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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Few-body interactions in cold Rydberg atoms / Interaction à quelques corps entre atomes de Rydberg

Faoro, Riccardo 03 December 2015 (has links)
L’objectif de cette thèse est l’étude des différents aspects de l’interaction à quelques corps entre des atomes de Rydberg froids. Cette thèse a été réalisée dans le cadre d’une cotutelle entre l’Université Paris-Saclay et l’Université de Pise en travaillant sur deux différents montages expérimentaux sur des atomes de Rydberg froids : respectivement sur le Cs au Laboratoire Aimé Cotton et sur le Rb au département de Physique de l’Université de Pise. Au Laboratoire Aimé Cotton nous avons démontré l’existence des nouvelles interactions à quelques corps dans un gas gelé d’atomes de Rydberg. Ces nouvelles résonances sont la généralisation des résonances de Förster bien connues dans le domaine des atomes de Rydberg. Ces résonances agissent sur les degrés de liberté interne des atomes de Rydberg et ont l’effet d’un transfert résonant d’énergie et de population comme dans le cas des FRET (Fluorescence Resonance Energy Transfer). Comme dans le cas de la résonance de Förster à deux corps, les résonances FRET à trois corps sont accordées à la résonance avec un champ électrique externe et peuvent être observées pour différents nombres quantique principaux. Les effets à trois corps sont observés en absence de tout effet à deux corps et sont qualifiés de Borroméens. La présence d’un champ externe peut générer d’autres résonances entre atomes de Rydberg qui sont interdites en absence de champ électrique. Ces résonances, qu’on peut qualifier des résonances quasi-interdites, sont dues à un couplage dipole-dipole de type Förster. Nous avons identifié toutes ces résonances liées au couplage entre les niveaux de multiplicité de n différents.Dans le montage expérimental à Pise on a étudié les effets mécaniques liés à la répulsion van der Waals entre atomes de Rydberg. Nous avons étudié l’expansion due à l’interaction van der Waals dans une chaîne 1D des atomes de Rydberg de Rb qui ont étés excités avec une excitation laser hors résonance. La comparaison entre les différents désaccords de l’excitation laser démontre le rôle central joué par l’interaction van der Waals. / The aim of this thesis is to investigate different aspects of few-body interactions in cold Rydberg atoms. It has been realized in a co-tutelle program between the University of Paris-Saclay and the University of Pisa working on two different experimental set ups: one at Laboratoire Aimé Cotton on cold Cs Rydberg atoms and a second at Physics Department of Pisa on cold Rb Rydberg atoms. In Laboratoire Aimé Cotton we demonstrated the existence of new few-body interactions we observed in a frozen Rydberg gas of Cs atoms. These new resonances are a generalization of already known two-body Förster resonances. They act on the internal degrees of freedom of the Rydberg atoms leading to a resonant energy transfer analogous to the one in FRET (Fluorescence Resonance Energy Transfer). In analogy with Förster resonance, three-body FRETs are tuned with an external electric field and can be observed for different principal quantum number. The three-body interaction appeared in the absence of any two-body ones and for this reasons it has a Borromean character. The presence of this external electric field leads to additional resonances between Rydberg atoms supposedly forbidden. These resonances, we call quasi-forbidden Förster resonances, are due to dipole-dipole interaction as in the case of Förster resonance. We investigated these resonances finding a large number close to the allowed two-body and three-body FRET. A precise study was necessary in order to identify and discriminate these resonances from the allowed ones.In the experiment in Pisa we instead focus our attention on the mechanical effect of van der Waals repulsion between Rydberg atoms. We studied the spatial expansion due to a van der Waals interaction in a 1D chain of Rb Rydberg atoms excited with an off-resonant laser excitation. The comparison of the spatial expansion for different detuning of the laser excitation reveals the central role of the van der Waals interaction whose strength is equal to the detuning of the laser excitation.
12

Study of GaN Based Nanostructures and Hybrids

Forsberg, Mathias January 2016 (has links)
GaN and its alloys with Al and In belong to the group III nitride semiconductors and are today the materials of choice for efficient white light emitting diodes (LEDs) enabling energy saving solid state lighting. Currently, there is a great interest in the development of novel inexpensive techniques to fabricate hybrid LEDs combining high quality III-N quantum well (QW) structures with inexpensive colloidal nanoparticles or conjugated polymers. Such hybrid devices are promising for future micro-light sources in full-color displays, sensors and imaging systems. Organics can be engineered to emit at different wavelengths or even white light based on functional groups or by blend of several polymers. This is especially important for the green region, where there is still a lack of efficient LEDs. Besides optoelectronics, other applications such as biochemical sensors or systems for water splitting can be realized using GaN-based nanostructures. Despite a significant progress in the field, there is still a need in fundamental understanding of many problems and phenomena in III-nitride based nanostructures and hybrids to fully utilize material properties on demand of specific applications. In this thesis, hybrid structures based on AlGaN/GaN QWs and colloidal ZnO nano-crystals have been fabricated for down conversion of the QW emission utilizing non-radiative (Förster) resonant energy transfer. Time-resolved photoluminescence (TRPL) was used to investigate the QW exciton dynamics depending on the cap layer thickness in the bare QW and in the hybrid samples. Although the surface potential influences the exciton dynamics, the maximum pumping efficiency assuming a non-radiative energy transfer mechanism was estimated to be ~40 % at 60 K in the structure with thin cap layer of 3 nm. Since bulk GaN of large area is difficult to synthesize, there is a lack of native substrates. Thus, GaN-based structures are usually grown on SiC or sapphire, which results in high threading dislocation density in the active layer of the device and can be the reason of efficiency droop in GaN based LED structures. Fabricating GaN nanorods (NR) can be a way to produce GaN with lower defect density since threading dislocations can be annihilated toward the NR wall during growth. Here, GaN(0001) NRs grown on Si(111) substrates by magnetron sputtering using a liquid Ga target have been investigated. A high quality of NRs have been confirmed by transmission electron microscopy (TEM) and TRPL. Two strong near band gap emission lines at ~3.42 eV and ~3.47 eV related to basal plane stacking faults (SF) and donor-bound exciton (DBE), respectively, have been observed at low temperatures. TRPL properties of the SF PL line suggest that SFs form a regular structure similar to a multiple QWs, which was confirmed by TEM. The SF related PL measured at 5 K for a single NR has a significantly different polarization response compared to the GaN exciton line and is much stronger polarized (> 40 %) in the direction perpendicular to the NR growth axis. Hybrids fabricated using GaN NRs and the green emitting polyfluorene (F8BT) have been studied using micro-TRPL. In contrast to the DBE emission, the recombination time of the SF-related emission was observed to decrease, which might be due to the Förster resonance energy transfer mechanism. Compared to chemical vapor deposition, sputtering allows synthesis at much lower temperatures. Here, sputtering was employed to grow InAlN/GaN heterostructures with an indium content targeted to ~18 %, which is lattice matched to GaN. This means that near strain-free GaN films can be synthesized. It was found that using a lower temperature (~25 C) while depositing the top InAlN results in an improved interface quality compared to deposition at 700 C. In latter case, regions of quaternary alloy of InAlGaN forming structural micro-defects have been observed at the top InAlN/GaN interface in addition to optically active flower-like defect formations.
13

A new approach to the analyses of fluorescence depolarisation experiments in the presence of electronic energy transport

Opanasyuk, Oleg January 2011 (has links)
A new and general procedure is described for a detailed analysis of time-resolved fluorescence depolarisation data in the presence of electronic energy migration. An isotropic ensemble of bifluorophoric molecules (D1-R-D2) has been studied to demonstrate its utility. Intramolecular donor-donor energy migration occurs between the two donor groups (D), which are covalently connected to a rigid linker group (R). These groups undergo restricted reorientational motions with respect to the R group. The analysis of depolarisation data basically involves the search for best-fit parameters which describe the local reorienting motions, the interfluorophore D1-D2 distance, as well as the mutual orientations of the donors. For this, the analysis is partly performed in the Fourier domain and the best-fit parameters are determined by using an approach based on a Genetic Algorithm. The energy migration process has been described by using Monte Carlo simulations and an extended Förster theory. It is found that this theory provides the least time-consuming computational method. Since one-photon and two-photon excited fluorescence experiments can be applied for energy migration studies, a general and unified theoretical formulation is given. To exemplify the developed quantitative approach the depolarisation of the fluorescence in the presence of electronic energy migration within a bis-(9-anthrylmethylphosphonate) bisteroid molecule has been studied by time-resolved two-photon excited fluorescence depolarisation experiments. To solely obtain information about local reorientations of the 9-anthrylmethyl group, also the mono-(9-anthrylmethylphosphonate) bisteroid was studied, which enabled modelling of the ordering potential of the donor. Values of the two-photon absorption tensor components were obtained. To describe the discrepancy between the measured values of the initial anisotropy and fundamental anisotropy predicted by theory the distribution of absorption tensor caused by fast processes have been introduced. An angular parameter of absorption tensor was determined. Reasonable values of the distance between the 9-anthrylmethyl groups, as well as for their mutual orientation were obtained.
14

FRET-based detection and quantification of HIV-1 Virion Maturation / FRETを用いたHIV-1成熟ウイルス粒子の検出と定量

Sarca, Anamaria Daniela 23 March 2021 (has links)
付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 新制・課程博士 / 博士(医学) / 甲第23106号 / 医博第4733号 / 新制||医||1050(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 小柳 義夫, 教授 松田 道行, 教授 朝長 啓造 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM
15

Weber, Karl Förster und der Dresdner Liederkreis im Spiegel ihrer Tagebuchaufzeichnungen

Beck, Dagmar 19 March 2018 (has links)
No description available.
16

Two-photon Cross Section Enhancement of Photochromic Compounds for Use in 3D Optical Data Storage

Luchita, Gheorghe 01 January 2011 (has links)
Rewritable photochrome-based 3D optical data storage requires photochromic molecules with high two-photon absorption (2PA) cross sections. Currently, the low value of two-photon absorption cross sections of existing photochromes makes them unsuitable for practical application in 3D data storage. Worldwide attempts to increase the cross section of photochromic molecules by altering the chemical structure have yielded poor results. In this work, two ways to increase the two-photon absorption cross sections of photochromes were investigated. In the first method, partial success demonstrated by extending the conjugation of a photochromic molecule, a high two-photon absorption cross section of the closed form isomer and high photoconversion to the closed form were realized. At the same time, a decrease in photoswitching quantum yield and low photoconversion to open form was observed. A discussion is provided to explain the results, suggesting that the proposed method of extending the conjugation may not solve the problem. For this reason a new method for effective two-photon absorption cross section enhancement of photochromes was proposed. As a proof of principle, a new two-photon absorbing dye with a hydrogen bonding moiety was synthesized and used for the formation of supramolecular structures with a photochromic compound. Theoretical reasoning and experimental demonstration of energy transfer from the dye to the photochrome under one and two-photon excitation confirmed the practical value of the method. The effects of a 2PA dye on the photochromic properties of a diarylethene were investigated using a model compound to simplify data analysis. Formation of supramolecular structures was revealed using ¹H NMR spectroscopic methods. The model compound, having the same hydrogen bonding moiety as 2PA dye, has been demonstrated to bind with photochrome molecules at very low concentrations. Photochromic properties of 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, including conversions at the photostationary state, extinction coefficients, photoisomerization reaction rates and quantum yields, were shown to be affected by hydrogen bonding with the model compound - 2,6-bis-(acetamido)pyridine. The extent of this change was determined and discussed, demonstrating a balanced supramolecular strategy to modulate photochemical and photophysical properties of this important class of photochromic material.
17

Förster Resonance Energy Transfer from Terbium Complexes to Quantum Dots for Multiplexed Homogeneous Immunoassays and Molecular Rulers / Transfert d'énergie par résonance de type Förster entre des complexes de terbium et des boîtes quantiques pour des immunodosages et des reglettes moléculaires multiplexés

Wegner, David Karl 24 June 2015 (has links)
Le transfert d'énergie par résonance de type Förster (FRET) est un transfert d'énergie non radiatif d'un donneur à un accepteur à proximité. En raison de sa dépendance de la distance extrêmement sensible entre env. 1 et 20 nm, FRET joue un rôle important dans la nanobiotechnologie. Ainsi FRET peut être utilisé comme système de transduction du signal, mais aussi pour l'estimation de la distance entre le donneur et l'accepteur.Les accepteurs de FRET utilisés dans ce travail étaient des nanocristaux semi-conducteurs (quantum dots, QD). Ce type de luminophore est bien connu pour ses propriétés photophysiques supérieures. Leur absorption forte et spectralement large, et leur photoluminescence (PL) brillante et spectralement fine et de l'accordabilité spectrale de la PL sont idéalement adaptés aux applications de FRET. La combinaison des QDs comme accepteurs de FRET avec des complexes luminescents de terbium (CLT) comme donneurs permet des grandes distances de FRET (> 10 nm). La distance de FRET est caractéristique d'une paire FRET et décrit la distance à laquelle l'efficacité de FRET est égale à 50%. CLT sont idéal comme donneurs de FRET parce qu'ils fournissent des longues durées de vie des états excités à l'ordre de la milliseconde. Cette longue période de décroissance de PL permet de mesurer en temps décalé pour une répression d’autofluorescence et la PL des QDs directement excités, ce qui augmente fortement la sensibilité de détection. Les bandes d'émission de PL structurés de CLT et la PL accordable de QDs sont idéales pour l'application dans le diagnostic multiplexé.La thèse se compose de deux parties. Dans la première le couple FRET CLT-QD a été utilisé dans des immunodosages de FRET homogènes pour la détection de marqueurs biologiques antigène prostatique spécifique (TPSA), énolase specifique des neurones (NSE), antigène carcino-embryonnaire (CEA), et le récepteur du facteur de croissance épidermique (EGFR). La sensibilité du dosage immunologique a été optimisé en utilisant des différents types d'anticorps IgG, F (ab')2, F (ab), et pour EGFR un anticorps de chaîne lourde unique. Des limites de détection picomolaires étaient réalisées en utilisant des échantillons de sérum de petit volume et des mesures sur des lecteurs de microplaques cliniques. Une étude détaillée des différents systèmes de FRET en utilisant la spectroscopie résolue en temps a été réalisée pour étudier l'influence des différents anticorps sur la distance, la fonctionnalité, et la sensibilité des immunodosages. L'étude a été complétée par la mesure de NSE et CEA dans un format duplexé et des échantillons réels de patients.Dans la deuxième partie le FRET pour des mesures de distance nanométriques (réglette moléculaire ou spectroscopique) étaient étudiés. FRET en résolution temporelle a permis de calculer la distance entre le donneur et l’accepteur. Par conséquent, deux stratégies de liaisons différentes ont été étudiées pour établir une proximité entre le CLT et le QD : la reconnaissance biotine-streptavidine et l’auto-assemblage médié par polyhistidine. Une étude en résolution temporelle détaillée a été effectuée avec des QDs de différentes tailles, formes et revêtements de surface combiné avec des CLT liés à trois différentes biomolécules. L'analyse des courbes de décroissance multiexponentielle des donneurs et accepteurs permettait à obtenir des informations sur la taille, la forme et la biofonctionnalité des bioconjugués CLT-QD. Les résultats étaient en accord avec d'autres méthodes d'analyse de structure, telles que la microscopie électronique à transmission (MET) ou la diffusion de lumière dynamique (DLS), mais avec l'avantage d'une mesure homogène à la résolution 3-dimensionelle (impossible pour le MET), sans l'inclusion d'une couche d'hydratation (l’inconvénient de DLS) et en faible concentration dans le même environnement que celui utilisé pour l'application biologique. / Förster resonance energy transfer (FRET) is a non-radiative energy transfer from a donor to an acceptor in close proximity. Due to its extremely sensitive distance dependence in the 1 – 20 nm range, FRET plays an important role in nanobiotechnology. Thereby FRET can be used as signal transduction system but also for the distance estimation between donor and acceptor. The selected FRET acceptors in this work were semiconductor nanocrystals (quantum dots, QDs). This type of luminophore is well known for its superior photophysical properties. Their strong and broad absorption and their bright, narrow-band, and size-tunable photoluminescence (PL) emission make QDs ideally suited for FRET application. Combing QDs as FRET acceptors with luminescent terbium complexes (LTC) as FRET donors offers exceptionally large Förster distances of more than 10 nm. The Förster distance is characteristic of a FRET pair and is the distance at which the FRET efficiency equals 50 %. A large Förster distance is desirable as it offers the detection of biological interactions over large distances. LTC are suitable FRET donors for QDs because they provide long excited-state lifetimes in the millisecond range. This long PL decay time enables time-gated measurements for the suppression of autofluorescence and PL of directly excited QDs, which strongly increases the detection sensitivity. Additionally, the structured PL emission bands of LTCs together with the size-tunable PL emission bands of QDs make this FRET pair ideal for the application in multiplexed diagnostics, which is the measurement of multiple biomarkers in a single sample.The PhD thesis consists of two parts. In the first part the LTC-QD FRET pair was used within homogeneous FRET immunoassays for the detection of the biomarkers prostate specific antigen (TPSA), neuron-specific enolase (NSE), carcinoembryonic antigen (CEA), and epidermal growth factor receptor (EGFR). The immunoassay sensitivity was optimized using different types of antibodies IgG, F(ab’)2,F(ab), and for EGFR single heavy chain antibodies, which differ largely in their size. The use of small-volume serum samples and measurements on clinical as well customized fluorescence plate readers result in picomolar detection limits for all measured biomarkers. In addition to these QD-based in vitro diagnostic tests, a detailed study of the different FRET-systems using time-resolved spectroscopy was performed. The investigation revealed the influence of the different antibodies on distance, functionality, and sensitivity of the FRET immunoassays. The study was completed by the measurement of NSE and CEA in a duplexed format and real patient samples were investigated.The second part was to use FRET for nanometric distance measurements as molecular or spectroscopic ruler. Time-resolved FRET measurements enabled the calculation of the distance between donor and acceptor. Therefore two different binding strategies were investigated to establish a close proximity between the LTC-donor to the QD-acceptor, namely biotin-streptavidin recognition and polyhistidine mediated self-assembly. A detailed time-resolved study was performed of QDs with different sizes, shapes, and surface coatings in combination with LTC bound to three different host biomolecules, which also possessed different sizes, shapes, orientations, and binding conditions. The analysis of the multi-exponential decay curves of donor and acceptor allowed to obtain information about the size, shape, and biofunctionality of the investigated QD bioconjugates. The results were in agreement with other structural analysis methods, such as transmission electron microscopy (TEM) or dynamic light scattering (DLS), but with the advantage of a homogeneous measurement with three-dimensional resolution (not possible for TEM), without the inclusion of a hydration shell (drawback for DLS), and at low concentration in the same environment as used for the biological application.
18

Energy Transfer in Organic-Inorganic Semiconductor Structures

Bianchi, Francesco 09 July 2018 (has links)
In HIOS-Strukturen, die auf einem Quantengraben und einer angrenzenden organischen Deckschicht basieren, wurde eine effiziente Umwandlung von Wannier-Exzitonen in Frenkel-Exzitonen mittels resonantem Förster Energietransfer (FRET) demonstriert. Das hier verwendete Design besteht aus einem spiro-annulierten Quarter-phenyl (L4P-SP3), das auf einen ZnO-Quantengraben (SQW) aufgewachsen wurde, um inkohärente Kopplung zu erreichen. Mittels optischer Spektroskopie haben wir demonstriert, dass diese hybriden Strukturen Energietransfer vom SQW zu den organischen Molekülen mit einer Effizienz von bis zu 77% zeigen. Allerdings zeigen UPS-Messungen eine typ-II-artige Energieniveau-Anpassung zwischen ZnO und der molekularen Schicht, die zu einem sehr effizienten Ladungstrennungsvorgang (ηCT=0.9) führt, der die molekulare Emission unterdrückt. Die erste beruht auf einer schnellen und hocheffizienten Energietransfer-Kaskade: nach der ersten Transferstufe wird die Anregungsenergie von der hybriden Grenzfläche weggeleitet, indem eine zweite Energietransferstufe eingeführt wird, bevor die Dissoziation der Exzitonen an der Grenzfläche statt-finden kann. Wir verwenden Sexiphenyl, L6P als endgültigen Akzeptor. In solch einer Struktur können wir eine Wiederherstellung der molekularen Emission um einen Faktor acht demonstrieren und zeigen, dass der Energietransferprozess zwischen L4P-SP3 und L6P den Ladungstrennungsprozess fast vollständig überholt. Als andere Option haben wir die Energieniveaus angepasst, indem eine organometallische Donor-Monolage [RuCp*mes] ergänzt wird. Diese Zwischenschicht senkt die Austrittsarbeit von ZnO deutlich ab und führt so zu einer Anpassung der Niveaus zwischen die zwei Halbleiter. Während die Effizienz des Energietransfers unverändert bleibt, steigen die Emission von L4P-SP3 sowie die Lebenszeit der molekularen Photoluminescenz um einen Faktor sieben verglichen mit entsprechenden Strukturen ohne Zwischenlage. / In HIOS structures based on a quantum well and an adjacent organic overlayer, efficient conversion of Wannier excitons into Frenkel excitons via Förster-type resonant energy transfer (FRET) has been demonstrated. The design here in use consists of a spiro-annulated ladder-type quarter-phenyl (L4P-SP3), deposited on ZnO-based single quantum wells (SQW) to obtain incoherent electronic coupling. The SQWs we use are grown with extremely thin (2 nm) capping layer. With photoluminescence excitation and time-resolved spectroscopy, we demonstrate that these hybrid structures exhibit energy transfer from the inorganic material to the organic molecules with an efficiency up to 77%. However, UPS measurements show a type-II energy level alignment between ZnO and the molecular layer, resulting in a very efficient charge separation process (ηCT=0.9) that suppresses the molecular emission. The first idea relies on a fast and highly efficient cascade FRET: following the primary transfer step from the QW, the excitation is conveyed away from the hybrid interface by a secondary transfer-step within the organic layer. As final acceptor we select ladder-type sexiphenyl (L6P). In such a structure, we demonstrate a recovery of the molecular emission by a factor eight, showing that the intermolecular FRET outpaced almost entirely the charge separation process. As alternative option, we tune the energy levels at the interface by introducing an organometallic donor monolayer [RuCp*mes]. The interlayer reduces substantially the ZnO work function, aligning the frontier levels of the inorganic and organic semiconductor. Optical experiments show the benefits of the interlayer: while the FRET efficiency is unaffected, the L4P-SP3 emission and its photoluminescence lifetime increase by a factor of seven, when compared to the same structure without interlayer.
19

Synthesis of New lonic Functional Polymers by Free Radical Polymerization via the RAFT Process

Baussard, Jean-François 26 January 2004 (has links)
Within the emerging methods of controlled free radical polymerization, the Reversible Addition-Fragmentation chain Transfer (RAFT) process has been recently established as a powerful technique to synthesize standard polymers with controlled characteristics (narrow polydispersity and predictable molar masses). This method is now employed to synthesize well-defined, reactive precursor polymers that are subsequently converted into speciality polymers such as fluorescent-labeled polycations. Those are suitable for Electrostatic Self-Assembly (ESA). The observation of the Förster Resonance Energy Transfer (FRET) in such films is established, contributing to the understanding of the self-organization during thin film growth. The RAFT process using Benzyl Dithiobenzoate (BDTB) is shown to enable the control of the free radical polymerization of vinylbenzyl chloride (VBC). The high tolerance of the method to functional groups allows the preparation of such reactive polymers with narrow polydispersities and predictable molar masses. The well-defined precursors are easily converted, for instance, to polycations. Also they are easily functionalized by fluorophores, here derived from coumarin and perylene. The fluorophores, as pendent side chains, served as label to investigate the alternating deposition process, while the influence of molecular variations on the self-assembly can be systematized. Furthermore, when using complementary fluorophores, Fluorescence Resonance Energy Transfer (FRET) studies in organized media become possible. The alternating deposition cycles are followed by UV-Vis spectroscopy, ellipsometry, and X-Ray reflectivity. Regular growth is observed for three complementarily labeled polycations. Noteworthy, fluorescence and UV-Vis studies reveal the formation of large fluorescent dye aggregates for one coumarin and for the perylene derivative in the ESA multilayers. When these polycations are used in mixed thin films, Förster Resonance Energy Transfer (FRET) between fluorophores is observed. The non-radiative nature of the different energy transfer was confirmed by fluorescence decay time measurements/ Parmi les récentes méthodes pour contrôler la polymérisation radicalaire, le procédé RAFT (Reversible Addition-Fragmentation chain Transfer) a été récemment établi et s'impose comme une méthode performante pour la synthèse de polymères standards possédant des caractéristiques contrôlées (faibles polydispersités et masses molaires prédictibles). Cette méthode est désormais utilisée pour la synthèse de précurseurs réactifs bien définis qui sont par la suite convertis en polymères spécialisés, par exemple en polycations marqués a l'aide de sondes fluorescentes. Ces polycations peuvent être ensuite auto-assemblés électrostatiquement afin d'élaborer des films minces. Le phénomène de transfert de fluorescence (Förster Resonance Energy Transfer –FRET-) dans de tels films a été établi, contribuant par là-même à une meilleure compréhension du phénomène d'auto-organisation durant la croissance des films. Le procédé RAFT, utilisant le dithiobenzoate de benzyle (BDTB), a démontré sa capacité à contrôler la polymérisation radicalaire du chlorométhlstyrène (VBC). La tolérance de cette méthode vis à vis des groupes fonctionnels permet la synthèse de polymères réactifs possédant de faibles polydispersités et des masses molaires prédictibles. Les précurseurs ainsi définis sont facilement convertis, en polycations par exemple. Ils sont tout aussi facilement fonctionnalisés par des fluorophores dérivés de la coumarine ou du pérylène. Les fluorophores en tant que chaînes pendantes servent de marqueurs pour étudier le processus de dépôts alternés, alors que l'influence des variations au niveau moléculaire peut être systématisée. De plus, en utilisant des fluorophores complémentaires, il devient possible de mener des études sur le transfert de fluorescence (FRET) au sein de milieux organisés. Les cycles de dépôts alternés ont été suivis par spectroscopie UV-Vis, éllipsométrie et reflexion des rayons X. Une croissance régulière est observée dans le cas des trois polycations marqués. Il convient de noter que les études UV-Vis et de fluorescence révèlent la formation de larges aggrégats de fluorophores au sein des multicouches, dans le cas d'une coumarine et du dérivé de pérylène. Lorsque les polycations complémentaires sont utilisés dans des films minces mixtes, le FRET est observé. La nature radiative ou non-radiative du processus de transfert d'énergie a été confirmée par des mesures de déclin de fluorescence.
20

New challenges in biophotonics : laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring

Löhmannsröben, Hans-Gerd, Beck, Michael, Hildebrandt, Niko, Schmälzlin, Elmar, van Dongen, Joost T. January 2006 (has links)
Two examples of our biophotonic research utilizing nanoparticles are presented, namely laser-based fluoroimmuno analysis and in-vivo optical oxygen monitoring. Results of the work include significantly enhanced sensitivity of a homogeneous fluorescence immunoassay and markedly improved spatial resolution of oxygen gradients in root nodules of a legume species.

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