L’utilisation de fluides non vaporisables tels que les gaz pour tremper différentes pièces d’acier rend possible, avec les outils numériques actuels, la simulation de l’ensemble des phénomènes physiques mis en jeu dans ce traitement thermique et ainsi de prédire les comportements thermique, métallurgique et mécanique des pièces. Plusieurs auteurs s’intéressent à la construction de ce type de modèles dont les enjeux sont de promouvoir l’utilisation de la trempe gazeuse haute pression, en cherchant à remplacer les trempes à l’huile plus polluantes et/ou à maîtriser les déformations pendant ou après la trempe. Lors de notre travail, un modèle décrivant ces phénomènes physiques, de l’écoulement gazeux aux déformations, et leurs couplages a été construit par étapes en couplant les deux codes de calcul commerciaux Fluent et Sysweld. Les résultats de simulations ont ensuite été confrontés à des mesures de vitesses d’écoulements de gaz (par PIV), de températures et de déformations in situ (détection de contours). Malgré quelques écarts dont les origines ont été analysées, la comparaison a révélé une très bonne concordance des résultats de calculs et expérimentaux, validant ainsi la démarche de calcul. Le modèle pourrait maintenant être testé pour des refroidissements plus rapides que ceux considérés mais son utilisation pour des applications industrielles (pièces de géométrie plus complexe, refroidissement de charges entières, …) peut d’ores et déjà être envisagée avec confiance / The use of non vaporizable fluids such as gas to quench steel bodies makes the simulation of all the coupled physical phenomena involved in this heat treatment possible thanks to current numerical simulation tools. It gives access to the prediction of thermal, metallurgical and mechanical behaviour of steel pieces during quenching operation. Several authors have tried and build such kind of models in order to promote gas quenching use either by trying to replace less environmental friendly oil treatments or by trying to control distortions during or after quenching. In our work a model describing the physical coupled phenomena, from gas flow to distortion has been built step by step by coupling both commercial numerical codes Fluent and Sysweld. Simulation results have then been compared to gas flow velocities measurements (by PIV), temperature measurements and in situ distortions measurements (contour’s detection method). This confrontation revealed a very good agreement between calculated and experimental data despite some slight differences, which have been analysed in detail. This validated the calculation method used in the model. One of the perspectives of this work could be the validation of the model for higher quenching rate. However, some industrial applications (tridimensional more complex bodies quenching simulation, quenching of full loads, …) can be run from now on with confidence

Dans les collisions Pb-Pb au LHC, un milieu chaud et dense formé de quarks et de gluons déconfinés est formé, communément appelé Plasma de Quarks et de Gluons (PQG). Le PQG est l’état hypothétique de l’univers primordial quelques microsecondes après le Big Bang et constituerait encore à ce jour le cœur des étoiles à neutrons. Une des signatures les plus frappantes de l’occurrence du PQG lors de collisions d’ions lourds est la suppression des jets. Ce phénomène appelé étouffement des jets est attribué au mécanisme de perte d’énergie du parton à l’origine du jet lors de son trajet au travers du milieu formé par le PQG.Les deux dernières décennies ont vu l’émergence d’une formulation théorique du phénomène d’étouffement des jets dans le cadre de la Chromo Dynamique Quantique. La perte d’énergie étant le plus fréquemment attribuée dans la littérature à des processus radiatifs et collisionnels. Un nouveau mécanisme de perte d’énergie à été étudié dans ce travail de thèse qui outre la description des effets de diffusions multiples, met en œuvre une perte d’énergie radiative induite par un champ chromomagnétique, de sorte qu’un parton rapide se propageant au travers du milieu ressentira l’effet des champs magnétique et de couleur tout en subissant des diffusions multiples avec les particules du milieu.De plus, les modèles théoriques prédisent une dépendance de la perte d’énergie avec la charge de couleur et la masse du parton issu d’une diffusion à grand transfert d’impulsion lors de sa traversée du milieu.Une telle dépendance en masse peut être étudiée en mesurant la production de hadrons et de jets contenant des quarks lourds dans les collisions pp, p-Pb et Pb-Pb au LHC. Dans cette thèse, un modèle original du milieu est présenté, décrit comme un ensemble de centres de diffusion statiques colorés en présence d’un champ chromomagnétique, de même qu’une description du mécanisme de perte d’énergie associé. Enfin, la mesure de la production de jets issus de quarks beaux avec le détecteur ALICE dans les colllsions pp et p-Pb à l’énergie de 5.02 TeV au LHC à l’aide d’une méthode d’étiquetage utilisant le paramètre d’impact des traces est présenté dans cette thèse. / In Pb-Pb collisions at the LHC, a hot and dense medium of deconfined quarks and gluons is formed, the so-called Quark-Gluon Plasma (QGP).The QGP is conjectured to be the state of matter of the early Universe up to few microseconds after the Big Bang and may still exist in the core of neutron stars. One of the most striking signatures of the QGP formation in heavy-ion collisions is the suppression of jet production. This phenomenon, called jet quenching, is ascribed to the energy lost by the initial parton while traveling through the QGP medium.In the last two decades, many theoretical developments of the theory of jet quenching have been formulated within pQCD.The main energy loss mechanisms proposed in the literature are attributed to radiative and collisional processes. Another kind of energy loss is developed in this work comprises a background field induced radiative energy loss which besides that besides scattering effects. Under the suggested model, a fast parton propagating through the medium will feel the effect of the color magnetic and the color electric fields while undergoing multiple scatterings with the particles in the medium.Besides, theoretical models predict that energy loss depends on the color charge and mass of the hard-scattered parton traversing the medium. Such mass dependence can be studied by measuring the production of hadrons and jets containing heavy-quarks in pp, p-Pb and Pb-Pb collisions at the LHC.In this thesis report, a new model for the medium is presented, which is described as a collection of static colored scattering centers in the presence of a chromomagnetic field, together with the description of the related energy loss mechanism. The ALICE measurement of b-jet production in pp and p-Pb collisions at $sqrt{s_{mathrm{NN}}}=5.02$ TeV using an impact parameter based tagger is also presented.

L'une des stratégies mise en œuvre pour améliorer la prise en charge thérapeutique des patients concerne le développement d'outils diagnostiques sensibles et spécifiques. Les aptamères sont des oligonucléotides artificiels obtenus par SELEX avec une très haute affinité ainsi qu'une excellente spécificité pour leurs cibles. L'immobilisation de ces motifs de reconnaissance moléculaire à la surface de nanomatériaux tels que des nanoparticules d'or (AuNPs), dont les propriétés optiques et électroniques sont uniques, permet d'amplifier le signal généré par l'interaction du ligand avec sa cible. Deux systèmes de biosensing ont été élaboré en fonctionnalisant des AuNPs avec des aptamères, l'un dirigé contre la thrombine et le second dirigé contre une marque épigénétique portée par une protéine histone. La réduction des sels d'or aurique précurseurs a été réalisée en présence de PEG4 et a conduit à l'obtention d'une population homodisperse de AuNPs sphériques d'un diamètre moyen de 14 nm et présentant une isotropie de taille et de forme. Ces AuNPs ont ensuite été fonctionnalisées par des bras espaceurs de longueur variable constitués d'unités tétraéthylène glycol successives reliées entre elles par des ponts éthers ou triazoles. L'acide lipoique a été utilisé comme motif d'ancrage à la surface des AuNPs via une liaison covalente Au-S et a été couplé aux différents bras espaceurs via une réaction de Steglich. Les linkers étaient porteurs d'un groupement terminal azoture afin de réaliser le couplage par chimie-click avec les aptamères. La stratégie de détection de la thrombine utilisait les propriétés de quenching de fluorescence des AuNPs alors que la détection de l'histone était colorimétrique et mettait à profit l'effet de résonance plasmonique de surface des nanoparticules d'or. / Improving patients therapeutic care needs the development of sensitive and specific diagnostic tools. Aptamers are synthetic oligonucleotides obtained by SELEX with a very high affinity and excellent specificity for their targets. Grafting of these molecular recognition patterns onto nanomaterials such as gold nanoparticles (GNPs), which unique optical and electronic properties, can amplify the signal induce by the interaction between the ligand and its target. Two biosensing systems have been developed by GNP functionalization with aptamers, one is directed against thrombin and the second against an epigenetic mark carried by a histone protein. Gold precursors was reduced in the presence of PEO4 and led to a homodisperse population of spherical GNP with an average diameter of 14 nm and an isotropy of size and shape. GNP were functionalized with tetraethylene glycol units interconnected by ether or triazoles bridges as a linker. Lipoic acid was used as an anchor moiety onto gold surface via a covalent Au-S bond and was coupled to the spacer through a Steglich reaction. The linkers were functionalized with an azide group to perform the coupling with aptamers by click chemistry. The thrombin sensing strategy used the fluorescence quenching properties of GNPs while the histone detection involved the gold nanoparticle plasmon resonance surface effect.

O objetivo deste trabalho é analisar a distribuição das tensões residuais que resultam da combinação das variações volumétricas resultantes dos gradientes térmicos e das transformações de fase que ocorrem durante a têmpera de cilindros de aço AISI/SAE 1045, 4140 e 4340. O modelo matemático usado para este objetivo utiliza o programa AC3 de modelagem de tratamentos térmicos (curvas de transformação, curvas de resfriamento, microestrutura e a dureza do material), para alimentar um modelo de elementos finitos, considerando acoplamento termo-mecânico e comportamento não linear elasto-plástico, para previsão de tensões residuais em cilindros de aço AISI/SAE 1045, 4140 e 4340 temperados em água. São apresentados, também, os resultados de observações metalográficas e perfis de dureza que confirmam qualitativamente as previsões do programa AC3. A verificação do modelo numérico por elementos finitos foi efetuada através da medição das tensões residuais nos cilindros de aço com o emprego da técnica de difração de raios X. A simulação numérica, através do método dos elementos finitos comprova, nos três casos estudados, a existência de tensões residuais de compressão na região superficial após o processo de têmpera e indica de maneira quantitativa e qualitativa que as tensões mais significativas são as tangenciais. Os resultados obtidos a partir do modelo numérico mostraram uma aderência significativa em comparação com os resultados experimentais. / The aim of this work is to analyze the distribution of residual stresses resulting from combination of volumetric changes due to heat gradients and phase changes occurring during the quenching process of AISI/SAE 1045, 4140 and 4340 steel cylinders. The mathematical model used for this objective uses the AC3 program for modeling thermal treatments (transformation curves, cooling curves, microstructure and material hardness), whose results were fed into a finite element model, considering thermal-mechanical coupling and non-linear elastic-plastic behavior for forecasting of residual stresses in AISI/SAE 1045, 4140 and 4340 steel cylinders quenched in water. The observed microstructures and measured hardness confirmed qualitatively the previsions of the AC3 program. The results of finite element modeling were compared to experimental measurements of residual stresses measured at the surface, using X-Ray diffraction techniques. The finite element numerical simulation shows, for the three studied cases, the presence of compressive residual stresses in the surface region after a quenching process and indicates qualitatively and quantitatively that the most significant stresses are the tangential ones. The results obtained from the numerical model showed a significant adherence in comparison with the experimental results.

A aplicação do novo conceito de tratamento térmico, chamado de têmpera e partição (Q&P), desenvolvido para a obtenção de aços da terceira geração da classe AHSS (Advanced high strengh steel ou aços avançados de alta resistência), mostra-se uma alternativa para o processamento de ferros fundidos nodulares com alta resistência mecânica. No processo Q&P, o carbono presente na martensita supersaturada, formada na etapa de têmpera, é utilizado para estabilizar a austenita não transformada durante a etapa de partição, mantendo-a estável na temperatura ambiente. Essa rota de tratamento térmico consiste em realizar uma têmpera no material (após uma etapa prévia de austenitização) numa faixa de temperatura entre o Ms e Mf (temperatura de início e fim da transformação martensítica, respectivamente), seguido de um reaquecimento e manutenção a uma temperatura acima do Ms (etapa isotérmica de partição) com o objetivo de que o carbono migre da martensita supersaturada para a austenita remanescente promovendo sua estabilização. Essa partição do carbono só é possível caso a precipitação da cementita seja suprimida, e isso é conseguido com a presença de elementos de liga, como o Si e/ou Al. Neste trabalho foi feito um estudo sobre as características microestruturais e mecânicas de um ferro fundido nodular (3,47%C; 2,47%Si; 0,2%Mn) submetido ao tratamento térmico de têmpera e partição, o qual foi denominado neste trabalho como, Q&PDI (Quenched and Partitioned Ductile Iron ou Ferro Fundido Nodular Temperado e Particionado). Para isso foi realizada uma austenitização plena nas amostras, a 880°C, por duas horas, seguida de uma têmpera em óleo pré-aquecido nas temperaturas de 140 e 170°C. A etapa de partição foi feita nas temperaturas de 300, 375 e 450°C, com intervalos de tempo variando de 5 a 120 minutos. A caracterização microestrutural foi realizada através de microscopia ótica, microscopia eletrônica de varredura e EBSD. A técnica de difração de raios-X foi empregada para quantificar a fração volumétrica e o teor de carbono na austenita retida. Ensaios de dilatometria, difração de raios-X \"in situ\" e nanoindentação foram empregados para auxiliar na análise das transformações de fases que ocorreram na etapa de partição, como a transformação bainítica e a precipitação de carbonetos de transição nas placas de martensita. A caracterização mecânica foi feita através de ensaios de tração, impacto, dureza, nanoindentação, tenacidade à fratura e resistência à fadiga. Ensaios de compressão auxiliaram na análise da transformação martensítica induzida por deformação. Os resultados obtidos mostraram que é possível obter ferros fundidos nodulares com alta resistência mecânica (limite de resistência >1450 MPa), com consideráveis ductilidade (de até 9%) e energia absorvida sob impacto (de até 81 J), bem como tenacidades à fratura de 55 MPa.m1/2 e limites de fadiga de 550 MPa. Este comportamento é proporcionado por uma microestrutura singular, constituída por uma dispersão homogênea de placas de martensita numa matriz de ausferrita bastante refinada, com consideráveis frações volumétricas de austenita retida (max. 23%). / Quenching and partitioning (Q & P), a new heat treatment concept developed to obtain third generation AHSS (Advanced High Strength Steel), is an alternative for processing of nodular cast irons in order to obtain high mechanical strength. In the Q & P process, the carbon present in the supersaturated martensite formed in the quenching step diffuses towards the untransformed austenite during the partition step, keeping it stable at room temperature. This heat treatment route consists of quenching the material (after a previous step of austenitization) in a temperature range between Ms and Mf (beginning and end temperature of the martensitic transformation, respectively), followed by reheating and maintenance at a temperature above the Ms (isothermal stage of partition) allowing the carbon to migrate from the supersaturated martensite to the remaining austenite, promoting its stabilization. This partition of carbon is only possible if precipitation of cementite is suppressed; this is achieved adding alloying elements such as Si and/or Al. In this work a study was made on the microstructural and mechanical characteristics of a ductile iron (3.47%C; 2.47%Si; 0.2%Mn), submitted to a Q&P heat treatment, in this work named Q & PDI (Quenched and Partitioned Ductile Iron). A full sample austenitization was carried out at 880 ° C for two hours, followed by a pre-heated oil quanching at temperatures of 140 and 170 ° C. The partitioning step was at temperatures of 300, 375 and 450Â ° C, with time intervals ranging from 5 to 120 minutes. Microstructural characterization was performed through optical microscopy, scanning electron microscopy and EBSD. The X-ray diffraction technique was used to quantify the volumetric fraction and the carbon content in the retained austenite. Dilatometry, X-ray diffraction \"in situ\" and nanoindentation were also used to aid in the analysis of the phase transformations that occurred in the partitioning stage, such as the bainitic transformation and the precipitation of transition carbides in the martensite plates. Mechanical characterization was performed through tensile, impact, hardness, nanoindentation, fracture toughness and fatigue strength tests. Compression tests aided in the analysis of the deformation induced martensitic transformation. The results showed that it is possible to obtain nodular cast irons with high mechanical strength (resistance limit> 1450 MPa), with considerable ductility (up to 9%) and energy absorbed under impact (up to 81 J), as well as fracture toughness of 55 MPa.m -1 / 2 and fatigue limits of 550 Mpa. This behavior is provided by a unique microstructure, consisting of a homogeneous dispersion of martensite plates in a very refined ausferrite matrix, with considerable volumetric fractions of retained austenite (max. 23%).

A têmpera dos aços envolve a austenitização de uma peça seguida por um resfriamento rápido para promover a formação de microestrutura martensítica. É necessário avaliar os meios de têmpera para manter o processo de têmpera sob controle. Os parâmetros mais importantes no processo de resfriamento são o coeficiente de transferência de calor e/ou o fluxo de calor entre o meio de têmpera e a peça a ser resfriada. Um dos métodos de se avaliar os meios de têmpera (meios de resfriamento) e saber o que está acontecendo dentro da peça durante o resfriamento do ponto de vista térmico é o problema inverso de condução de calor. O problema inverso de condução de calor consiste na determinação de parâmetros como fluxo de calor, taxa de resfriamento e temperatura em qualquer posição através da peça, assim como o coeficiente de transferência de calor. Esses parâmetros são obtidos a partir de medições de temperatura em um ou mais pontos dentro da peça. O escopo deste trabalho foi desenvolver um software baseado no problema inverso condução de calor para avaliar meios de resfriamento para têmpera. A validação deste código foi feita usando água, óleo de soja, óleo mineral e solução aquosa de NaNO3. / Steels quenching involves part austenitization followed by a fast cooling to promote martensitic microstructure formation. It is necessary to evaluate quenchants in order to keep the quenching process under control. The most important cooling process parameters are the heat transfer coefficient and/or the heat flux between the quenchant and the part to be cooled. One of the methods to evaluate quenchants (cooling media) and to know what is happening inside the part during the cooling in the thermal point of view is the inverse heat conduction problem. The inverse heat conduction problem consists in the determination of parameters like heat flux, cooling rate and temperature in any position across the part, as well as the heat transfer coefficient. These parameters are obtained from temperature measurements in one or more points inside the part. The scope of this work was to develop a software based in the inverse heat conduction problem in order to evaluate quenchants for quenching. The validation of this code was made using water, soybean oil, mineral oil and NaNO3 aqueous solution.

Abstract This thesis describes a detailed investigation of new glass 10Li₂O−10Na₂O−20K₂O−60MoO₃ (LNKM), ceramic (α-MoO₃) and ceramic-commercial glass (PZ29-GO17, rutile TiO₂-GO17) composites to satisfy the future requirements for ultra-low fabrication temperature materials and their associated processes. The initial part of the thesis is devoted to the development of the LNKM glass by a glass-melting and quenching process, followed by an investigation into its structural, microstructural and microwave dielectric properties. The prepared glass had ultra-low glass transition and melting temperatures of 198 and 350 °C, respectively. The glass pellet heat-treated at 300 °C had a relative permittivity (εr) of 4.85 and a dielectric loss (tan δ) of 0.0009 at 9.9 GHz. The temperature dependence of the relative permittivity was (τε) 291 ppm/°C. Another part of the work concerns α-MoO₃ ceramic, its preparation by uniaxial pressing and sintering at 650 °C followed by an investigation of its structural, microstructural, thermal and microwave dielectric properties. It had an εr of 6.6, tan δ of 0.00013 (at 9.9 GHz) and τε of 140 ppm/°C. In addition to this, a functional ultra-low temperature co-fired composite was developed based on commercial PZ29 and 50 wt.% of GO17 glass followed by tape casting and co-firing with Ag at 450 °C. The average values of the piezoelectric (d₃₃) and voltage (g₃₃) coefficients were 17 pC/N and 30 mV/N, respectively. The sintered sample had an average CTE value of 6.9 ppm/°C measured in the temperature range of 100–300 °C. The εr and tan δ of the sintered substrates were 57.8 and 0.05 at 2.4 GHz, respectively. Additionally, a new ceramic-glass composite was developed using rutile TiO₂-GO17, and co-fired with Ag at 400 °C. It had an average CTE value of 8.3 ppm/°C measured in the temperature range of 100–300 °C. This composite substrate showed εr of 15.5 and tan δ 0.003, at 9.9 GHz. Moreover, it also had τε of -400 ppm/°C at 9.9 GHz measured in the temperature range of −40 to 80 °C. The findings of the thesis reveal the feasibility of the ultra-low temperature co-fired ceramic (ULTCC) technology for high-frequency telecommunication devices as well as for electronics packages. Additionally, a first step to develop functional ULTCC has been taken. / Tiivistelmä Tässä väitöskirjassa kuvataan uuden lasin 10Li₂O−10Na₂O−20K₂O−60MoO₃ (LNKM), keraamin (α-MoO₃) sekä keraami-lasi (PZ29-GO17, rutiili TiO₂-GO17) komposiittien tutkimustulokset, jotka mahdollistavat tulevaisuuden sähkökeraamisten materiaalien ja komponenttien valmistuksen ultra-matalissa valmistuslämpötiloissa. Väitöskirjan alkuosa keskittyy LNKM lasin kehitykseen lasin sulatus- ja karkaisuprosessilla, sekä tämän materiaalin mikrorakenteen sekä mikroaaltoalueen dielektristen ominaisuuksien tarkasteluun. Valmistetulla lasilla oli ultra-matala lasittumislämpötila 198 °C sekä sulamislämpötila 350 °C. Lasipelletin, joka lämpökäsiteltiin 300 °C:ssa, suhteellinen permittiivisyys (εr) oli 4,85 ja dielektriset häviöt (tan δ) 0,0009 9,9 GHz taajuudella. Suhteellisen permittiivisyyden lämpötilariippuvuus (τε) oli 291 ppm/°C. Toinen osa työtä käsittelee α-MoO₃ keraamia, josta valmistettiin näytteet mikrorakenne ja mikroaaltoalueen dielektristen ominaisuuksien tutkimuksiin aksiaalisella puristuksella ja sintraamalla 650 °C:ssa. Valmistetun materiaalin suhteellinen permittiivisyys oli 6,6, häviöt 0,00013 (9,9 GHz:ssa) ja permittiivisyyden lämpötilariippuvuus 140 ppm/°C. Näiden lisäksi kehitettiin toiminnallinen ultra-matalan lämpötilan yhteissintrattu komposiitti perustuen kaupalliseen pietsosähköiseen keraamiin (PZ29) ja lasiin (GO17). Komposiitista valmistetiin monikerrosrakenne nauhavalulla ja yhteissintraamalla hopeaelektrodien kanssa 450 °C:ssa. Keskimääräiset arvot pietsosähköiselle varausvakiolle (d₃₃) sekä jännitevakiolle (g₃₃) olivat 17 pC/N ja 30 mV/N. Sintratun näytteen keskimääräinen lämpölaajenemiskerroin oli 8,3 ppm/°C lämpötila-alueella 100–300 °C. Tämän komposiittisubstraatin suhteellinen permittiivisyys oli 15,5 ja häviötangentti 0,003 9,9 GHz:n taajuudella. Lisäksi suhteellisen permittiivisyyden lämpötilariippuvuus oli -400 ppm/°C samalla 9,9 GHz:n taajuudella, kun lämpötilan mittausalue oli −40–80 °C. Tämän väitöstyön tulokset osoittavat ultra-matalan lämpötilan yhteissintrattavan keraamiteknologian (ULTCC) soveltuvuuden korkean taajuuden tietoliikennesovelluksiin ja elektroniikan pakkausteknologiaan. Lisäksi työssä on otettu ensimmäiset askeleet funktionaalisten ULTCC materiaalien kehittämiseksi.

L’encapsulation dans des nanomatériaux de polymères de colorants ioniques à l’aide de contre-ions hydrophobes volumineux apparaît être une méthode très efficace pour générer des nanoparticules (NPs) fluorescentes ultra-brillantes pour la bioimagerie. Nous avons d’abord étendu cette approche par contre-ions aux colorants cyanine opérant dans la gamme du bleu au proche infra-rouge. A partir de NPs chargés en cyanines, une methode de code-barre multicolore pour le traçage cellulaire à long terme a été développé. Ensuite, le rôle des contre-ions hydrophobes volumineux dans l’auto-assemblage des colorants cationiques à l’intérieur des NPs de polymères a été étudié en testant une large collection d’anions. Nous avons montré qu’une forte hydrophobicité du contre-ion augmente l’encapsulation du colorant, régule son clustering et empêche l’agrégation de nanoparticules, alors qu’une grande taille empêche l’auto-inhibition de fluorescence. Enfin, nous avons introduit les contre-ions à base d’aluminates et de barbiturates, qui sur-performent les tetraphénylborates fluorés. Ce travail procure une base solide au concept d’émission et d’encapsulation augmentées par contre-ions pour la préparation de NPs chargés en colorants fluorescents. / Encapsulation of ionic dyes with help of bulky hydrophobic counterions into polymer nanomaterials emerged as powerful method for generating ultrabright fluorescent nanoparticles (NPs) for bioimaging. Here, this counterion-based approach is extended to cyanine dyes, operating from blue to near-infrared range. Based on cyanine-loaded NPs, a multicolour cell barcoding method for long-term cell tracking is developed. Second, the role of bulky hydrophobic counterion in self-assembly of cationic dyes inside polymeric NPs is studied by testing a large library of anions. We show that high hydrophobicity of a counterion enhances dye encapsulation, prevents particle aggregation and tunes dye clustering, while large size prevents dyes from self-quenching. Third, counterions based on aluminates and barbiturates are shown to outperform fluorinated tetraphenylborates. This work provides a solid basis for counterion-enhanced encapsulation and emission concept in preparation of dye-loaded fluorescent NPs.

Increased knowledge into the physics and chemistrycontrolling emissions from flame-surface interactions shouldhelp in the design of combustion engines featuring improvedfuel economy and reduced emissions. The overall aim of this work has been to obtain afundamental understanding of wall-related, premixed combustionusing numerical modeling with detailed chemical kinetics. Thiswork has utilized CHEMKIN®, one of the leading softwarepackages for modeling combustion kinetics. The simple fuels hydrogen and methane as well as the morecomplex fuels propane and gasified biomass have been used inthe model. The main emphasis has been on lean combustion, andthe principal flow field studied is a laminar boundary layerflow in two-dimensional channels. The assumption has been madethat the wall effects may at least in principle be the same forlaminar and turbulent flames. Different flame geometries have been investigated, includingfor example autoignition flames (Papers I and II) and premixedflame fronts propagating toward a wall (Papers III and IV).Analysis of the results has shown that the wall effects arisingdue to the surface chemistry are strongly affected by changesin flame geometry. When a wall material promoting catalyticcombustion (Pt) is used, the homogeneous reactions in theboundary layer are inhibited (Papers I, II and IV). This isexplained by a process whereby water produced by catalyticcombustion increases the rate of the third-body recombinationreaction: H+O2+M ⇔ HO2+M. In addition, the water produced at higherpressures increases the rate of the 2CH3(+M) ⇔ C2H6(+M) reaction, giving rise to increased unburnedhydrocarbon emissions (Paper IV). The thermal coupling between the flame and the wall (theheat transfer and development of the boundary layers) issignificant in lean combustion. This leads to a sloweroxidation rate of the fuel than of the intermediatehydrocarbons (Paper III). Finally in Paper V, a well-known problem in the combustionof gasified biomass has been addressed, being the formation offuel-NOx due to the presence of NH3 in the biogas. A hybridcatalytic gas-turbine combustor has been designed, which cansignificantly reduce fuel-NOx formation. Keywords:wall effects, premixed flames, flamequenching, numerical modeling, CHEMKIN, boundarylayerapproximation, gasified biomass, fuel-NOx, hybrid catalytic combustor. / QC 20100504

Prokaryotic cells such as Escherichia coli use glucose as their preferred carbon source. In the absence of glucose, these cells resort to other sources to generate glucose and this process of de novo synthesis of glucose is termed gluconeogenesis. Phosphoenolpyruvate carboxykinase (Pck) is one of the three enzymes important in regulating gluconeogenesis. It converts oxaloacetic acid (OAA) from the Krebs cycle to phosphoenolpyruvate (PEP), a glycolytic intermediate. The Pck structural gene (pckA) is regulated by catabolite repression. There is a 100-fold induction of pckA-lacZ fusions at the onset of stationary phase concurrent with induction of glycogen synthesis. Mutants affecting the expression of pckA were analysed to shed some light on the mechanism of its genetic regulation.<p>Spontaneous mutants isolated with Pck- (lack of PEP carboxykinase activity) and Suc- (inability to utilise succinate as carbon source) phenotypes were previously characterised as atpG mutants defective in the ã subunit of ATP synthase.<p>In this work we find by reverse transcriptase and real time quantitative PCR that levels of pckA mRNA are normal in the atpG mutants and that the defects in expression of pckA are therefore likely at the level of translation, protein assembly and/or protein degradation. As expected, ATP synthase activity and proton pumping in inside-out membrane vesicles were defective in these atpG mutants. It is likely that one of these defects is affecting regulation or expression of the pckA gene. It was observed that atpG mutants were defective in calcium-dependent transformation although they could be made competent for electroporation. The atpG mutants were also defective for growth of P1 bacteriophage although they could serve as recipients for P1-dependent generalised transduction. These latter phenotypes are also likely due to defects in energy metabolism.