple Silicon vacancy picture: In both cases we observed a Jahn-Teller distortion (lowering the symmetry of the center). The adopted model showed to be able to describe satisfactorily their electronic structures, and quantitative results are given, which are compared with the experimental data.
|
209 |
Níveis profundos associados a vacância e nitrogênio em diamante / Deep levels associated with vacancy and nitrogen in diamondHoracio Wagner Leite Alves 05 July 1985 (has links)
Neste trabalho estudamos a estrutura eletrônica de defeitos pontuais em diamante , os quais introduzem níveis profundos na faixa proibida deste material. Utilizamos o modelo de aglomerado molecular dentro de dois formalismos: o Método do Espalhamento Múltiplo X (MS- X), que é um método de primeiros princípios e o método \"Complete Neglect of Differential Overlap\" (CNDO/ BW), que é semi-empírico. Foi empregado um tratamento adequado para os orbitais de superfície em cada um dos dois formalismos . Foram estudados dois sistemas: o Nitrogênio substitucional e a vacância simples. Para o Nitrogênio, analisamos as possíveis distorções associadas a este centro, procurando interpretar os resultados experimentais. A vacância simples mostrou-se ser um sistema bastante semelhante à vacância simples em Silício: em ambos os casos observa - se uma distorção Jahn-Teller. O modelo adotado mostrou- se capaz de descrever satisfatoriamente as estruturas eletrônicas dos dois centros estudados, fornecendo resultados quantitativos que são comparados com a experiência . / In this work we studied the electronic structure of point defects in diamond. To do this we used the molecular cluster model within two formalisms: the first-principles X Scattered wave method MS-X ) and the semiempirical Complete Neglect of Differential Overlap (CNOO/BW) method. In each case, an adequate surface orbitals treatment was utilized. We studied the following systems: the substitutional Nitrogen and the simple neutral vacancy. For the substitutional Nitrogen. We analyzed the possible distortion related to this center trying to interprete the experimental results. For the simple neutral vacancy in diamond. The results showed to be similar to the simple Silicon vacancy picture: In both cases we observed a Jahn-Teller distortion (lowering the symmetry of the center). The adopted model showed to be able to describe satisfactorily their electronic structures, and quantitative results are given, which are compared with the experimental data.
|
210 |
Análise estereosseletiva do cloridrato de cis-tramadol e de suas impurezas em matéria-prima e formulação farmacêutica / Estereoselective analysis of cis-tramadol hydrocloride and its impurities in raw material and pharmaceutical formulationBernardo, Naíssa Prévide 10 October 2008 (has links)
O cloridrato de tramadol, analgésico sintético de ação central, possui dois centros quirais: o isômero cis é ativo e o isômero trans é uma impureza de processo. Ambos os enantiômeros do cloridrato de cis-tramadol contribuem para o efeito analgésico, mas através de mecanismos diferentes, complementares e interativos farmacologicamente. Os dois isômeros do cis-tramadol apresentam efeitos terapêuticos, e a presença de impurezas, incluindo os isômeros trans - decorrentes do processo de síntese ou devido à decomposição - podem comprometer a qualidade do produto comercializado. Assim, este trabalho teve como objetivo desenvolver e validar metodologia estereosseletiva para análise do cloridrato de cis-tramadol e das possíveis impurezas quirais ou não na matéria-prima e formulações farmacêuticas. Para a separação e quantificação dos enantiômeros do cloridrato de cis-tramadol e das impurezas trans-tramadol, 1,2-olefina e 1,6-olefina, foi utilizada a coluna Chiralcel® OD-H, fase móvel constituída por hexano (60% e 100% de n-hexano, 1:1, v/v):isopropanol:dietilamina:ácido trifluoracético (99,5:0,5:0,3:0,1, v/v/v/v), na vazão de 0,7 mL min-1 e detecção em 274 nm. A coluna Chiralpak® AD fase móvel constituída por hexano (60% de n-hexano):etanol absoluto:dietilamina (95:5:0,1, v/v/v), na vazão de 1,0 mL min-1 e o comprimento de onda para detecção dos compostos foi de 228 nm foi utilizada para a separação e quantificação das impurezas O-desmetiltramadol, N-desmetiltramadol e tramadol N-óxido. Os métodos desenvolvidos foram devidamente validados através dos parâmetros seletividade, linearidade, precisão, exatidão, intervalo, limite de detecção e limite de quantificação. Os resultados obtidos na validação mostraram que os métodos são adequados para a determinação do cis-tramadol e de suas impurezas na matéria prima e na formulação farmacêutica. / Tramadol hydrochloride is a centrally acting analgesic with two chiral centers; the cis isomer is the active drug and the trans isomer is a process impurity. Both enantiomers of cis-tramadol hydrochloride contribute to the analgesic effect through different, but complementary and interactive pharmacological mechanisms. Although both isomers of cis-tramadol hydrochloride show therapeutic effects, the presence of impurities, originated from the synthesis process or due to degradation, can compromise the quality of the marketed product. The aim of this present work was the development and validation of a stereosselective methodology for the analysis of the drug cis-tramadol hydrochloride and the possible chiral or non-chiral impurities in raw materials and pharmaceutical formulations. The separation and quantitation of cis-tramadol enantiomers and the impurities trans-tramadol, 1,2-olefin and 1,6-olefin were carried out using a Chiralcel® OD-H column, mobile phase of hexane (60% and 100% of n-hexane, 1:1, v/v):2-propanol:diethylamine:trifluoroacetic acid (99,5:0,5:0,3:0,1, v/v/v/v) at a flow rate of 0,7 mL min-1 and detection at 274 nm. For the separation and quantitation of the impurities O-desmethyltramadol, N-desmethyltramadol and tramadol N-oxide, a Chiralpak® AD column was used with a mobile phase of hexane (60% of n-hexane):ethanol absolute: diethylamine (95:5:0,1, v/v/v) at a flow rate of 1,0 mL min-1 and detection at 228 nm. The methods were validated using the parameters selectivity, linearity, precision, accuracy, range, detection limit and quantitation limit. The results obtained show that the methods are suitable for the analysis of cis-tramadol and its impurities in raw material and pharmaceutical formulation.
|
Page generated in 0.0169 seconds