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This thesis reports an investigation of hydroxypropylmethylcellulose (HPMC) as a new solid-surface room-temperature phosphorescence (SSRTP) sample matrix. The high background phosphorescence originating from filter paper substrates can interfere with the detection and quantitation of trace-level analytes. High-purity grades of HPMC were investigated as SSRTP substrates in an attempt to overcome this limitation. When compared directly to filter paper, HPMC allows the spectroscopist to achieve greater sensitivity, lower limits of detection (LOD), and lower limits of quantitation (LOQ) for certain phosphor/heavy-atom combinations since SSRTP signal intensities are stronger. For example, the determination of the analytical figures of merit for a naphthalene/sodium iodide/HPMC system resulted in a calibration sensitivity of 2.79, LOD of 4 ppm (3 ng), and LOQ of 14 ppm (11 ng). Corresponding investigations of a naphthalene/sodium iodide/filter paper system produced a calibration sensitivity of 0.326, LOD of 33 ppm (26 ng), and LOQ of 109 ppm (86 ng). Extended purging with dry-nitrogen gas yields improved sensitivities, lower LOD's, and lower LOQ's in HPMC matrices when LOD and LOQ are calculated according to the IUPAC guidelines.To test the universality of HPMC, qualitative SSRTP spectra were obtained for a wide variety of probe phosphors offering different molecular sizes, shapes, and chemical functionalities. Suitable spectra were obtained for the following model polycyclic aromatic hydrocarbons (PAHs): naphthalene, p-aminobenzoic acid, acenaphthene, phenanthrene, 2-naphthoic acid, 2-naphthol, salicylic acid, and triphenylene.Filter paper and HPMC substrates are inherently anisotropic, non-heterogeneous media. Since this deficiency cannot be addressed experimentally, a robust statistical method is examined for the detection of questionable SSRTP data points and the deletion of outlying observations. If discordant observations are discarded, relative standard deviations are typically reduced to less than 10% for most SSRTP data sets. Robust techniques for outlier identification are superior to traditional methods since they operate at a high level of efficiency and are immune to masking effects.The process of selecting a suitable sample support material often involves considerable trial-and-error on the part of the analyst. A mathematical model based on Hansen's cohesion parameter theory is developed to predict favorable phosphor-substrate attraction and interactions. The results of investigations using naphthalene as a probe phosphor and sodium iodide as an external heavy-atom enhancer support the cohesion parameter model.This document includes a thorough description of the fundamental principles of phosphorimetry and provides a detailed analysis of the theoretical and practical concerns associated with performing SSRTP. In order to better understand the properties of both filter paper and HPMC, a chapter is devoted to the discussion of the cellulose biopolymer. Experimental results and interpretations are presented and suggestions for future investigations are provided. Together, these results provide a framework that will support additional advancements in the field of solid-surface room-temperature phosphorescence spectroscopy. / Ph. D.

Ce travail porte sur la stabilisation de flammes prémélangées et swirlées de mélanges combustibles méthane/hydrogène/air avec différents taux de dilution d’azote et de dioxyde de carbone. Une tige centrale permet de stabiliser des flammes pour de faibles nombres de swirl. Le sommet de la flamme interagît éventuellement avec les parois de la chambre de combustion. L’objectif ces travaux est d’améliorer la connaissance des mécanismes qui gouvernent la stabilisation et la topologie de ces flammes. Ces travaux démontrent que le nombre de swirl, la composition du mélange combustible, la géométrie de la chambre de combustion ainsi que les conditions aux limites thermiques ont une grande influence sur la forme prise par la flamme. Le dispositif expérimental permet de modifier la forme et la taille de la chambre de combustion, le diamètre du tube d’injection et le nombre de swirl. Des conditions opératoires propices aux transitions de forme de flamme sont ensuite étudiées pour différentes configurations de brûleur. Une caractérisation expérimentale fouillée d’un point de fonctionnement est réalisée grâce à la Fluorescence Induite par Laser sur le radical Hydroxyle (OH-PLIF), la Vélocimétrie par Images de Particules (PIV) et la Phosphorescence Induite par Laser de phosphores sensibles à la température (LIP). Une base de donnée de l’écoulement et des conditions aux limites associées est obtenue sans et avec combustion. Les mécanismes qui contrôlent les transitions de formes de flamme sont ensuite analysés lorsque la flamme interagit avec les parois de la chambre de combustion. L’influence de la composition du mélange combustible, de la vitesse débitante et du nombre de swirl est caractérisée et il est démontré que la transition d’une flamme en V vers une flamme en M est déclenchée par un retour de flamme dans la couche limite le long d’une des parois latérales de la chambre de combustion. Les nombres sans dimension contrôlant ces transitions sont identifiés et un modèle de prévision de la forme de ces flammes est développé. La physique déterminant les transitions de forme de flammes est différente lorsque celles-ci n’interagissent pas avec les parois de la chambre de combustion. En utilisant le signal de chimiluminescence OH* et la OH-PLIF, il est montré que la teneur en hydrogène dans le combustible a une grande influence sur la forme de flamme. L’utilisation de la LIP et de thermocouples a également permis de montrer que les conditions aux limites thermiques jouent un rôle prépondérant sur la forme de flamme. Les effets combinés de l’étirement et des pertes thermiques sont examinés par l’utilisation conjointe de la PIV et de la OH-PLIF. Il est montré que les limites d’extinction de flammes pauvres prémélangées sont réduites par les pertes thermiques et que la transition d’une flamme en M vers une flamme en V est consécutive à l’extinction du front de flamme situé dans la couche de cisaillement externe du jet soumis à un étirement trop important. Ces expériences sont complétées par une analyse de la dynamique de ces flammes. Des modulations de la vitesse débitante à basse fréquence et à haute amplitude modifient la forme de flamme. La stabilisation de flammes CH4/H2/air diluées par du N2 ou du CO2 est finalement examinée. La zone de recirculation produite par la tige centrale permet d’alimenter la base de la flamme avec des gaz brûlés chauds et de stabiliser des flammes fortement diluées. Augmenter la fraction molaire de diluant dans le combustible réduit l’intensité de lumière émise par le radical OH*. Il est également montré que la composition du diluant a un impact sur le champ de température des gaz brûlés et des surfaces de la chambre de combustion. La dilution par du CO2 augmente les pertes thermiques par rayonnement des gaz brûlés. Cela réduit l’efficacité de la chambre de combustion équipée de quatre parois transparentes. [...] / This work deals with the stabilization of premixed turbulent swirling flames of methane/hydrogen/air combustible mixtures with different dilution rates of nitrogen and carbon dioxide. A central bluff body helps stabilizing the flames at low swirl numbers. The flame tip eventually impinges the combustor peripheral wall. The general objective is to gain understanding of the mechanisms governing the stabilization and the topology of these flames. It is found that the swirl number, the combustible mixture composition, the geometry of the combustor, and the thermal boundary conditions have a strong impact on the shape taken by these flames. The experimental setup used to characterize flames topologies is first described. Flames prone to topology bifurcations are selected and are studied for different arrangement of the combustor when the combustion chamber shape and size, the injection tube diameter, and swirl number are varied. One operating condition is fully characterized under non-reactive and reactive conditions using Planar Hydroxyl Laser Induced Fluorescence (OH-PLIF), Particle Imaging Velocimetry (PIV), and Laser Induced Phosphorescence of thermographic phosphors (LIP) to generate a detailed database of the flow and the corresponding boundary conditions. An analysis is then conducted to understand the mechanisms controlling shape bifurcations when the flame interacts with the combustor peripheral wall. Effects of the combustible mixture composition, the bulk flow velocity, and the swirl number are analyzed. It is shown that the transition from a V to an M flame is triggered by a flashback of the V flame tip in the boundary layer of the combustor peripheral wall. Dimensionless numbers controlling these transitions are identified and a simplified model is developed to help the prediction of the flame shapes. The physics of these shape bifurcations differs when the flame does not interact with the combustor wall. The large influence of the hydrogen enrichment in the fuel on the flame shape is analyzed using flame chemiluminescence and OH-PLIF. LIP and thermocouple measurements demonstrate that the thermal boundary conditions still have a strong impact on the flame topology. The combined effects of strain and heat losses are investigated using joint OH-PLIF and PIV experiments. It is shown that flammability limits of premixed flames are reduced due to heat losses and the transitions from M to V shaped flames is consecutive to localized extinctions of flame front elements located in the outer shear layer of the jet flow that are submitted to large strain rates. These experiments are completed by an analysis of the dynamics of methane/hydrogen/air flames. It is shown that low frequency and high amplitude velocity modulations generated by a loudspeaker alter the shape taken by these flames. The stabilization of methane/hydrogen/air flames diluted by nitrogen and carbon dioxide is finally examined. It was possible to stabilize swirled flames featuring important dilution rates due to the presence of the bluff body, installed on the axis of the injection tube. The recirculation zone behind this element supplies hot burnt gases to the flame anchoring point. Using OH* chemiluminescence imaging, it is shown than increasing the molar fraction of diluent in the fuel reduces the light emission from excited OH* radicals. The influence of dilution on the flame chemistry is emphasized with experiments conducted at a fixed thermal power and fixed adiabatic flame temperature. It is also demonstrated that the composition of the diluent has a strong influence on the temperature field of the burnt gases and of the combustor wall surfaces. Dilution with carbon dioxide increases radiative heat losses from the burnt gases in comparison to dilution with nitrogen. This penalizes the combustor efficiency equipped with four transparent quartz walls. [...]

Les espèces réactives de l'oxygène sont générées dans l'environnement biologique dans le cadre du métabolisme, mais elles peuvent aussi être produites en excès dans le cas de stress oxydatif provoqué par exemple par une exposition aux rayons UV. Dans le travail présenté ici, nous sommes intéressés par l'oxydation des protéines par deux de ces espèces réactives de l'oxygène : le peroxyde d'hydrogène, oxydant plutôt faible avec un temps de vie long, et l'oxygène singulet, oxydant fort avec un temps de vie court. L'action de ce dernier sur les protéines est étudiée en utilisant la spectroscopie de phosphorescence résolue en temps et l'oxydation des protéines par le peroxyde d'hydrogène est suivie par spectroscopie Raman. Dans ce cas, un travail préliminaire a été nécessaire afin d'attribuer de manière précise les bandes Raman des chaînes latérales des résidus d'acides aminés. Pour les deux types d'oxydations, les constantes de vitesse des réactions ont été déterminées pour trois protéines modèles. La stratégie suivie est d'utiliser de petits fragments de protéines tels que des acides aminés libres et des tripeptides pour comprendre ce qui se passe à l'échelle de la protéine. Cela nous aide à souligner l'importance de l'environnement protéique. Dans le cas de l'étude par spectroscopie Raman, l'influence du nombre de liaisons peptidiques sur les spectres obtenus depuis l'acide aminé libre, au tripeptide, jusqu'à la protéine est aussi mis en évidence. / Reactive species of oxygen are generated in biological environment as part of metabolism but they can also be produced in excess in case of oxidative stress provoked by UV exposure for example. In the present work we are interested in the oxidation of proteins by two of those reactive species of oxygen : hydrogen peroxide, rather weak oxidant with a long life time, and singlet oxygen, a strong oxidant with a short life time. The action of the latter one on the proteins is studied by using time-resolved phosphorescence spectroscopy and oxidation of the proteins by hydrogen peroxide is monitored by using Raman spectroscopy. In this case a preliminary work was necessary to attribute accurately the Raman bands of amino-acid residues side chains. For both oxidations, reaction rate constants of the reactions were determined for three model proteins. The strategy followed is to use small fragments of proteins such as free amino-acids and tripeptides to understand what is happening at the protein scale. This helps us underlining the importance of the proteic environment. In the case of Raman spectroscopy study, it also shows the influence of the number of peptidic bonds on the spectra obtained from free amino-acid to tripeptide and then to protein.Keywords : Raman Spectroscopy, protein, oxidation, hydrogen peroxide, singlet oxygen, time-resolved phosphorescence spectroscopy, reaction rate constant.

Here, the design, synthesis and characterisation and the optoelectronic properties of Ir(III) complexes for application in nonlinear optical and electroluminescent devices are described. The type of complexes varies from those of the form [Ir(C^N)2(N^N)]+ with conjugated and nonconjugated ligands (where C^N = cyclometalating ligand and N^N = neutral ligand) to those of the form [Ir(C^N^C)(N^N)Cl] (where C^N^C = tridentate tripod ligand). Chapter 1 gives an introduction into photophysics occurring in transition metal complexes and possible applications in visual displays. The background of nonlinear optical (NLO) properties and the use of transition metal complexes as NLO chromophores is described. In Chapter 2, the impact of the use of sterically congested cyclometalating ligands on the photoluminescence properties of cationic iridium(III) complexes and their performance in light-emitting electrochemical cells is investigated. Chapter 3 explores the use of electron donors on the cyclometalating ligand towards modulating the NLO properties of the complexes. Combining strongly electron-donating substituents on the C^N ligand and electron-accepting substituents on the N^N ligand results in strong NLO activity. Chapter 4 summarises a new series of cationic iridium(III) complexes bearing benzylpyridinato as cyclometalating ligands. The methylene spacer in the C^N ligands provides flexibility, resulting in two conformers. NMR studies combined with density functional theory (DFT) studies show how the fluxional behaviour is influenced by the choice of the ancillary ligand. In Chapter 5, Ir(III) complexes bearing an unusual nonconjugated bis(six-membered) tridentate tripod ligand of the form [Ir(C^N^C)(N^N)Cl] are introduced. Depending on the substitutions of the C^N^C ligand phosphorescence ranging from yellow to red was obtained. Substitution of the N^N results in a panchromatic NIR dye, suitable for DSSC applications. In Chapter 6, the concept of a nonconjugated ligand was expanded to the N^N ligand. Blue-green and sky-blue emission was obtained, demonstrating a strategy to successfully tune the emission to the blue.

Luminescent materials can be found in a broad range of everyday applications. While in the seventies and eighties, the field of luminescent materials seemed to be fairly well covered, research in nineties has been revitalized both in industry and academia. Improvements over the last three decades have led to phosphor materials that operate close to their physical limits. It cannot be expected that properties such as quantum yield and spectral energy distribution will be significantly improved or that distinctly better materials will be found in the near future. Recently, there is a considerable research activity in the field of luminescent materials for lighting and displays to improve the chemical stability and to adopt the materials to the production technology. Ongoing miniaturization, lifetime improvement and spectral stability of fluorescent lamps on the one hand and brightness and contrast improvement in imaging systems on the other hand demand luminescent materials with very high stability that is invariable to operating conditions. All of the today's efficient lighting sources are based on either direct or indirect light emission from plasma discharges. During the pioneering stage, fluorescent lamp industries predominantly used mixtures of two photo luminescent materials: (Zn,Be)2SiO4.'Mn2+ having two emission maxima at 520 and 600 nm and MgW04 with 480 nm emission. The emission from these two phosphors covers the major portion of the visible spectrum. However, the compound (Zn,Be)2Si04 is hazardous to health because of its beryllium content. In 1942, Jenkins showed that Ca5(PO4)3(F,Cl):Sb,Mn was a very efficient emitter. The halophosphates emit both in the blue (Sb3+) as well as in the orange (Mn2+) spectral region, thus in addition yield white light. By carefully adjusting the ratio of Sb3+ and Mn2+ ion concentrations, a white light emitting phosphor was obtained with color temperatures ranging between 6500 and 2700K. However, the drawback of the halophosphate lamps is that it is impossible to have simultaneously high brightness and high color rendering; if the brightness is high (efficacy -80 lm W"1), the color rendering index (CRI) is of the order of 60, the CRI value can be improved up to 90, but then brightness decreases (-50 lm W"1). In 1974, another important breakthrough came in the form of compact fluorescent lamp, based on the trichromatic phosphor blend which resulted color rending values of 80-85 (color 80 lamps) at high efficiencies of 100 lm W"1. The fluorescent lamps with very high color rendering and efficiency can be obtained if three narrow band emitters with emission maxima at 450, 540 and 610 nm are employed. A typical trichromatic lamp phosphor blend comprises of (i) Sr5(PO4)3Cl:Eu2\ BaMgAl1()O,7:Eu2' as blue component, (ii) Ce0.67Tbo.33MgAl,,0,9, LaPO4,Le3\Tb3+ as green component and (iii)Y2C>3:Eiru as the red component. The color 80 lamps employ line emitters that generated light in discrete wavelength intervals. Colored objects that absorb outside these spectral regions appear with a slightly different body color when illuminated with these lamps rather than with a black body radiator such as the light bulb. For these purposes, color 90 or Deluxe lamps have been developed. The emission maximum of the blue phosphor can be shifted towards longer Wavelength by substituting BaMgAli0Oi7:Eu2+ with Sr4Ali4025:Eu2+. The red and green line emitters can be substituted by broad band emitters covering the whole spectral range. For this concept, (Ce,Gd,Tb)MgB5Oi0:Mn has been developed as a red emitter in which energy transfer from Ce3+ via Gd3+ to Mn2+ gives rise to an additional broad band at 630 nm. On the other hand, (Ba,Sr,Ca)2Si04:Eu has been developed as an alternative green-band emitter in which depending on the exact composition, the phosphor emits between 550 and 580 nm with a high quantum yield. Unfortunately, the host lattice is not stable in water, which prevents its deposition on the lamp bulb from aqueous suspensions and for environmental reasons more and more lamps producers use water as the suspending solvent in production instead of butyl acetate. Therefore, it is necessary to develop a new full color emitting phosphors, which has both thermal and chemical stability for application in luminescent lighting. The classical cathode ray tube (CRT) invented as the brown tube more than 100 years ago has developed into a remarkably mature product considering the complexity of its manufacturing process. Cathode rays are a beam of fast electrons, the accelerating voltage in a television picture tube is high (>10 kV). Basic requirements of display phosphors are stability (2000 hr operation) and emission color purity according to the standards set by the European Broadcasting Union (EBU). The blue and green phosphors are still the very cheep ZnS based materials, essentially the same ever since color-TV was introduced in fifties. On the other hand, (Zn,Cd)S, Ag+,C1" was originally used as the red phosphor however, the broad emission centered at 650 nm due to intrinsic donor-acceptor transition leads to rather low lumen equivalent as large fraction of the emission integral lies outside the eye sensitivity curve. For this and the environmental reasons, it has been replaced by the much more expensive Y2O2S:Eu with main emission lines at 612 and 628 nm. Recently, the big electronic companies are trying to enforce flat panel displays e.g. PDPs (plasma display panels) and FEDs (field emission displays). This is because of the fact that when compared to the CRT screen pigments, FED phosphors are required to operate at lower voltages and higher current densities. Although the voltages used in FEDs are only 0.1 to < 2 kV, the high-energy surface excitation on the phosphor particles causes degradation of sulfides, leaving the oxide hosts as the only favorable choice. The phosphor blends used are mixtures of SrTiO3:Pr3+ (red), Y2Si05:Tb (green) and Y2Si05:Ce (blue). However, the white light generation efficiency is very low (-5 lm W"1) and required improvement of phosphor efficacy because of its distinct advantages such as a very wide range of operational temperatures, stability under rugged conditions and wide viewing angle of emission. Similarly, in PDPs blue emitting BaMgAlioOniEu, green emitting Z^SiO^Mn and red emitting (Y,Gd)BO3:Eu are mostly used which shows a screen efficiency of about 1.5 lm W"1, just only half that of a CRT used in today's TV sets. However, the advantages of PDPs over CRTs are that it is not sensitive towards the display manufacturing process, which includes high temperature annealing up to about 600°C and it is stable under the harsh conditions of a Ne/Xe plasma used in PDPs (ion bombardment, VUV radiation). This puts pressure on the development of phosphor for maximum brightness and high stability to replace completely the classical CRTs. On the other hand, the invention of the blue-light emitting diode (LED) based on GaN can be regarded as a triumph of materials chemistry. In principle, it is possible to vary the emission wavelength of blue GaN-based LEDs between 370 nm (band-gap of pure GaN) and 470 nm by increasing the indium (In) content in InGaN devices. Assuming a conversion from the incident light by a phosphor material emitting at 555 nm, InGaN is coated with (Yi.xGdx)3(Ali-yGay)5Oi2:Ce (YAG:Ce) which has broad yellow band varying between 510 and 580 nm. This allows the adjustment of white color temperature from 8000 down to 3000 K. Recently, S^SiCU and S^SiOs have attracted current interest due to their potential applications in developing white light-emitting-diodes (LEDs) because GaN (400 nm chip)-coated with Sr2Si04:Eu2+ or Sr3SiC>5;Eu2+ exhibits better luminous efficiency than that of the industrially available product such as InGaN (460 nm chip)-coated with YAG:Ce. However, the major drawback of this combination is the strongly decreasing overall efficiency upon lowering the color temperature. This can be solved by using a phosphor material that has sufficient absorption at the emission wavelength of the blue diode, the quantum yield should be high under UV/Vis excitation and the FWHM of the emission band should be as small as possible in order to achieve high luminous output. The search for stable inorganic rare-earths phosphors with high absoiption in the near UV/blue spectral region is therefore an attractive research work. Since luminescence materials are a key component for lighting and display concept, research in the field of rare-earths doped oxide phosphors is carried out. Although state-of-the-art materials fulfill most requirements, improvements are still necessary to further boost the efficiency of the phosphor materials. Since it is not expected that materials will be found that perform better than the already established phosphor, the present work concentrates on the improvements of the phosphor by modifying the chemical and niicrostructurai features as well as the crystal structure. Chapter I gives a brief introduction to luminescence in solids, physical aspects and applications. Chapter II describes the synthesis and various experimental techniques employed in the investigation. Chapter III deals with photoluminescence and energy transfer involving charge transfer states in Sr2-xLnxCe04+x/2 (Ln = Eu and Sm) leading to an efficient full color emitting phosphor for luminescent lighting. Chapter IV and V describe charge transfer transition involving interface states associated with transitional nanophaseprecipitates leading to photoluminescence enhancement of SrTiO3:Pr3+,Al3+ and SrAli2Oi9:Pr3+,Ti4\ The light induced charge transfer leading to changing oxidation state of Eu in Sr2Si04 involving transient crystal structure results an efficient material for optical storage is presented in Chapter VI.Photoluminescence due to efficient energy transfer from Ce3+ to Tb3+ and Mn2t in SnAlioSi02o leading to an efficient phosphor for FEDs is presented in Chapter VII. Chapter VIII describes charge transfer transition involving trap states leading to long phosphorescence in SrAl2-xBxO4 (0<x<0.2) and Sr4Al14.xBxO25 (0.1<x<0.4) co-doped with Eu2+ and Dy3+. Chapter IX presents the role of particle size on the charge transfer associated luminescence of GdVO4:Ln3+ (Ln = Eu and Sm). A summary of the important findings and the conclusions arrived on the basis of results from these investigations are presented at the end of the thesis.

The electronics industry today is one that stands as a multi-billion dollar industry that is increasingly incorporating more and more products that have ever escalating applications in our everyday life. One of the main sectors of this industry, and one that is likely to continue expanding for a considerable number of years are flat-panel displays. Traditionally, the displays market has been dominated by cathode ray tube (CRT) and liquid crystal displays (LCDs) display types. The drawback of such display displays is that they can be bulky, heavy and/or expensive and so there is considerable room for an alternative and superior technology. One possibility is organic semiconductor displays where light-emitting molecules can be dissolved in common solvents before being inkjet printed, spin-coated or even painted onto any surface giving the benefits of simple and cost effective processing. Organic light-emitting diodes (OLEDs) have recently become ever more evident as a major display type. This thesis focuses on the advancement of light-emitting dendrimers towards flat-panel display applications. The particular interest in dendrimers arises because it has been found they are capable of giving solution-processed phosphorescent devices with high efficiency. Throughout the thesis the benefits of the dendrimer concept are repeatedly shown revealing why this could become the ideal organic material for display applications. The thesis introduces various techniques of electroluminescence and photoluminescence measurements before applying such methods to study a large number of light-emitting dendrimers in order to explore the role of intermolecular interactions, how they are related to molecular structure, and how this determines photophysical and charge transporting properties of the dendrimers. By such studies a number of highly efficient solution-processed phosphorescent light-emitting dendrimers have been identified while the efficiency of devices made from these dendrimers has been improved. This has been demonstrated in each of the three primary display colours of red, green and blue. The work detailed thus brings closer the prospect of dendrimer light-emitting diodes being the future flat-panel display type of choice.

An extension of the current acetone Planar Laser-Induced Fluorescence (PLIF) was formulated for mixing studies of fluids at subcritical and supercritical conditions. The new technique, called Planar Laser-Induced Fluorescence and Phosphorescence (PLIFP), employs the difference in the mass diffusivity of the denser (liquid) to the less dense (vapor/supercritical fluid) to delineate the interface where a phase change occurs. The vapor/supercritical acetone fluorescence signal is utilized to measure of the acetone vapor density, the mixture fractions and liquid acetone phosphorescence signal to determine the location of the phase interface. The application of the technique requires the photophysical properties of vapor and liquid acetone to be known. Therefore, a series of controlled experiments were done to determine their photophysics at elevated temperatures and pressures up to T/TC = 1.2 and p/pC =1.25. The demonstration of the techniques shows it was able to provide quantitative measurements of acetone number density and the overall mixture fraction within the test chamber. Also, the size and mass of droplets that have broken off from the main jet were determined as well, though the ability is limited to small droplets (d~100 μm). In addition, the technique was able to delineate the low diffusivity (subcritical)/high diffusivity (supercritical) interface very well.

[pt] Um estudo foi realizado visando avaliar nova abordagem analítica para a determinação de um hidrocarboneto poliaromático nitrogenado (carbazol, CBZ) e um sulfurado (dibenzotiofeno, DBT) em amostras orgânicas líquidas usando fosforimetria na temperatura ambiente. Para isto, microemulsões sem detergente foram usadas para viabilizar a determinação destes compostos em solução. Um estudo preliminar das propriedades fosforescentes desses dois analitos foi realizado, sendo este dividido em duas etapas: (i) definição da composição da microemulsão (ME) e (ii) estudo do efeito da concentração da ME sobre o sinal fosforescente do analito. Como resultado, sinais fosforescentes com potencial analítico e em ambiente livre de interferências de fluorescência foram obtidos para várias das composições testadas. As condições experimentais foram otimizadas usando planejamento fatorial visando à maximização desses sinais fosforescentes para o CBZ (292/436 nm) e para o DBT (286/442 nm). A concentração de I- (íon de átomo pesado indutor de fosforescência), concentração de Na2SO3, pH e tipo de ME foram avaliadas. Essa abordagem permitiu que, na ME diluída, os valores de LD e de LQ para o CBZ fossem 2,6 ng mL-1 e 8,6 ng mL-1 e para o DBT de 7,4 ng mL-1 e 24,5 ng mL-1. As faixa lineares estenderam-se até 800 ng mL-1 (CBZ) e até 1400 ng mL-1 (DBT). Amostras orgânicas líquidas (frações combustíveis do petróleo e extratos orgânicos de amostras ambientais) fortificadas com os analitos foram usadas para testar os métodos. Estratégias apropriadas para cada tipo de amostra são apresentadas. Porcentuais de recuperação para CBZ e para o DBT ficaram dentro da faixa de 90 a 110 %. Interferências mútuas e de outras substâncias foram avaliadas. / [en] A new approach for the determination of one nitrogen- containing PAH (carbazole, CBZ) and one sulfur-containing PAH (dibenzothiophene, DBT) in organic liquid samples using room-temperature phosphorimetry was evaluated. Detergentless microemulsions were used to allow the determination of these compounds in aqueous solution. A preliminary study of the phosphorescent properties of the analytes was made in two steps: (i) definition of the ME composition and (ii) effect of the concentration of the ME on the analyte phosphorescent signal. As a result, phosphorescent signals with analytical potential, in a fluorescence free environment, were obtained for several tested compositions. Experimental conditions were optimized using a factorial design aiming the maximization of the phosphorescence from CBZ (292/436 nm) and DBT (286/442 nm). The concentration of I- (phosphorescence inducer heavy atom ion), concentration of Na2SO3, pH and ME type were evaluated. The method allowed, in the diluted ME, values for LD and for LQ of 2,6 ng mL-1 and 8,6 ng.mL-1for CBZ and of 7,4 ng mL-1 and 24,5 ng mL-1 for DBT. Linear dynamic ranges extended up to 800 ng mL-1 (CBZ) and up to 1400 ng mL-1 (DBT). Organic liquid samples (petroleum fuel fractions and organic extracts of environmental samples) spiked with the analytes of interest were used to test the methods. Proper strategies for analyzing each type of sample were described. Recoveries for CBZ and for DBT were within the 90 to 110 % range. Mutual interferences and interferences from other substances were evaluated.

Phosphorescent transition metal complexes make up an important group of compounds that continues to attract intense research owing to their intrinsic bioimaging applications that arise from bright emissions, relatively long excited state lifetimes, and large stokes shifts. Now for biomaging assay a model organism is required which must meet certain criteria for practical applications. The organism needs to be small, with a high turn-over of progeny (high fecundity), a short lifecycle, and low maintenance and assay costs. Our model organism C. elegans met all the criteria. The ideal phosphor has low toxicity in the model organism. In this work the strongly phosphorescent platinum (II) pyrophosphito-complex was tested for biological applications as a potential in vivo hypoxia sensor. The suitability of the phosphor was derived from its water solubility, bright phosphorescence at room temperature, and long excited state lifetime (~ 10 µs). The applications branched off to include testing of C. elegans survival when treated with the phosphor, which included lifespan and fecundity assays, toxicity assays including the determination of the LC50, and recovery after paraquat poisoning. Quenching experiments were performed using some well knows oxygen derivatives, and the quenching mechanisms were derived from Stern-Volmer plots. Reaction stoichiometries were derived from Job plots, while percent scavenging (or antioxidant) activities were determined graphically. The high photochemical reactivity of the complex was clearly manifested in these reactions.