Neste trabalho, estudou-se o efeito da adição de acetonitrila nas propriedades de micelas do detergente aniônico, dodecil sulfato de sódio (SDS), e do detergente catiônico, cloreto de hexadeciltrimetilamônio (CTACl). Medidas de condutividade foram utilizadas para determinar a concentração micelar crítica, cmc, e o grau de dissociação, α, das micelas em função da fração molar de acetonitrila, XAc. Medidas de supressão de fluorescência, resolvida no tempo, com pireno como sonda, foram utilizadas para determinar a influência de acetonitrila no número de agregação das micelas, N, e na dinâmica de migração de solutos entre as fases aquosa e micelar. Em baixas frações molares XAc < 0,2), a acetonitrila insere-se nas cavidades da água, quebrando parcialmente as pontes de hidrogênio da água com a formação de novas pontes de hidrogênio entre as moléculas de acetonitrila e as moléculas de água. Nesta faixa de concentração, ocorre um aumento da cmc e do α, acompanhada de uma diminuição de N. Observa-se também alterações na dinâmica da interação de contra-íons e co-íons supressores na micela. Assim, as micelas de SDS e CTACl formadas em misturas acetonitrila-água são menores, mais dissociadas e apresentam maior fluidez interna. Ao redor de XAc = 0,2, as misturas de água-acetonitrila tornam-se microheterogêneos com o aparecimento de microdomínios ricos em acetonitrila e microdomínios ricos em água. A proporção das regiões ricas em acetonitrila aumenta com o aumento da fração molar de acetonitrila, com apenas pequenas modificações das propriedades dos dois tipos de microdomínios. Em XAc > 0,2 a variação de cmc e de α com a XAc passa a ser menos acentuada, sugerindo que o detergente forma agregados preferencialmente nas regiões mais aquosas; a sonda fluorescente pireno começa sair das micelas durante o tempo de vida do estado excitado; e há claras mudanças na dinâmica de incorporação de íons nos agregados. / This work presents a study of the effect of added acetonitrile on the properties of the micelles of the anionic detergent sodium dodecylsulfate (SDS) and the cationic detergent hexadecyltrimethylammonium chloride (CTACl). Conductimetric measurements were employed to determine the critical micelle concentration, cmc, and the degree of counterion dissociation, α, of the micelles as a function of the mole fraction of added acetonitrile, XAc. Time resolved fluorescence quenching measurements with pyrene as probe were employed to determine the effect of acetonitrile on the micellar aggregation number, N, and the dynamics of solute migration between the micellar and aqueous phases. At low mole fractions (XAc < 0.2), acetonitrile inserts into the cavities present in liquid water, partially disrupting the hydrogen bonding of water, with formation of new hydrogen bonds between water and acetonitrile. In this range, both the cmc and α increase, while N decreases. The dynamics of incorporation of counterionic and coionic quenchers into the micelles is also altered. Thus, the SDS and CTACl micelles formed in these acetonitrile-water mixtures are smaller, more highly dissociated and internally more fluid than those in aqueous solution. Above XAc of ca. 0,2, acetonitrile-water mixtures become microheterogeneous, the solution containing microdomains rich in acetonitrile and microdomains rich in water. The proportion of acetonitrile-rich microdomians increases with increasing XAc, with only small changes in the properties of the two types of microdomains. Correspondingly, at XAc > > ca. 0.2: the variation of the cmc and α with XAc is much less pronounced, suggesting that the detergent forms aggregates preferentially in the aqueous-rich domains; the fluorescence probe pyrene begins to exit the micelles during its excited state lifetime; and there are distinct changes in the rate constants for the incorporation of ions into the micelles.

Ce travail de thèse a démontré la possibilité de mesurer la relaxation d’un complexe biomoléculaire ainsi que son hétérogénéité structurale, en associant la microfluidique et la fluorescence résolue en temps (FRT). Je présente de quelle façon la FRT permet d’obtenir une information sur la structure d’une molécule et comment on la mesure, notamment grâce à une caméra à balayage de fente. J’introduis ensuite la microfluidique de gouttes, permettant de mélanger deux réactifs en quelques millisecondes et de suivre la relaxation du complexe au cours de la propagation des micro-réacteurs. Puis, la mesure d’une cinétique avec un couple de molécules modèle démontre la preuve de principe, faisant l’objet d’un article soumis. Enfin la mesure de FRT par comptage de photons uniques dans des gouttes uniques est décrite. Elle ouvre une perspective d’application pour le criblage à haut débit : un brevet a été déposé. / This thesis has proven the feasibility of measuring the relaxation of a biomolecular complex as well as its structural heterogeneity, by associating microfluidics and time resolved fluorescence (TRF). I present in which way TRF allows for probing the structure of a molecule and how it is measured, in particular by using a streak camera. I then introduce droplet microfluidics, which enables to mix two reagents in a few milliseconds and to follow the relaxation of the complex, along propagation of the micro-reactors. Next, the measurement of a kinetics with test molecules validates the proof of concept, reported in a submitted article. Finally, the measurement of TRF by single photon counting in single droplets is described. It opens a perspective for an application in high-throughput screening: a patent has been registered.

The rise in the world population can be correlated with an increase in energy need. Fossil fuels are not going to able to cover this need in energy because not only are they limited, they also have a negative effect on the environment. A reason the more to switch renewable energy. One of the most popular renewable energy source is solar energy. The organic solar cell could be a low-cost, light-weight and flexible option for photovoltaics. This thesis will discuss the morphology of the active layer of an organic solar cell. The polymer poly(9,9-dioctylfluorenyl-2,7-diyl) and the fullerene derivate [6,6]-phenyl C61-butyric acid methyl ester were used as model components for the active layer. These two components were processed in different solvents, different ratios, different total concentrations and were either dip- or spin-coated on glass substrates. These samples were analyzed with atomic force microscopy, steady state and time resolved fluorescence and UV/Vis spectroscopy. The analysis show that the morphology of the films processed in chloroform and tetrahydrofuran would react very similar in α-phase and β-phase by dip- and spin-coated samples. Xylene would react the opposite as tetrahydrofuran and chloroform while ethylbenzene would react little with different samples. / De stijging in wereldpopulatie kan gelinkt worden met een stijging in energieverbruik. Het is niet aan te raden om fossiele brandstoffen te gebruiken voor deze energiestijging want niet alleen zijn ze beperkt aanwezig op aarde ook zijn ze niet goed voor het milieu. Een reden te meer om naar duurzame energie over te schakelen. Één van de meeste populaire energiebronnen is zonne-energie. Hierbij zou de organische zonnecel een goedkope, lichte en flexibele optie zijn. Deze thesis zal de morfologie van de actieve laag van een zonnecel bespreken. Het polymeer poly(9,9-dioctylfluorenyl-2,7-diyl) en het fullereen derivaat [6,6]-fenyl C61-butylzuur waren de twee model componenten voor de actieve laag. Deze twee componenten werden in verschillende oplosmiddelen, verschillende verhoudingen en verschillende totaal concentraties bereidt en werden vervolgens gedipcoated of gespincoated op glazen substraten. De stalen werden vervolgens geanalyseerd door atomic force microscopy, steady state en time resolved fluorescence en UV/Vis spectroscopy. De analyse toont dat de morfologie van de films bereidt in chloroform en tetrahydrofuraan gelijkaardig reageren in α- fase en β-fase bij gedipt- en gespincoaten stalen. Terwijl xyleen net omgekeerd reageert als chloroform en tetrahydrofuraan. Bij ethylbenzeen zou de fases maar heel weinig veranderen bij de verschillende stalen.

Hyaluronan is a chemical, which can be qualified as essential for vertebrates. It is a part of the extracellular matrix in most of tissues and also a major component of some other tissues. Besides of the mechanical functions this compound is important for many biological processes such as growth of tumor cells. The objective of this thesis was development of carrier systems containing native hyaluronan and hydrophobic drugs. For purposes of this work fluorescence probes (pyrene, prodan, perylene, DPH, mereocynine 540) instead of drugs were used. By using further mentioned sophisticated methods the properties of these systems were studied. The systems were prepared by freeze-drying. The effect of freeze-drying on support of interactions was observed by fluorescence spectrometry (steady-state and time-resolved). The stability of freeze-dried systems was determined by zeta potential, which was measured by electrophoretic light scattering. Cakes obtained by freeze-drying were analyzed by several methods. First one was effluence gas chromatography connected with FT-IR spectrometry. In this method the present of tertiary butyl alcohol in product was observed. The cakes were also analyzed by scanning electron microscopy, which can provide the information about the surface and elemental constitution of the material. The results of this work can shed light on the area of developing of drugs with targeted distribution of active compound.

The deprotonation characteristics of fluorescent probes -naphthol and 8-hydroxypyrene-1,3,6-trisulphonic acid (HPTS) were studied in this diploma thesis, using steady-state and time-resolved fluorescence spectroscopy. Two cationic surfactants, Septonex and cetyltrimethylammonium bromide (CTAB), were studied. These surfactants were measured in the complex with hyaluronan (1.75 MDa, 1 MDa and 300 kDa). Steady-state fluorescence was used for determination of critical aggregation concentration of each surfactant and pKa*. Time-resolved fluorescence decays were used to calculate the average lifetimes and the deprotonation constants of naphthol and HPTS. The measurement with hyaluronan were compared with the polystyrenesulfonate (PSS) – surfactant system. The effect of hydration shell of hyaluronan on hyaluronan – surfactant complex formation results from the comparison of above mentioned systems. Large differences were found in the deprotonation characteristic between surfactants and even between individual molecular weights of hyaluronan. The measurement shows that the hydration shell is located near to the dissociated carboxyl groups of hyaluronan chain, where the interaction with the positively charged surfactants occurs. Furthermore, the aggregation number of Septonex was determined by quenching of pyrene using cetylpyridinium chloride (CPC) as a quencher. The aggregation number for 20 mM Septonex solution was determined as a value of 104 molecules. CPC was used for confirmation of the localization of -naphthol in the micelles of CTAB and polymer – CTAB, respectively.

L’application de la photoluminescence suscite un intérêt croissant de la part des chercheurs et ceci dans de nombreux domaines. Dans notre cas, différents complexes à base de lanthanide seront détectés par une méthode spectrophotométrique avancée, la fluorescence résolue en temps. Ces derniers peuvent être ainsi détectés même à l’état de traces au sein des milieux complexes tel que ceux rencontrés dans l’industrie pétrolière (saumures, traces de pétrole, éléments solides en suspension, etc.). L'utilisation de la détection de fluorescence résolue en temps combinée à des complexes de lanthanides a été démontrée comme une stratégie simple et efficace pour éliminer la fluorescence de fond des matrices présentes dans le milieu étudié et fournir un rapport signal sur bruit élevé. Le sujet de cette thèse consiste à répondre avec les outils précédents à différentes problématique existants au sein de l’industrie pétrolière, de l’extraction du pétrole au processus de marquage de différents produits raffinés à des fins commerciales. Dans la première partie du manuscrit décrira différents protocoles capables d’extraire de l’information de différents additifs chimiques employés sur les champs pétrolifères lors de l’extraction de pétrole et de gaz. Les additifs en questions peuvent être des inhibiteurs de dépôts minéraux, des inhibiteurs de corrosion, des polymères viscoélastiques, dans différentes eaux de synthèse et de production issues de différentes plateformes. Les impacts de certains facteurs ont été analysés afin d’améliorer la sensibilité et les performances. Nous démontrerons la possibilité de quantifier avec succès la teneur résiduelle de différents types d'additifs chimiques. L'effet de matrice de l’échantillon a été limité par le développement de deux stratégies d'addition standard. Nous montrerons par ailleurs qu’il est possible de quantifier la présence non seulement d’un additif mais encore, dans certaines situations optimisées, de deux additifs en mélange. Outre la détermination de la concentration en additifs chimiques, nous présenterons également une méthode permettant de déterminer l’anionicité d’un polymère en milieu complexe. Dans la deuxième partie du document, nous détaillerons le développement de complexes de lanthanides utilisés en tant que marqueurs ainsi que la méthode de détection par fluorescence résolue en temps visant à la lutte contre la contrefaçon de différents pétroles bruts et de carburants raffinés. La synthèse et le processus d’incorporation de trois types de marqueurs de photoluminescence et leur stabilité dans différents carburants seront ensuite discutés. Les résultats obtenus démontrent qu’il est possible, à l’aide de cette technologie de marquage, de détecter efficacement les fraudes à la taxe dans les carburants, même à haute dilution. Ces travaux présente potentiellement un fort impact dans les domaines académiques comme industriels. Toutes les études se concentrent sur la mise au point d’une procédure simple, qui fournit une sensibilité élevée permettant de réduire le coût de production et qui repose sur l’emploi du fluorimètre résolu en temps Inibox™ développé pendant ma thèse pour porter sur le terrain les technologies développé au laboratoire / The application of photoluminescence is receiving an increasing interest from researchers coming from many fields. The previous laboratory works introduced a time-resolved fluorescence (TRF) detection method for the quantification of chemicals in complex medium (petroleum, production brine, and synthetic sea water) tagged with lanthanides, the additives form complexes that exhibit specific TRF signal which overcomes autofluorescence of sample and provide a high signal to noise ratio. The subject of this thesis concerns the development of specific methods based on patented technique to answer problematics arising in the oil industry from the extraction of crude product to the distribution of fuels. In the first part of the document, we focus on the monitoring of residual amount of chemical additives such as scale inhibitors, corrosion inhibitors, viscoelastic polymers in different synthetic and production waters. The impacts of some key factors were analyzed in order to improve the sensitivity and performance, also proves that under optimized conditions it is possible to quantify simultaneously two products in the same matrix. We successfully quantified various types of chemical additives with satisfying precision. Furthermore, the matrix effect was controlled by the development of two standard addition strategies. In addition to the determination of the concentration of chemical additives, we will also introduce a method to determine the anionicity of a polymer in difficult conditions. In the second part of the manuscript we follow the development of lanthanide complex markers and their detection for anti-counterfeiting on different crude oils and refined fuels. The synthesis, incorporation process and stability of three types of photoluminescence markers in different fuels have been discussed. The obtained results will prove that the technology can be used to detect fraud on fuels. This work has a potential great impact for both the academic and industrial domains. All studies focus on the creation of a simple procedure, with high sensitivity and low cost. All method are relying in the end on a specific field apparatus developed during my thesis to support the exportation of the technologies from the laboratory to the industry: The Inibox™

In this diploma thesis was studied time-resolved fluorescence in polymer-surfactant system. At first aggregation numbers of cationic (cetyltrimethylammonium bromide), anionic (sodium dodecylsulfate) and nonionic (Triton X-100) surfactants were studied by steady-state and time-resolved fluorescence spectroscopy. These two methods were compared. Aggregation numbers by steady-state method were always lower than aggregation numbers measured by time-resolved method. Steady-state method of determination aggregation numbers is useless for surfactants with high aggregation number and for aerated samples. Addition of hyaluronan to surfactant system was studied. There was observed change in aggregation number after addition of hyaluronan and change in percentage of dynamic quenching after addition of hyaluronan. Hyaluronan affected aggregation number of cetyltrimethylammonium bromide and Triton X-100. Hyaluronan increased percentage of dynamic quenching in cetyltrimethylammonium bromide and in Triton X-100. Pyren in sodium dodecylsulfate was quenched by sphere of action with negligible percentage of dynamic quenching and addition of hyaluronan had no effect on quenching. As next goal of this thesis, the determination of the position of fluorescence probe pyrene in cetyltrimethylammonium bromide, sodium dodecylsulfate and Triton X-100 micelles was chosen. Position of pyrene changed with charge and structure of micelles. Next was studied how percentage of dynamic quenching by iodide compounds changes with different charge of micelle. In all cases majority of dynamic quenching was calculated.

No description available.

Ce travail de thèse est principalement centré sur l’étude des processus photophysiques fondamentaux de nouveaux composés organiques à transfert de charge dérivés de styrylpyridine, réalisée grâce à des mesures de fluorescence résolue en temps à l’échelle picoseconde et d’absorption transitoire à l’échelle femtoseconde. Nous nous sommes tout d’abord intéressés au comportement des états excités de deux nouvelles hémicyanines. Les molécules de diméthoxystyrylpyridine méthylées ont montré l’établissement d’un équilibre entre les conformations syn et anti différent à l’état excité comparé à l’état fondamental, représenté par un temps de décroissance rapide de fluorescence. La deuxième constante de temps correspond à la dépopulation de l’état excité par les voies non radiatives telles que l’isomérisation et le twist du donneur de charge (effet « loose-bolt »). Concernant le dérivé de styrylpyridinium où le groupement phényl a été remplacé par diméthlaminothiophene, nos études ont prouvé l’implication du mouvement de rotation du groupement méthylpyridinium ainsi que l’intervention du croisement inter-système comme voies de relaxation. Dans un second temps, nous nous sommes penchés sur les propriétés de complexation de la molécule de styrylpyridine sur laquelle a été substitué un éther-couronne. Nos études nous ont permis de mettre en évidence la présence de deux centres de complexation (un au centre de la couronne, l’autre sur l’azote de la pyridine) montrant une sélectivité différente vis-à-vis des cations métalliques. Les stoechiométries ont pu être confirmées par une analyse des temps de réorientation des complexes formés. Après avoir étudié les divers composés constituant des « briques » élémentaires en vue de systèmes supramoléculaires plus élaborés, nous nous sommes intéressés à leurs éventuelles applications avec l’étude de systèmes pour la collecte et le transfert d’énergie. Nous avons tout d’abord démontré l’existence d’un transfert d’énergie ultra-rapide (180 fs à 6 ps) et ultra-efficace (>99.7%) dans des systèmes bichromophoriques contenant deux styrylpyridines avec un éther-couronne et asymétrisés par l’introduction d’un cation Mg2+ dans une seule couronne. Celui-ci se fait de la partie complexée vers la partie non complexée par interaction coulombienne. Une autre application envisagée réside dans la construction de complexes à métaux de transition pour le stockage d’énergie ou le stockage d’information. Nous avons tout d’abord étudié la formation d’un système supramoléculaire basé sur le phénanthroline et contenant quatre éther-couronnes libres. Nous avons mis en évidence l’existence d’un équilibre entre états singulets et triplets excités dans ces composés complexés avec Cuivre(I) ou Argent(I). Dans un second temps, nous avons étudié la formation de complexes liant deux bipyridines substitués contenant un éther-couronne à un ion Fe2+. Un tel complexe présente des propriétés de transition de spin BS?HS. Nos études ont ensuite révélé la formation de complexes à métaux de transition de taille nanométrique lors de l’ajout d’ions Ba2+. / This Ph.D. work mainly deals with the study of fundamental photophysical processes of new styrylpyridine-type organic compounds showing charge transfer, realised using picosecond fluorescence and femtosecond transient absorption. We were interested first in the excited-state behaviour of two new hemicyanines. Methylated dimethoxystyrylpyridines molecules showed the establishment of an equilibrium between syn and anti conformations which is different in the excited state compared to the ground state, represented by a fast relaxation time of fluorescence. The second time constant corresponds to depopulation of the the excited state by non-radiative pathways as isomerization and donor twist (« loose-bolt »). Concerning styrylpyridinium derivative where phenyl group was replaced by dimethylaminothiophene, our studies proved involvment of rotation of methylpyridinium group and intersystem crossing as relaxation pathways. Secondly, we were interested in complexation properties of ether-crown susbstituted styrylpyridine molecule. Our studies showed the presence of two complexation centers (one in the center of the crown, the other one on the nitrogen of pyridine) having a different selectivity for metallic cations. Stoichiometries were confirmed by analysis of the reorientation times of formed complexes. After the study of our different compounds as elementary « building–blocks » for more complex supramolecular systems, we were interested in their potential applications with the study of systems for collection and energy transfer. First, we highlighted the existence of an ultra fast (180 fs to 6 ps) and ultra efficient (>99.7%) intramolecular energy transfer in bichromophoric systems containing two ether-crowned styrylpyridines and dissymetrised by binding of a Mg2+ cation in only one crown. It occurs from the complexed part to the non-complexed one by coulombic interaction. Another envisaged application can be the construction of complexes containing transition metals for energy or information storage. We studied first the building of a supramolecular system based on phenanthroline and containing four free ether-crowns We also proved that there exists an equilibrium between singlet and triplet excited states in these compounds complexed with Copper(I) or Silver(I). Secondly, we studied formation of complexes binding two ether-crown substituted bipyridines to a Fe2+ ion. Such a complex has got some spin crossover properties. Then, we showed that the addition of Ba2+ ions induce formation of transition metals complexes with nanometric size.

Une nouvelle famille de complexes de difluorure de bore photosensibles est développée. Elle est basée sur des structures moléculaires contenant une unité β-dicétone à conjugaison électronique π.La grande variété de groupements aromatiques et la nature donneur ou accepteur d'électrons des différents substituants permet l'élaboration de systèmes électroniques donneur-accepteur-donneur d'électrons (D1-A-D1) et donneur-accepteur (D2-A).L'absorption électronique de cette famille de molécule se situe dans la partie visible du spectre électromagnétique et une partie du spectre ultraviolet, et est caractérisée par une bande d'absorption π-π* intense avec des coefficients d'absorption molaire supérieurs à 50 000 M-1cm-1.L'émission de fluorescence couvre une plage spectrale qui va du visible au proche infrarouge avec des rendements quantiques de fluorescence en solution relativement élevés pouvant atteindre 62 %.En fin, cette famille de molécule est photochimiquement stable et est, contrairement à d'autres familles de complexes de difluorure de bore, chimiquement très stable en solution.Mots-clés : Difluorure de bore, β-dicétone, matériaux π-conjugués, luminescence, fluorescence stationnaire et résolue dans le temps (TRES), synthèse organique, RMN-19F dynamique, complexes & colorants fluorescents, curcumine & curcuminoide, complexe BF2, photophysique. / A new photosensitive family of boron difluoride complex is developed. It is based on π-conjugated molecular structures containing β-diketonates unit.The wide variety of aromatic groups and the nature of donor or electron acceptor of the different substituents allow the development of electron donor-acceptor-donor (DAD) and donor-acceptor (DA) electronic systems.The electronic absorption of this family of molecules is in the visible part of the electromagnetic spectrum and a portion of the ultraviolet spectrum, and is characterized by an intense π-π* absorption band with molar absorption coefficient greater than 50 000 M-1.cm-1.The fluorescence emission covers a spectral range going from visible to near infrared, with relatively high fluorescence quantum yields of up to 62 % in solution.This new material family is photochemically stable and, unlike some other families of boron difluoride complexes, chemically very stable in solution.