Tesis sobre el tema "Fluorescence yield"

The apparent fluorescence quantum yield of chlorophyll-a (ΦF ), i.e. the ratio of photons emitted as chlorophyll-a fluorescence to those absorbed by phytoplankton, serves as a first order measure of photosynthetic efficiency and a photophysiological indicator of the resident phytoplankton community. Drivers of ΦF variability, including taxonomy, nutrient availability, and light history, differ in magnitude of influence across various biogeographic provinces and seasons. A Multi-Exciter Fluorometer (MFL, JFE Advantech Co., Ltd.) was selected for use in in situ ΦF derivation and underwent an extensive radiometric calibration for this purpose. Wavelength-specific ΦF was determined for 66 in situ field stations, sampled in the Atlantic Southern Ocean during the austral winter of 2012 and summer of 2013/ 2014. Phytoplankton pigments, macronutrient concentrations, and light levels were simultaneously measured to investigate their influence on ΦF . While no relationship was observed between macronutrient levels and ΦF , an inverse relationship between light and ΦF was apparent. This was likely due to the influence of speciesspecific fluorescence quenching mechanisms employed by local populations. ΦF derived from ocean colour products (Φsat) from the Moderate Resolution Imaging Spectroradiometer (MODIS) were compared to in situ ΦF to assess the performance of three existing Φsat algorithms. Results indicate that accounting for chlorophyll-a fluorescence reabsorption, the inherent optical properties of the surrounding water column, and the sensor angle of observation, is crucial to reducing Φsat uncertainty. A hybrid combination of two of the algorithms performed best, and was used to derive Φsat for stations co-located to in situ iron measurements in the Atlantic Southern Ocean. A significant negative relationship was observed, indicative of the effects of iron availability on quantum yield and its potential as a proxy for iron limitation. However, separating the individual contributions of light, taxonomy, and iron limitation to Φsat variability remains a challenge. A time series analysis of Φsat was also undertaken, which revealed a prominent Φsat seasonal cycle. Ultimately, increased in situ sampling would expedite the development of improved Φsat algorithms; the routine retrieval of Φsat would offer insight into phytoplankton dynamics in undersampled regions such as the climate relevant Southern Ocean.

Le travail de cette thèse porte sur l’étude de la télédétection de la fluorescence chlorophyllienne avec un instrument imageur passif depuis une orbite géostationnaire pour le suivi de l’état physiologique de la végétation. Le concept instrumental est étudié théoriquement pour aboutir à la création d’uninstrument et à sa validation. La possibilité de mesurer des cycles diurnes de la fluorescence végétale depuis une orbite géostationnaire est évaluée à l’aide de simulations qui permettent de dresser les spécifications d’un instrument spatial.L’instrument imageur passif mesure dans la bande O 2 -A d’absorption atmosphérique. Il utilise une roue à filtres interférentiels dont la fonction de transmittance varie avec l’angle d’incidence des rayons les traversant. L’étude théorique a permis d’optimiser le placement spectral des filtres en vuede minimiser l’incertitude liée à la mesure de fluorescence.Grâce à la comparaison des mesures de l’instrument imageur avec d’autres instrument de mesure de la fluorescence, l’instrument et son concept instrumental ont été validés. Néanmoins, à cause d’effets de structure de la végétation intervenant sur le transfert radiatif de la fluorescence et de la lumière solaire au sein du couvert végétal, ces mesures ont confirmé la difficulté d’estimer le rendement de fluorescence de la végétation à partir des flux de fluorescence mesurés.Une étude théorique menée grâce à une modélisation du transfert radiatif de la fluorescence dans le couvert végétal jusqu’au capteur a permis d’expliquer la difficulté à retrouver le rendement de fluorescence à partir des flux. Cette étude a mis en avant l’accessibilité du rendement pour des couverts à fortedensité de feuilles et lorsque la distribution de l’orientation des feuilles est centrée sur l’horizontale.Cette modélisation a été étendue pour simuler des mesures spatiales dans le but d’étudier la possibilité de mesurer la fluorescence depuis une orbite géostationnaire dans les bandes O 2 -A et O 2 -B. Les résultats de ces simulations montrent la possibilité de mesurer préférentiellement dans la bandeO 2 -A avec une faible incertitude sur les flux de fluorescence et une bonne répétabilité temporelle pour le suivi des cycles diurnes de la fluorescence de la végétation
Le travail de cette thèse porte sur l’étude de la télédétection de la fluorescence chlorophyllienne avec un instrument imageur passif depuis une orbite géostationnaire pour le suivi de l’état physiologique de la végétation. Le concept instrumental est étudié théoriquement pour aboutir à la création d’uninstrument et à sa validation. La possibilité de mesurer des cycles diurnes de la fluorescence végétale depuis une orbite géostationnaire est évaluée à l’aide de simulations qui permettent de dresser les spécifications d’un instrument spatial.L’instrument imageur passif mesure dans la bande O 2 -A d’absorption atmosphérique. Il utilise une roue à filtres interférentiels dont la fonction de transmittance varie avec l’angle d’incidence des rayons les traversant. L’étude théorique a permis d’optimiser le placement spectral des filtres en vuede minimiser l’incertitude liée à la mesure de fluorescence.Grâce à la comparaison des mesures de l’instrument imageur avec d’autres instrument de mesure de la fluorescence, l’instrument et son concept instrumental ont été validés. Néanmoins, à cause d’effets de structure de la végétation intervenant sur le transfert radiatif de la fluorescence et de la lumière solaire au sein du couvert végétal, ces mesures ont confirmé la difficulté d’estimer le rendement de fluorescence de la végétation à partir des flux de fluorescence mesurés.Une étude théorique menée grâce à une modélisation du transfert radiatif de la fluorescence dans le couvert végétal jusqu’au capteur a permis d’expliquer la difficulté à retrouver le rendement de fluorescence à partir des flux. Cette étude a mis en avant l’accessibilité du rendement pour des couverts à fortedensité de feuilles et lorsque la distribution de l’orientation des feuilles est centrée sur l’horizontale.Cette modélisation a été étendue pour simuler des mesures spatiales dans le but d’étudier la possibilité de mesurer la fluorescence depuis une orbite géostationnaire dans les bandes O 2 -A et O 2 -B. Les résultats de ces simulations montrent la possibilité de mesurer préférentiellement dans la bandeO 2 -A avec une faible incertitude sur les flux de fluorescence et une bonne répétabilité temporelle pour le suivi des cycles diurnes de la fluorescence de la végétation

Le travail de cette thèse porte sur l’étude de la télédétection de la fluorescence chlorophyllienne avec un instrument imageur passif depuis une orbite géostationnaire pour le suivi de l’état physiologique de la végétation. Le concept instrumental est étudié théoriquement pour aboutir à la création d’uninstrument et à sa validation. La possibilité de mesurer des cycles diurnes de la fluorescence végétale depuis une orbite géostationnaire est évaluée à l’aide de simulations qui permettent de dresser les spécifications d’un instrument spatial.L’instrument imageur passif mesure dans la bande O 2 -A d’absorption atmosphérique. Il utilise une roue à filtres interférentiels dont la fonction de transmittance varie avec l’angle d’incidence des rayons les traversant. L’étude théorique a permis d’optimiser le placement spectral des filtres en vuede minimiser l’incertitude liée à la mesure de fluorescence.Grâce à la comparaison des mesures de l’instrument imageur avec d’autres instrument de mesure de la fluorescence, l’instrument et son concept instrumental ont été validés. Néanmoins, à cause d’effets de structure de la végétation intervenant sur le transfert radiatif de la fluorescence et de la lumière solaire au sein du couvert végétal, ces mesures ont confirmé la difficulté d’estimer le rendement de fluorescence de la végétation à partir des flux de fluorescence mesurés.Une étude théorique menée grâce à une modélisation du transfert radiatif de la fluorescence dans le couvert végétal jusqu’au capteur a permis d’expliquer la difficulté à retrouver le rendement de fluorescence à partir des flux. Cette étude a mis en avant l’accessibilité du rendement pour des couverts à fortedensité de feuilles et lorsque la distribution de l’orientation des feuilles est centrée sur l’horizontale.Cette modélisation a été étendue pour simuler des mesures spatiales dans le but d’étudier la possibilité de mesurer la fluorescence depuis une orbite géostationnaire dans les bandes O 2 -A et O 2 -B. Les résultats de ces simulations montrent la possibilité de mesurer préférentiellement dans la bandeO 2 -A avec une faible incertitude sur les flux de fluorescence et une bonne répétabilité temporelle pour le suivi des cycles diurnes de la fluorescence de la végétation
Le travail de cette thèse porte sur l’étude de la télédétection de la fluorescence chlorophyllienne avec un instrument imageur passif depuis une orbite géostationnaire pour le suivi de l’état physiologique de la végétation. Le concept instrumental est étudié théoriquement pour aboutir à la création d’uninstrument et à sa validation. La possibilité de mesurer des cycles diurnes de la fluorescence végétale depuis une orbite géostationnaire est évaluée à l’aide de simulations qui permettent de dresser les spécifications d’un instrument spatial.L’instrument imageur passif mesure dans la bande O 2 -A d’absorption atmosphérique. Il utilise une roue à filtres interférentiels dont la fonction de transmittance varie avec l’angle d’incidence des rayons les traversant. L’étude théorique a permis d’optimiser le placement spectral des filtres en vuede minimiser l’incertitude liée à la mesure de fluorescence.Grâce à la comparaison des mesures de l’instrument imageur avec d’autres instrument de mesure de la fluorescence, l’instrument et son concept instrumental ont été validés. Néanmoins, à cause d’effets de structure de la végétation intervenant sur le transfert radiatif de la fluorescence et de la lumière solaire au sein du couvert végétal, ces mesures ont confirmé la difficulté d’estimer le rendement de fluorescence de la végétation à partir des flux de fluorescence mesurés.Une étude théorique menée grâce à une modélisation du transfert radiatif de la fluorescence dans le couvert végétal jusqu’au capteur a permis d’expliquer la difficulté à retrouver le rendement de fluorescence à partir des flux. Cette étude a mis en avant l’accessibilité du rendement pour des couverts à fortedensité de feuilles et lorsque la distribution de l’orientation des feuilles est centrée sur l’horizontale.Cette modélisation a été étendue pour simuler des mesures spatiales dans le but d’étudier la possibilité de mesurer la fluorescence depuis une orbite géostationnaire dans les bandes O 2 -A et O 2 -B. Les résultats de ces simulations montrent la possibilité de mesurer préférentiellement dans la bandeO 2 -A avec une faible incertitude sur les flux de fluorescence et une bonne répétabilité temporelle pour le suivi des cycles diurnes de la fluorescence de la végétation

Currently, organic electronics is one of the most expanding technology of semiconductor devices. This direction is rapidly developing due to the constant synthesis of new organic compounds and sophisticated advances in device engineering. Currently, organic materials are used in organic light-emitting diodes (OLEDs), organic thin-film transistors, solar cells and sensors. Low-cost manufacturing techniques such as wet casting or inkjet printing enable organic materials use in large-area and flexible electronic devices. Modern organic electronic materials are multifunctional – this enables not only to improve the material properties, but also to simplify the device architecture. However, the complexity of the molecular structure brings new problems associated with complex phenomena of the new multifunctional molecules -such as the formation of aggregates, intramolecular charge transfer, intramolecular torsion and others. Therefore, the control of the features of new multifunctional molecules is the main problem of organic electronics today. This work focuses on the control of photophysical characteristics of multifunctional organic emitters. Here we study aggregation induced emission and quenching of multifunctional molecular emitters and the possibilities to control these phenomena by optimizing functional properties of the film such as film forming properties, charge transfer, the emission efficiency, amplified spontaneous emission threshold and others.
Organinė elektronika pastaruoju metu yra viena sparčiausiai besiplėtojančių puslaidininkių prietaisų krypčių. Ši kryptis labai sparčiai vystoma dėl nuolat kuriamų naujų organinių junginių ir tobulėjančių inžinerijos galimybių. Šiuo metu organinės medžiagos naudojamos organiniuose šviestukuose (OLED), plonasluoksniuose tranzistoriuose, saulės celėse, jutikliuose ir kt. Organinės medžiagos įgalina gaminti didelio ploto bei lanksčius elektronikos prietaisus, gamybai pasitelkiant pigias gaminimo technologijas. Modernios organinės elektronikos medžiagos yra daugiafunkcinės – tai leidžia ne tik pagerinti medžiagos savybes, bet ir supaprastinti technologiją, kur viename sluoksnyje daugiafunkcinė molekulė atlieka keletą funkcijų. Tačiau molekulinės struktūros sudėtingėjimas iškelia naujas problemas susijusias su naujais sudėtingais reiškiniais daugiafunkciniame molekuliniame darinyje, tokiais kaip agregatų formavimas, vidujemolekulinė krūvio pernaša, vidujemolekulinė sąsūka ir kt. Todėl naujų daugiafunkcinių molekulinių darinių savybių optimizavimas yra aktuali nūdienos organinės elektronikos problema. Šiame darbe didžiausias dėmesys skiriamas daugiafunkcinių organinių spinduolių fotofizikinių savybių valdymui. Čia nagrinėjami daugiafunkcinių molekulinių spinduolių agregacijos nulemti reiškiniai ir jų valdymo galimybės, optimizuojant sluoksnio funkcines savybes tokias kaip plėvėdaros savybės, krūvio pernaša, emisijos našumas, sustiprintos savaiminės spinduliuotės slenkstis ir kt.

La fluorescence de la chlorophylle (ChlF) est directement liée au processus photosynthétique. Cependant, au niveau de la canopée, ce lien physiologique entre la fluorescence et la photosynthèse peut être brouillé par les changements structurels de la végétation et les interactions entre la lumière du soleil et la structure 3D de la canopée. De plus, une grande partie de nos connaissances sur la relation entre la fluorescence et l'état physiologique des plantes provient d'études au niveau des feuilles réalisées dans des conditions de laboratoire. La signification physiologique de la ChlF au niveau de la canopée et dans des conditions naturelles est toujours un sujet de recherche majeur. Ce projet doctoral avait pour objectifs : 1. Etude du rendement de fluorescence de la chlorophylle au niveau de la canopée: nous décrivons un nouvel instrument, Ledflex, qui est un micro-LIDAR dédié à effectuer des mesures continues du rendement de fluorescence de la végétation. Ledflex a été appliqué avec succès dans des conditions de plein soleil pour établir la signature du stress hydrique sur la canopée du pois (Pisum Sativum). Dans des conditions bien irriguées, le cycle diurne du rendement de fluorescence observé (Fs) présente une forme en M avec un minimum (Fmin) vers midi supérieur au niveau observé à l’obscurité (Fo). Après plusieurs jours sans irrigation, Fs diminue et Fmin
The chlorophyll fluorescence (ChlF) is directly related to the photosynthetic process. However, at canopy level this physiological link between fluorescence and photosynthesis may be blurred by structural vegetation changes and geometrical effects linked to interactions between sunlight and the three-dimensional structure of the canopy. Furthermore, much of our knowledge about the relationship between fluorescence and the physiological status of plants come from leaf level studies carried out under laboratory conditions. The physiological significance of ChlF at canopy level and under natural conditions is still a major subject of research and a source of uncertainties in the interpretation of SIF. This doctoral project aims were: 1. To study chlorophyll fluorescence yield at canopy level: we describe a new instrument, Ledflex, which is a micro-LIDAR dedicated to perform continuous measurements of vegetation fluorescence yield. Ledflex has been successfully applied under full sunlight conditions to establish the signature of water-stress on a pea (Pisum Sativum) canopy. Under well-watered conditions the Fs diurnal cycle present an M shape with a minimum (Fmin) at noon which is higher than the fluorescence level observed at predawn (Fo). After several days withholding watering, Fs decreases and Fmin

La fluorescence chlorophyllienne induite par le soleil (SIF) est désormais utilisée comme outil pour suivre la production primaire brute (GPP) du couvert végétal de différents écosystèmes. La SIF est importante pour comprendre le cycle global du carbone dans un contexte de changements climatiques. Cependant, l’usage de la SIF pour suivre les variations de la GPP est entravée par des facteurs confondants (propriétés biochimiques des feuilles, facteurs abiotiques, etc.). Dans cette thèse, on propose d’utiliser des observations à plusieurs échelles [satellitaires (TROPOMI et MODIS) et au sol] de la SIF, de réflectance, de la GPP et du rendement de la fluorescence chlorophyllienne par mesure active (FyieldLIF), utile pour observer les variations physiologiques de la végétation, afin d’abord 1) d’évaluer la force des liens GPP-SIF et de prédire la GPP à l’aide de mesures spatiales ; ensuite, 2) d’examiner les liens FyieldLIF-SIFy (SIF normalisé par le rayonnement photosynthétiquement actif, PAR) et les effets de structure du couvert végétal sur la SIF; et enfin 3) d’explorer l’influence de la structure de la canopée et des facteurs abiotiques sur les variations de la SIF et de la GPP et sur leurs liens. On constate que la force et la nature des liens GPP-TROPOMI SIF sur 40 sites de tours à flux dépendent du site et du type de végétation, reflétant l’hétérogénéité spatiale et temporelle de la couverture végétale du pixel TROPOMI. En outre, les mesures satellitaires de la SIF et de la réflectance prédisent plus de 80 % des variations de la GPP. Toutefois, on remarque que les réflectances à différentes bandes prises ensemble prédisent mieux la GPP que TROPOMI SIF, mais l’importance relative montre que la SIF est la variable la plus importante pour prédire la GPP (SIF plus les indices de végétation (VIs) comme variables explicatives). Ce résultat soutient qu’à des échelles spatiales larges la réflectance pourrait être utilisée pour estimer la GPP et que l’usage de la SIF comme proxy de la GPP soulève la question de savoir si l’information physiologique liée à la photosynthèse issue de la SIF pourrait être détectée à cette échelle. Par ailleurs, à partir de mesures au sol effectuées à Fontainebleau-Barbeau, on montre que FyieldLIF n’est pas corrélé avec SIFy à l’échelle diurne à cause des effets de géométrie d’éclairement. On constate aussi que les dynamiques diurnes de la SIF et du PAR décorrèlent lors des jours de ciel clair, montrant les effets de l’ombre sur la SIF. On montre aussi que la SIF et la réflectance peuvent être utilisées pour prédire FyieldLIF, tandis Φk (SIFy/FyieldLIF) (indicateur de l’interaction structure-éclairement) est corrélé à la réflectance et à la géométrie de la canopée. On souligne que les liens GPP-SIF et leurs variations dépendent de l’échelle temporelle considérée. Particulièrement, à l’échelle saisonnière, on observe que les variations de GPP, SIF, SIFy et FyieldLIF répondent au développement structurel et biochimique des canopées, ainsi qu’aux facteurs abiotiques. Lors des vaques de chaleurs, on constate que la SIF et les VIs (NDVI, NIRv et mNDI) d’une part et la SIF et le PAR d’autre part ne sont pas corrélés, tandis que GPP, SIF et FyieldLIF diminuent fortement. Ceci indique que SIF et FyieldLIF peuvent être utilisés pour suivre la photosynthèse du couvert en conditions de stress alors que les VIs ne peuvent pas. Cette réponse spécifique de la SIF et FyieldLIF comparée aux VIs souligne l’intérêt croissant de l’usage de la SIF comme proxy de la GPP dans des conditions climatiques changeantes. Toutefois, à l’échelle diurne, les interactions entre structure de la canopée et géometrie d’éclairement contrôlent les variations de la SIF, de la GPP et de la relation GPP-SIF. On recommande l’usage de la synergie réflectance-SIF et des mesures actives pour mieux comprendre les variations de la SIF et son lien avec la GPP sur d’autres types de couverts végétaux
Sun-Induced chlorophyll Fluorescence (SIF) is used as a tool to monitor Gross Primary Production (GPP) across different ecosystems. SIF is important to understand the global carbon cycle under changing climate conditions. However, the use of SIF to probe variations in GPP is challenged by confounding factors (canopy biochemical properties, abiotic factors, etc.). In this thesis, we proposed to use multiple scale measurements (spaceborne with the TROPOMI and MODIS sensors, and ground-based) of SIF, reflectance, GPP, and active chlorophyll fluorescence yield (FyieldLIF), useful to observe the physiological variations of the vegetation. In order, first, to evaluate the strength and the nature of the relationship between GP-SIF and to predict GPP using remote sensing metrics; second, to examine the relationship between FyieldLIF and SIFy (SIF normalized by the photosynthetically active radiation, PAR) and the effects of canopy structure and sun-canopy geometry on SIF signal, and third, to explore the influence of canopy structure, light intensity and abiotic factors on SIF and GPP variations and on their links. We found that the strength and the nature of the links between GPP and TROPOMI SIF, across forty flux sites, depend on sites and vegetation types. Further, combined use of SIF and reflectance from satellite observations predicted over 80% of GPP variations. However, we observed that daily surface reflectance at different bands when taken as a whole outperformed daily TROPOMI SIF in predicting GPP, but the relative importance of variables in the random forest model using SIF and VIs (NDVI, PRI and NIRv) as inputs to predict GPP shows that SIF is the most important variable for predicting GPP. This result indicates that at a broad spatial scale, reflectances could be used to predict GPP and the use of SIF as a proxy of GPP raises the question of whether the physiological information related to photosynthesis contained in SIF could be detected at this scale. Based on top-of-canopy measurements in Fontainebleau-Barbeau, we show that active FyieldLIF was not correlated with passive SIFy at the diurnal timescale due to sun-canopy geometry effects. We also observed that the diurnal patterns in SIF and PAR did not match under clear sky conditions, underlining the effects of shadows on the measured canopy SIF. We also showed that the SIF and the reflectance can be used to predict FyieldLIF, while Φk =SIFy/FyieldLIF (an indicator of the interaction between canopy structure and irradiance geometry) is strongly correlated with reflectance and sun-canopy geometry. The analyses show that the links between GPP and SIF and their variations, resulting from ground-based measurements, depend on the temporal scale considered. More specifically, at the seasonal scale, we observed that variations in GPP, SIF, SIFy and FyieldLIF respond to the structural and biochemical development of canopies and to variations in abiotic factors, especially during the heatwaves in 2022. During these extreme weather conditions, we observed that, on one hand, SIF and VIs (NDVI, NIRv and mNDI), and on the other hand, SIF and PAR are not correlated, while GPP, SIF and FyieldLIF strongly decreased. This indicates that SIF and FyieldLIF can be used to monitor impact on photosynthetic activity under stress conditions, while VIs cannot. This specific response of SIF and FyieldLIF compared to VIs highlights the growing interest in the use of SIF as a proxy of GPP under changing climate conditions. However, at the diurnal scale, the interactions between canopy structure and sun geometry, as well as the light intensity control the variations in SIF and GPP and their links. We strongly recommend the use of the synergy between reflectance, SIF and active fluorescence measurements to better understand the dynamics of SIF and its link to GPP in other vegetation types at the canopy scale

[EN] Pepper is a vegetable of extraordinary economic and social importance in our country. Unfortunately, the persistent exploitation of the land, the monoculture and the intensification of production processes, lead to the development of soil diseases. This coupled with the abiotic stress, mainly the salinity of waters and soil, suboptimal temperatures and water stress, can induce the appearance of physiological disorders in peppers as the Blossom-end rot (BER) and cracking or cracked, induce plant senescence and decrease not only production, but also the quality of the product. Salinity and water shortages are two among the biggest environmental problems that crops have to face in the Mediterranean area. A way to overcome the stresses under the prism of an ecological or integrated crop management, is the use of grafted plants as adaptation strategy. Although there has been remarkable progress in this technique (mainly in tomato, melon, watermelon), in the cultivation of pepper use remains rare. In this Doctoral thesis several pepper genotypes have been selected through different physiological parameters which indicate tolerance to salt and water stress. Commercial cultivars were grafted onto the selected genotypes and were grown under water stress, salinity and control conditions studying several physiological, agronomic responses and the interaction rootstock/scion. The results obtained concluded that genotypes selected and used as rootstocks improved commercial varieties to salt and water stress tolerance, both in terms of performance (commercial production) compared to other commercial characters and variety without grafting. Different physiological mechanisms explain the tolerance to stress, such as the ability to maintain the water potential through an osmotic adjustment, stimulation of the antioxidant system, exclusion or retention of toxic ions (Na+ and Cl-) in saline in the roots and the maintenance of photosynthesis which allows to maintain the metabolic functions of grafted plants and production.
[ES] El pimiento es una hortaliza de extraordinaria importancia económica y social en nuestro país. Lamentablemente, la persistente explotación del suelo, el monocultivo y la intensificación de los procesos de producción, conducen al desarrollo de enfermedades del suelo. Esto unido a los estreses abióticos, principalmente la salinidad de las aguas y del suelo, temperaturas subóptimas y estrés hídrico, puede inducir la aparición de fisiopatias en el pimiento como el Blossom-end rot (BER) y cracking o rajado, inducir senescencia vegetal y disminuir no solo la producción, sino también la calidad del producto. La salinidad y la escasez de agua son unos los mayores problemas medio ambientales a los que tienen que hacer frente los cultivos en el área Mediterránea. Un modo de sortear los estreses bajo el prisma de un manejo integrado o ecológico del cultivo, es la utilización de plantas injertadas como estrategia de adaptación. Aunque se ha producido un notable avance en esta técnica (principalmente en tomate, melón, sandía), en el cultivo del pimiento su utilización es poco frecuente aun. En esta Tesis Doctoral se han seleccionado mediante parámetros fisiológicos diferentes genotipos de pimiento tolerantes al estrés salino e hídrico. Los genotipos seleccionados fueron validados como patrones tolerantes a condiciones de estrés hídrico y salino injertados sobre una variedad comercial mediante el estudio de las respuestas fisiológicas, agronómicas y de la interacción patrón/variedad en ambas condiciones de estrés. De los resultados obtenidos se concluye que los genotipos seleccionados y utilizados como patrones mejoraron la tolerancia de las variedades comerciales a la salinidad, en términos de rendimiento (producción comercial) de frutos comparando con otros patrones comerciales y la variedad sin injertar. Diferentes mecanismos fisiológicos explican la tolerancia al estrés, como la capacidad de mantener el potencial hídrico mediante un ajuste osmótico, estimulación del sistema antioxidante, exclusión o retención de los iones tóxicos salinos (Na+ y Cl-) en las raíces y el mantenimiento de la fotosíntesis que permite mantener las funciones metabólicas de las plantas injertadas y la producción.
[CAT] El pimentó és una hortalissa d'extraordinària importància econòmica i social al nostre país. Lamentablement, la persistent explotació del sòl, el monocultiu i la intensificació dels processos de producció, conduïxen al desenrotllament de malalties del sòl. Açò unit als estressos abiòtics, principalment la salinitat de les aigües i del sòl, temperatures subòptimes i estrés hídric, pot induir l'aparició de fisiopaties en el pimentó com el Blossom-end rot (BER) i cracking, induir senescència vegetal i disminuir no sols la producció, sinó també la qualitat del producte. La salinitat i l'escassetat d'aigua són uns els majors problemes mitjà ambientals als que han de fer front els cultius en l'àrea Mediterrània. Una manera de sortejar els estressos davall el prisma d'un maneig integrat o ecològic del cultiu, és la utilització de plantes empeltades com a estratègia d'adaptació. Encara que s'ha produït un notable avanç en esta técnica (principalment en tomaca, meló, meló d'alger), en el cultiu del pimentó la seua utilització és poc freqüent. En esta Tesi Doctoral s'han seleccionat per mitjà de paràmetres fisiològics diferents genotips de pimentó tolerants a l'estrés salí i hídric. Els genotips seleccionats van ser validats com a patrons tolerants a condicions d'estrés hídric i salí empeltats sobre una varietat comercial per mitjà de l'estudi de les respostes fisiològiques, agronòmiques i de la interacció patrón/variedad en ambdós condicions d'estrés. Dels resultats obtinguts es conclou que els genotips seleccionats i utilitzats com a patrons van millorar la tolerància de les varietats comercials a la salinitat, tant en termes de rendiment (producció comercial) de fruits comparant amb altres patrons comercials i la varietat sense empeltar. Diferents mecanismes fisiològics expliquen la tolerància a l'estrés, com la capacitat de mantindre el potencial hídric per mitjà d'un ajust osmòtic, estimulació del sistema antioxidant, exclusió o retenció dels ions tòxics salins (Na+ i Cl-) en les arrels i el manteniment de la fotosíntesi que permet mantindre les funcions metabòliques de les plantes empeltades i la producció.
Penella Casañ, C. (2015). SCREENING PEPPER GENOTYPES TO OBTAIN TOLERANT ROOTSTOCKS TO SALT AND WATER STRESS: PHYSIOLOGICAL AND AGRONOMICAL RESPONSES OF THE GRAFTED PLANTS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58767
TESIS
Premiado

In this master thesis I have been dealt with the design and construction of an instrumental platform that used positioning focused laser beam (so-called optical tweezers) for manipulation with living cells without their damage.

The application of a method previously developed by Callis et al. to predict the quantum yields of Trp fluorescence has been successfully applied to the fluorescence of fluorescein and flavins in proteins. The calculated lifetime range of 2 ps - 4 ns is in agreement with experiment. The fluctuations in the electron transfer rate are shown to be dictated by the fluctuations in the density of states. This is evident by the comparison of the fractional deviation of the interaction, density of states and the rate. Here the fluctuations in the density of states is an order of magnitude larger than the fluctuations in the interactions and is nearly the same as that of the kET fluctuations. This demonstrates that the fluorescence lifetime variability is controlled by the electrostatic environment and not the distance dependence of the interaction.

Monomeric red fluorescent proteins (RFPs) are used extensively for applications in molecular biology research, and are especially suited for whole body imaging applications due to their longer excitation and emission wavelengths, which are less damaging and penetrate deeper into animal tissue. However, these proteins suffer from reduced brightness compared to other fluorescent proteins, and require further engineering, which is often achieved through random methods, incurring large time and resource costs. Here we propose a rational design approach to improve the quantum yield of RFPs by reducing conformational variability of the chromophore. We engineered mRojoA, a mutant containing a π-stack involving Tyr197 and the chromophore phenolate, to include the P63F/H/Y mutations on its other side, by simultaneously mutating neighbouring positions 16, 143, and 163. The brightest mutants that we found in each library, mRojo-VYGV, mRojo-VFAV, and mRojo-VHSV, exhibited 1.8- to 2.4-fold increases in brightness, and quantum yield increases of up to 2.1-fold. In all three mutants, the increases in brightness were predominantly due to improvements in the quantum yield and not the extinction coefficient. Solving the crystal structures of two of these mutants along with a dim variant allowed us to strongly infer a link between rigidity of the chromophore and increased quantum yield. In addition, back-mutating position 63 in the highest quantum yield mutant, mRojo-VYGV, reversed the improvement in quantum yield, indicating that Y63 was the primary residue responsible for the improved brightness of the protein. Unfortunately, the mCherry-VYGV mutant did not achieve a similar increase in quantum yield or brightness. This is likely due to the lack of a second bulky aromatic residue at position 197, which is present in mRojoA. Nevertheless, this rational approach could be applied to some other RFPs whose chromophores exhibit increased conformational variability in order to further improve their brightness.

Mesure du niveau de conduction d'alcanes et de cycloalcanes par difference de travaux de sortie metal/liquide, metal/vide de photocathodes en zinc ou en or irradiees par photons uv. Mise en evidence du role des etats de surface. Determination du seuil d'ionisation par photoionisation de liquides avec des photons de 7 a 10 ev. Comparaison des courbes a la theorie d'onsager. Etude de la nature des etats precurseurs a la paire separee ion-electron

A set of three benzophenoxazine dyes, two completely soluble and one partially soluble in aqueous media, has been prepared and their spectroscopic properties examined. These dyes can be used as either donor or acceptor in synthesis of through-bond energy transfer cassettes. Structural modifications prevented aggregation in water and improved their fluorescence properties in water. Their absorption and emission were studied in both organic and aqueous media. Two of the three dyes have superior quantum yields in aqueous media as compared to other reported dyes. Improved quantum yield makes these dyes attractive candidates for biological studies in aqueous media. We have also prepared alkynes and iodo derivatives of benzophenoxazines, which can be used for synthesis of water-soluble, through-bond, energy transfer cassettes. Alkynes were prepared via Sonogashira coupling.

Red fluorescent proteins (RFPs) are used extensively in biological research because their longer emission wavelengths are less phototoxic and allow deeper imaging of animal tissue. However, far-red RFPs generally display low brightness, emphasizing the need to develop brighter variants. Here, we investigate three approaches to rigidify the RFP chromophore to increase the quantum yield, and thereby brightness. We first used computational protein design on a maturation-efficient mRojo-VHSV variant previously engineered in our lab to introduce a Superdecker motif, a parallel pi-stack comprising aromatic residue side chains and the phenolate moiety of the chromophore, which we hypothesized would enhance chromophore packing and reduce non-radiative decay. The best mutants identified showed up to 1.7-fold higher quantum yield at pH 9, relative to their parent protein. We next postulated that brightness could be further increased by rigidifying the chromophore via branched aliphatic residues. Computational protein design was performed on a dim mCherry variant, mRojoA, followed by directed evolution on the brightest mutant. The combination of these methodologies yielded mSandy2, the brightest Discosoma-derived monomeric RFP with an emission maximum above 600 nm. Finally, we aimed to increase brightness by focusing on positions where residue rigidity correlated to quantum yield in mCherry-related RFPs according to NMR data that had been previously acquired in our lab. Combinatorial site-saturation mutagenesis was performed on two different surface patches of mCherry at positions 144/145/198 and 194/196/220. Our results demonstrated that surface residues may not be adequate targets for this approach. Altogether, the work herein presents unique rational design methodologies that can be used to increase brightness in RFPs.

The in origin intertidal marine brown alga Fucus vesiculosus L. grow permanently sublittoral in the brackish Bothnian Sea, side by side with the recently discovered F. radicans L. Bergström et L. Kautsky. Environmental conditions like salinity, light and temperature are clearly different between F. vesiculosus growth sites in the Bothnian Sea (4-5 practical salinity units, psu; part of the Baltic Sea) and the tidal Norwegian Sea (34-35 psu; part of the Atlantic Ocean). The general aims of this thesis were to compare physiological aspects between the marine ecotype and the brackish ecotype of F. vesiculosus as well as between the two Bothnian Sea species F. vesiculosus and F. radicans. The result in the study indicates a higher number of water soluble organic compounds in the marine ecotype of F. vesiculosus compared to the brackish ecotype. These compounds are suggested to be compatible solutes and be due to an intertidal and sublittoral adaptation, respectively; where the intertidal ecotype needs the compounds as a protection from oxygen radicals produced during high irradiation at low tide. The sublittoral ecotype might have lost the ability to synthesize these compound/compounds due to its habitat adaptation. The mannitol content is also higher in the marine ecotype compared to the brackish ecotype of F. vesiculosus and this is suggested to be due to both higher level of irradiance and higher salinity at the growth site. 77 K fluorescence emission spectra and immunoblotting of D1 and PsaA proteins indicate that both ecotypes of F. vesiculosus as well as F. radicans have an uneven ratio of photosystem II/photosystem I (PSII/PSI) with an overweight of PSI. The fluorescence emission spectrum of the Bothnian Sea ecotype of F. vesiculosus however, indicates a larger light-harvesting antenna of PSII compared to the marine ecotype of F. vesiculosus and F. radicans. Distinct differences in 77 K fluorescence emission spectra between the Bothnian Sea ecotype of F. vesiculosus and F. radicans confirm that this is a reliable method to use to separate these species. The marine ecotype of F. vesiculosus has a higher photosynthetic maximum (Pmax) compared to the brackish ecotype of F. vesiculosus and F. radicans whereas both the brackish species have similar Pmax. A reason for higher Pmax in the marine ecotype of F. vesiculosus compared to F. radicans is the greater relative amount of ribulose-1.5-bisphosphate carboxylase/oxygenase (Rubisco). The reason for higher Pmax in marine ecotype of F. vesiculosus compare to the brackish ecotype however is not due to the relative amount of Rubisco and further studies of the rate of CO2 fixation by Rubisco is recommended. Treatments of the brackish ecotype of F. vesiculosus in higher salinity than the Bothnian Sea natural water indicate that the most favourable salinity for high Pmax is 10 psu, followed by 20 psu. One part of the explanation to a high Pmax in 10 psu is a greater relative amount of PsaA protein in algae treated in 10 psu. The reason for greater amount of PsaA might be that the algae need to produce more ATP, and are able to have a higher flow of cyclic electron transport around PSI to serve a higher rate of CO2 fixation by Rubisco. However, studies of the rate of CO2 fixation by Rubisco in algae treated in similar salinities as in present study are recommended to confirm this theory.
Fucus vesiculosus L. (Blåstång) är en brunalg som i huvudsak växer i tidvattenzonen i marint vatten men arten klarar också att växa konstant under ytan i det bräckta Bottenhavet. Norska havet och den del av Bottenhavet, där algerna är insamlade i denna studie, har salthalterna 34-35 psu (praktisk salthaltsenhet) respektive 4-5 psu. F. radicans L. Bergström et L. Kautsky (Smaltång) är en nyligen upptäckt art (2005) som har utvecklats i Bottenhavet. F. radicans och Bottenhavets ekotyp av F. vesiculosus växer sida vid sida och har tidigare ansetts vara samma art. Sett till hela Östersjön, så ändras ytans salthalt från 25 till 1-2 psu mellan Östersjöns gräns mot Kattegatt och norra Bottenviken. Den låga salthalten i Östersjön beror på det höga flödet av sötvatten från älvarna och på ett litet inflödet av saltvatten i inloppet vid Kattegatt. Salthaltsgradienten är korrelerad med antalet arter som minskar med minskad salthalt. Östersjön är ett artfattigt hav och de arter som finns är till stor del en blandning av söt- och saltvattenarter. Det finns bara ett fåtal arter som är helt anpassade till bräckt vatten och F. radicans är en av dem. Exempel på miljöskillnader för F. vesiculosus i Norska havet och i Bottenhavet är salthalten, tidvattnet, ljuset och temperaturen. Tidvattnet i Norska havet gör att algerna växlar mellan att vara i vattnet och på land, vilket utsätter algerna för stora ljusskillnader, snabba och stora temperaturväxlingar samt även torka. De alger som växer i Bottenhavet har däremot en jämnare och lägre temperatur, istäcke på vintern och mindre tillgång på ljus eftersom de alltid lever under vattenytan. Skillnaderna i miljön mellan växtplatserna leder till skillnader i fysiologiska anpassningar. Anledningen till att F. vesiculosus och F. radicans valdes som studieobjekt i denna avhandling är att de är viktiga nyckelarter i Bottenhavet. F. vesiculosus och F. radicans är de enda större bältesbildande alger som finns i det artfattiga ekosystemet och de används därför flitigt som mat, gömställe, parningsplats och barnkammare för t.ex. fisk. Att de är nyckelarter gör det angeläget att försöka förstå hur algerna är anpassade och hur de reagerar på miljöförändringar för att få veta hur de kan skyddas och bevaras. F. radicans inkluderades även för att se hur en naturlig art i Bottenhavet är anpassad i jämförelse med den invandrade F. vesiculosus. Marin F. vesiculosus inkluderades för att vara en artreferens från artens naturliga växtplats. Studien visar att det finns fler vattenlösliga organiska substanser (finns vissa organiska substanser som har en proteinskyddande funktion) i den marina ekotypen av of F. vesiculosus än i Bottenhavets ekotyp. Anledningen till detta föreslås vara en anpassning till att växa i tidvattenzonen. Vid lågvatten utsätts F. vesiculosus från Norska havet för starkt ljus, uttorkning, och snabba temperatur- växlingar vilket gör att den kan behöva dessa organiska substanser som skydd mot fria syreradikaler som bildas under lågvattenexponeringarna. F. vesiculosus från Bottenhavet har troligen mist förmågan att syntetisera dessa substanser på grund av anpassning till att hela tiden växa under ytan. Mängden mannitol (socker) är högre i den marina ekotypen av of F. vesiculosus än i Bottenhavets ekotyp. Detta föreslås bero på högre fotosyntetiskt maximum i F. vesiculosus från Norska havet jämfört med ekotypen från Bottenhavet. Skillnaden i fotssyntetiskt maximum är bland annat kopplat till ljus- och salthaltskillnaden på algernas växtplatser. Denna teori styrks av att både fotosyntesen och halten av mannitol ökar i Bottenhavets ekotyp när den behandlas i högre salthalt. Studien visar även att båda ekotyperna av F. vesiculosus samt F. radicans har ett ojämnt förhållande mellan fotosystem II och I (PSII och PSI) med en dominans av PSI. Denna slutsats är baserad på fluorescens emissions mätningar vid 77 K (-196 °C) och mätning av den relativa mängden D1 protein (motsvarar PSII) och PsaA protein (motsvarar PSI). F. vesiculosus från Bottenhavet visar ett emission spektrum som pekar mot en jämnare fördelning av PSII och PSI jämfört med den marina ekotypen och F. radicans. Detta stämmer dock inte med förhållandet mellan D1/PsaA som indikerar att alla tre har mer PSI än PSII. Förklaringen till avvikelsen mellan metoderna antas vara att F. vesiculosus från Bottenhavet har större ljus-infångande antennpigment än marin F. vesiculosus och F. radicans. De tydliga skillnaderna i 77 K fluorescens emission spektra mellan Bottenhavets F. vesiculosus och F. radicans visar att denna metod kan användas som säker artidentifiering. Den marina ekotypen av F. vesiculosus har högre fotosyntetiskt maximum än de båda arterna från Bottenhavet. Mätningar av den relativa mängden av enzymet Rubisco, viktigt för upptaget av koldioxid hos växter och alger, visar att mängden enzym är en sannolik förklaring till skillnaden i fotosyntetiskt maximum mellan den marina ekotypen av F. vesiculosus och F. radicans och detta är troligen en normal artskillnad. Mängden Rubisco kan dock inte förklara skillnaden i fotosyntetiskt maximum mellan de båda ekotyperna av F. vesiculosus. För att undersöka vad skillnaden mellan dessa två beror på så föreslås istället mätningar av Rubisco’s koldioxidfixeringshastighet. Det är en ökning av fotosyntetiskt maximum i Bottenhavets ekotyp av F. vesiculosus när den behandlas i högre salthalt (10, 20 och 35 psu) och det högsta fotosyntetiska maximumet uppmättes i alger som behandlats i 10 psu. Denna ökning beror inte på ökning i den relativa mängden av Rubisco. Ökningen i fotosyntesen speglas dock av en ökning av den relativa mängden PsaA. Detta antas bero på att det behövs mer energi i form av ATP och att en ökning av detta kan ske på grund av att mer PsaA kan driva den cykliska elektrontransporten i fotosyntesreaktionen. Ökat behov av ATP antas bero på en ökning av Rubisco aktiviteten men mätning av aktiviteten krävs för att bekräfta detta.

Absolute K-shell x-ray cross sections and Auger-electron cross sections are measured for carbon for 0.6 to 2.0 MeV proton incident on CH₄, n-C₄H₁₀ (n-Butane), i-C₄H₁₀ (isobutane), C₆H₆ (Benzene), C₂H₂ (Acetylene), CO and CO₂. Carbon K-shell fluorescence yields are calculated from the measurements of x-ray and Auger-electron cross sections. X-ray cross sections are measured using a variable geometry end window proportional counter. An alternate method is described for the measurement of the transmission of the proportional counter window. Auger electrons are detected by using a constant transmission energy Π/4 parallel pi ate electrostatic analyzer. Absolute carbon K-shell x-ray cross sections for CH₄ are compared to the known results of Khan et al. (1965). Auger-electron cross sections for proton impact on CH₄ are compared to the known experimental values of RΦdbro et al. (1979), and to the theoretical predictions of the first Born and ECPSSR. The data is in good agreement with both the first Born and ECPSSR, and within our experimental uncertainties with the measurements of RΦdbro et al. The x-ray cross sections, Auger-electron cross sections and fluorescence yields are plotted as a function of the Pauling charge, and show significant variations. These changes in the x-ray cross sections are compared to a model based on the number of electrons present in the 2s and 2p sub shells of these carbon based molecules. The changes in the Auger-electron cross sections are compared to the calculations of Matthews and Hopkins. The variation in the fluorescence yield is explained on the basis of the multiconfiguration Dirac-Fock model.

L’imagerie moléculaire est devenue incontournable pour le diagnostic et le traitement de cancers. Cette discipline regroupe un ensemble de techniques telles que la tomodensitométrie (CT), l’Imagerie par Résonance Magnétique (IRM), l’imagerie optique ou encore l’imagerie nucléaire (tomographie par émission de positons TEP, tomographie d’émission monophotonique TEMP). Chacune de ces techniques possède ses propres avantages et inconvénients et ne peut apporter à elle seule des informations anatomiques et fonctionnelles suffisantes. Les travaux actuels sont portés sur la conception de systèmes dits multimodaux afin de combiner les avantages de différentes techniques, voire de bénéficier d’un effet synergique. De par leur sensibilité comparable et leur complémentarité, coupler l’imagerie nucléaire à l’imagerie optique devient alors avantageux. La conception des systèmes monomoléculaires (MOMIA) contenant deux fonctions détectables par imagerie nucléaire (complexe de radiométaux) et imagerie optique (sonde fluorescente) nécessite en amont la mise au point d’outils de synthèses performants. La première partie de ce travail de thèse est consacrée à la synthèse d’agents chélatants bifonctionnels à base de polyamines macrocycliques, destinés à une utilisation en imagerie médicale. Ces agents doivent présenter d’excellentes propriétés de coordination vis-à-vis du métal visé, et posséder une fonction de greffage pour assurer le couplage avec une biomolécule vectrice. L’accès à de tels systèmes a nécessité le développement d’outils de synthèse efficaces de précurseurs macrocycliques dérivés du cyclène et du 13aneN4. L’introduction sélective de diverses fonctions de greffage visant principalement les résidus de type lysine a permis la préparation de plusieurs familles de composés, dont certains ont pu être « bioconjugués» à des peptides ou anticorps au sein du laboratoire ou dans le cadre de diverses collaborations. Plus particulièrement, la facilité d’utilisation du système « DOTAGA anhydride » a permis l’introduction aisée d’unités DOTA sur des nanoparticules ou des anticorps monoclonaux. Egalement, l’introduction d’une fonction alcyne a permis l’accès à de nouvelles briques moléculaires préparées par « click chemistry ». Dans une seconde partie sont présentés les travaux relatifs à la synthèse d’agents bimodaux originaux. Pour accéder à de tels systèmes, l’introduction d’un fluorophore de la famille des bodipys a été envisagée. L’absence de travaux antérieurs relatifs au couplage d’une polyamine cyclique et une entité bodipy a nécessité la préparation préalable d’un système modèle « DOTA bodipy », permettant de s’assurer par des études photophysiques que la présence des complexes métalliques macrocycliques ne va pas, ou peu, interférer avec les propriétés de fluorescence du bodipy. L’utilisation d’un espaceur « acide aminé » a alors permis d’accéder à de nouveaux bodipys porteurs de deux groupes fonctionnels en position méso. La fonctionnalisation a posteriori de ces briques de construction a permis l’introduction en dernier lieu d’unités macrocycliques N- et/ou C- fonctionnalisés. La préparation de système émettant dans le proche I.R. a été également envisagée
Molecular imaging became a major tool for the diagnosis and the treatment of cancers. This research field includes different techniques, such as Tomography (CT), Magnetic Resonance Imaging (MRI), Optical Imaging or nuclear Imaging (PET Positron Emission Tomography, SPECT Single Photon Emission Computed Tomography). Each imaging modality has its own strengths and weaknesses, and thus, combining different and complementary systems can overcome inherent limitations associated with any one individual techniques and improve the accuracy of disease diagnosis and enhancing patient management. In particular dual-modality Optical/Nuclear imaging may find important preclinical and clinical applications. One possible approach seeks to fuse the two imaging systems into one molecule (MonOmolecular Multimodality Imaging Agent [MOMIA]) in order to ensure the same biodistribution of the two probes. Our strategy consists in combining a DOTA-like compound allowing complexation of radiometal for nuclear imaging (SPECT or PET) with a bodipy moiety, valuable probe those fluorescent properties can be finely adjusted. The first part of this work is dedicated to the synthesis of bifunctional chelating agents based on macrocyclic polyamines for medical imaging application. These compounds must show excellent coordination properties towards the aimed radiometal and possess a grafting function to allow the coupling with a biomolecule. Powerful and general routes for the synthesis of a wide range of N- and C-functionalized macrocycles derived from cyclen and 13aneN4 are described, which enable to access to a wide range of new BFCs by introduction of different functional groups reactive towards primary amines, such as carboxylic acid, isothiocyanate or anhydride function. Some compounds were conjugated to different biomolecules, such as peptides or antibodies. Morever, the introduction of an alkyne function yields a novel family of bifunctional agents allowing chemoselective attachment to functionalized biomolecules or to modified amino acids using « click chemistry ». In a second part, we focused on the introduction of a bodipy moeity to obtain new bimodal agents for dual Optical/Nuclear imaging. Interestingly, the attachment of the polyaminocarboxylate (DOTA derivative) to the bodipy makes it soluble in water and complexation of different metal cations of interest in the macrocyclic cavity does not significantly alter the luminescence properties of the whole system. In addition, the functionalization of the meso position by using an appropriate linker between the bodipy and DOTA-like units, i.e. a 4-nitrophenylalanine derivative, could provide a new bimodal tag for labeling antibodies or peptides. Optimisation of the second generation bodipy-DOTA, i.e. derivatization reaction to reach the near-IR range or introduction of C-functionalised macrocycles was also investigated

La présente thèse étudie les nanoparticules de ZnO incorporées dans une matrice d'acide polyacrylique (PAA) mésosphérique synthétisée via un protocole d'hydrolyse. La structure hybride mésosphérique de ZnO / PAA a précédemment démontré son efficacité pour émettre de la lumière visible dans une large gamme, qui résulte des défauts intrinsèques de niveaux profonds dans les nanocristaux de ZnO. Pour modifier davantage le spectre de photoluminescence (PL) et améliorer le rendement quantique de PL (PL QY) du matériau, le ZnO dopé au métal et le ZnO / PAA revêtu de silice sont fabriqués indépendamment. Au niveau du ZnO dopé avec des éléments métalliques, la nature, la concentration, la taille et la valence du dopant affectent la formation des mésosphères et par conséquent la PL et le PL QY. Les ions plus grands que Zn2+ avec une valence plus élevée ont tendance à induire des mésosphères plus grandes et des nanoparticules de ZnO non incorporées. Le dopage conduit généralement à l'extinction de la PL, mais le spectre PL peut toujours être ajusté dans une large plage (entre 2,46 eV et 2,17 eV) sans dégrader le PL QY en dopant avec de petits ions à une faible concentration de dopage (0,1 %). Concernant le ZnO / PAA revêtu de silice, un revêtement optimal est obtenu, qui dépend corrélativement de la quantité de TEOS et d'ammoniac dans le processus de revêtement. La quantité de TEOS n'affecte pas la structure cristalline de ZnO ou le spectre PL du matériau, mais une concentration élevée d'ammoniac peut dégrader les mésosphères de PAA et épaissir la couche de silice. Une fine couche de silice qui n'absorbe pas trop de lumière d'excitation mais recouvre complètement les mésosphères s'avère être la plus efficace, avec une amélioration drastique du PL QY d’un facteur six. En ce qui concerne l'application, les matériaux souffrent d’une dégradation thermique à des températures élevées jusqu'à 100 °C, auxquelles les diodes électroluminescentes blanches (WLEDs) fonctionnent généralement. Cependant, le ZnO / PAA revêtu de silice induit une intensité d'émission plus élevée à température ambiante pour compenser la dégradation thermique
The present thesis studies ZnO nanoparticles embedded in a mesospheric polyacrylic acid (PAA) matrix synthesized via a hydrolysis protocol. The mesospheric ZnO/PAA hybrid structure was previously proved efficient in emitting visible light in a broad range, which results from the deep-level intrinsic defects in ZnO nanocrystals. To further tune the photoluminescence (PL) spectrum and improve the PL quantum yield (PL QY) of the material, metal-doped ZnO and silica-coated ZnO/PAA are fabricated independently. For ZnO doped with metallic elements, the nature, concentration, size and valence of the dopant are found to affect the formation of the mesospheres and consequently the PL and PL QY. Ions larger than Zn2+ with a higher valence tend to induce larger mesospheres and unembedded ZnO nanoparticles. Doping generally leads to the quenching of PL, but the PL spectrum can still be tuned in a wide range (between 2.46 eV and 2.17 eV) without degrading the PL QY by doping small ions at a low doping concentration (0.1 %). For silica-coated ZnO/PAA, an optimal coating correlatively depends on the amount of TEOS and ammonia in the coating process. The amount of TEOS does not affect the crystal structure of ZnO or the PL spectrum of the material, but high concentration of ammonia can degrade the PAA mesospheres and thicken the silica shell. A thin layer of silica that does not absorb too much excitation light but completely covers the mesospheres proves to be the most efficient, with a drastic PL QY improvement of six times. Regarding the application, the materials suffer from thermal quenching at temperatures high up to 100°C, at which white light emitting diodes (WLEDs) generally operates. However, silica-coated ZnO/PAA induces higher emission intensity at room temperature to make up for the thermal quenching

I biofilm fototrofi sono comunità di microorganismi fototrofi ed eterotrofi che crescono adesi a ogni superficie sommersa degli impianti di depurazione delle acque grazie all’energia solare, che sostiene il processo fotosintetico, e al flusso costante di acqua, che consente un apporto continuo di nutrienti inorganici. Finora, l’ecofisiologia dei biofilm fototrofi di ambiente acquatico è stata scarsamente caratterizzata in coltura. Lo scopo di questa tesi è stato quello di valutare le caratteristiche fotosintetiche, la fotoacclimatazione e la capacità di rimozione dei nutrienti dalle acque di biofilm fotosintetici di impianti di depurazione in condizioni controllate di crescita. Questo studio è parte del progetto europeo PHOBIA che ha lo scopo di sviluppare un modello concettuale unitario per i biofilms fototrofi in ambiente acquatico. I biofilm venivano campionati dalle pareti della vasca di sedimentazione dell’impianto di depurazione delle acque reflue dell’aeroporto “Leonardo da Vinci”, Fiumicino (Roma, Italia) e messi in coltura in un prototipo di incubatore a diverse condizioni di irradianza, temperatura e velocità di flusso del terreno di coltura. L’effettiva resa quantica del fotosistema II (PSII) e curve di fotosintesi Electron Transport Rate versus Irradiance (ETR/I) erano registrate allo stadio iniziale, attivo e maturo di sviluppo dei biofilm mediante un fluorimetro PAM (Pulse Amplitude Modulated), e le clorofille, i carotenoidi e le ficobiliproteine quantificate per determinare la capacità fotosintetica e di fotoacclimatazione della comunità, e la variazione di biomassa nel tempo. Metodi spettrofotometrici erano utilizzati per quantificare l’azoto e il fosforo totali nei biofilm, con lo scopo di valutare la capacità di rimozione dei due nutrienti. Inoltre, dei campioni erano fissati per la microscopia elettronica a trasmissione e osservati per visualizzare le riserve di azoto e fosforo intracellulari. I biofim crescevano in coltura raggiungendo un’elevata biomassa nelle varie condizioni di crescita. L’utilizzo del fluorimetro PAM consentiva di valutare rapidamente e in maniera non invasiva la capacità fotosintetica dei biofilm. La resa quantica del PSII era significativamente influenzata dalle condizioni sperimentali, con valori più elevati a irradianza crescente e a valori bassi di temperatura e flusso. I risultati delle curve ETR/I mostravano la capacità di acclimatazione dei fototrofi alle diverse condizioni di irradianza, come confermato ulteriormente dalla variazione del contenuto dei pigmenti fotosintetici. I dati spettrofotometrici rivelavano alte concentrazioni di azoto e fosforo nei biofilm a indicare che i due nutrienti venivano rapidamente sottratti dal mezzo di coltura e accumulati dai biofilm durante la crescita. Inoltre, condizioni di bassa temperatura e flusso influenzavano positivamente l’accumulo dei nutrienti. I cianobatteri e le microalghe erano attivamente coinvolti nella rimozione di azoto e fosforo come evidenziato a livello ultrastrutturale dalla presenza di granuli di cianoficina e accumuli di polifosfato, rispettivamente. La comprensione dei processi di acclimatazione e della dinamica di rimozione dei nutrienti nei biofilm fototrofi di impianti di depurazione è di primaria importanza per lo sviluppo di un trattamento terziario alternativo e ecologicamente sicuro basato sull’impiego di comunità autoctone. In quest’ottica, il passo successivo è rappresentato dall’isolamento e coltura di specie che accoppiano elevata produttività e efficienza di rimozione dei nutrienti per la creazione in laboratorio di inoculi di biofilm da utilizzare nel processo di depurazione.
Phototrophic biofilms are an ensemble of photo- and heterotrophic microorganisms which grow attached to every submerged surface of wastewater treatment plants (WWTPs) thanks to the solar energy, which support the photosynthetic processes, and to the constant water flow, which provides a continuous load of inorganic nutrients. Hitherto, the ecophysiology of aquatic phototrophic biofilms from WWTPs has been poorly characterised in culture. The aim of this thesis was to assess the photosynthetic characteristics, photoacclimation and nutrient removal ability of phototrohic biofilms from an Italian WWTP under controlled conditions. This study was part of the PHOBIA EU-Project aimed at developing a unifying model of structure and functioning of aquatic phototrotrophic biofilms. Biofilms were collected from the walls of the sedimentation tank (ST) of the Leonardo da Vinci Airport WWTP, Fiumicino (Rome, Italy) and cultured in an incubator prototype at different irradiance, temperature and flow regime. Effective quantum yield of photosystem II (ΔF/Fm') and Electron Transport Rate versus Irradiance (ETR/I) curves were recorded at initial, active and mature stages of biofilm development by means of a Pulse Amplitude Modulated (PAM) fluorometer, and the chlorophylls, carotenoids and phycobiliproteins quantified to determine the community photosynthetic and photoacclimation ability, and phototrophic biomass variation over time. In order to assess the nutrient removal ability, spectrophotometric methods were used to quantify the total nitrogen (N) and phosphorus (P) content in cultured biofilms. Samples were also fixed for transmission electron microscopy (TEM) and observed to visualise intracellular N and P reserves. Biofilms were able to grow in culture attaining high biomass in the different conditions tested. PAM-fluorescence technique provided a rapid and non-invasive assessment of the photosynthetic performance. ΔF/Fm' was significantly affected by the different conditions tested, with higher values obtained at increasing growth irradiance, low temperature and low flow. Data obtained by ETR/I curves recordings demonstrated the acclimation ability of phototrophs to varying irradiance as further confirmed by the variation of photosynthetic pigments. Spectrophotometric data revealed high N and P concentrations in the biofilms indicating that the two nutrients were rapidly removed from the medium and stored by the biofilms during growth. In addition, low temperature and flow positively influenced P retention in the biofilms. Cyanobacteria and microalgae were actively involved in N and P removal and accumulation as evidenced at ultrastructural level by the occurrence of cyanophycin granules and polyphosphate bodies, respectively. Understanding acclimation processes and nutrient removal dynamics in WWTP phototrophic biofilms is of major importance to the development of alternative and environmentally sound tertiary water treatment exploiting autochthonous communities. On this basis, the following step is represented by the isolation and culturing of species that couple high productivity and nutrient removal efficiency for the laboratory creation of biofilm inocula to be used in the depuration process.

Manipulating light by controlling surface plasmons on metals is being discussed as a means for bridging the size gap between micrometer-sized photonic circuits and nanometer-sized integrated electronics. Plasmonic waveguides based on metal nanoparticles are of particular interest for circumventing the diffraction limit, thereby enabling high-speed communication over short-range distances in miniaturized micro-components. However, scalable, inexpensive fine-tuning of particle assemblies remains a challenge and near-field probing is required to reveal plasmonic interactions. In this thesis, self-assembled waveguides should be produced on DNA scaffolds. DNA origami is an extremely versatile and robust self-assembly method which allows scalable production of nanostructures with a fine control of assemblies at the nanoscale. To form the plasmonic waveguides, six-helix bundle DNA origami nanotubes are used as templates for attachment of highly monodisperse and monocrystalline gold nanoparticles with an inter-particle distance of 1-2 nm. In the first part of this thesis, the effects of parameters which are involved in assembly reactions are systematically investigated. The assembly yield and binding occupancy of the gold nanoparticles are determined by an automated, high-throughput image analysis of electron micrographs of the formed complexes. As a result, unprecedented binding site occupancy and assembly yield are achieved with the optimized synthesis protocol. In addition, waveguides with different sizes of gold nanoparticles and different inter-particle distances, quantum dots attachments to the waveguides and multimerization of the waveguides are successfully realized. In the second part of this thesis, direct observation of energy transport through a self-assembled waveguide towards a fluorescent nanodiamond is demonstrated. High-resolution, near-field mapping of the waveguides are studied by electron energy loss spectroscopy and cathodoluminescence imaging spectroscopy. The experimental and simulation results reveal that energy propagation through the waveguides is enabled by coupled surface plasmon modes. These surface plasmon modes are probed at high spatial and spectral resolutions. The scalable self-assembly approach presented here will enable the construction of complex, sub diffraction plasmonic devices for applications in high-speed optical data transmission, quantum information technology, and sensing
Die Manipulation des Lichts durch die Kontrolle von Oberflächenplasmonen auf metallischen Oberflächen und Nanopartikeln gilt als vielversprechende Methode zur Überbrückung der Größen-Lücke zwischen Mikrometer-großen photonischen und nanometer-großen elektronischen Schaltkreisen. Plasmonische Wellenleiter basierend auf metallischen Nanopartikeln sind vom besonderen Interesse, da sie die Umgehung des Beugungslimits und somit eine Hochgeschwindigkeitskommunikation über kurze Distanzen in immer kleiner werdenden Schaltkreisen ermöglichen könnten. Allerdings ist die skalierbare und kostengünstige Anordnung von Partikeln eine große Herausforderung und es werden Nahfelduntersuchungen benötigt um plasmonische Interaktionen detektieren zu können. Das Ziel dieser Arbeit ist die Selbstassemblierung von multi-partikel Wellenleitern auf DNA Gerüsten. Die Verwendung von DNA-Origami bietet eine äußerst vielseitige Plattform zur skalierbaren Herstellung von Nanostrukturen mittels Selbstassemblierung und ermöglicht eine präzise Kontrolle der Anordnungen im Nanobereich. Für den Aufbau der plasmonischen Wellenleiter werden DNA-Origami Nanoröhren, bestehend aus sechs Helices als Templat für die Anbindung von monodispersen und monokristallinen Goldnanopartikeln mit einem interpartikulären Abstand von 1-2 nm verwendet. Im ersten Abschnitt dieser Arbeit werden die beeinflussenden Faktoren dieser Assemblierungsreaktion systematisch untersucht. Die Ausbeute der assemblierten Strukturen und die Besetzung der Bindungsstellen werden durch eine automatisierte und effiziente Bildanalyse von Elektronenmikroskopieaufnahmen ausgewertet. Durch die Entwicklung eines optimierten Syntheseprotokolls werden bisher unerreichte Assemblierungsausbeuten ermöglicht. Zusätzlich erfolgen die experimentelle Realisierung von Strukturen mit verschieden großen Goldnanopartikeln und unterschiedlichen interpartikulären Abständen, sowie die Anbindung von Quantenpunkten an die Wellenleiter und eine Verknüpfung der assemblierten Strukturen. Der zweite Abschnitt dieser Dissertation befasst sich mit der Untersuchung des Energietransports in selbstassemblierten Wellenleitern über einen fluoreszierenden Nanodiamanten. Dazu erfolgen hochaufgelöste Nahfeldmessungen der Wellenleiter mittels Elektronenenergieverlustspektroskopie und Kathodolumineszenz-mikroskopie. Die experimentellen Ergebnisse und zusätzlich durchgeführte Simulationen bestätigen eine durch gekoppelte Oberflächenplasmonenmoden induzierte Weitergabe der Energie innerhalb des Wellenleiters. Diese Oberflächenplasmonenmoden werden bei hoher räumlicher und spektraler Auflösung untersucht. Das hier umgesetzte Konzept der Selbstassemblierung wird den Aufbau komplexer plasmonischer Geräte für Anwendungen im Bereich der optischen Hochgeschwindigkeitsdatenübertragung, der Quanteninformations-technolgie und der Sensorik ermöglichen

X-ray absorption spectroscopy (XAS) is a powerful probe of electronic and spatial structure that has been at the heart of many advances in physics, biology, chemistry, engineering and the earth sciences. Unfortunately, the existing experimental techniques are subject to fundamental limitations that complicate the interpretation of x-ray absorption spectra in many important cases. These limitations have motivated an effort to develop an alternative measure of the absorption cross-section that is not subject to the same set of limitations. In this thesis, a technique known as inverse partial fluorescence yield (IPFY) is described which addresses this problem. IPFY differs from existing approaches in a significant way — by using an energy-discriminating photon detector, one gains access to fluorescence information from both resonant and non-resonant x-ray emission processes. We will show that the non-resonant emission is fundamentally related to the total absorption cross-section of a material through an inverse relation. This will be proven by extension of the general theory of fluorescence yield for the case of a thick, homogeneous specimen. We will also demonstrate the utility of IPFY with measurements of NiO, NdGaO₃, LNSCO, and stainless steel 304 at soft and intermediate x-ray energies. These experiments will highlight some essential features of IPFY spectroscopy and demonstrate how it can be an invaluable tool when the other experimental techniques fail to provide reliable spectra. We will also demonstrate how one can exploit the geometry dependence of IPFY to quantitatively determine the composition of a sample and the total x-ray absorption coefficient. Additionally, we will consider the special cases of multilayers and powder specimens, where the theory of fluorescence yield requires approximations and is not as well-behaved as in thick, homogenous specimens. Ultimately, these experiments and theoretical developments will be used to support the claim that IPFY is a bulk sensitive measure of the total x-ray absorption coefficient. Moreover, we will show that IPFY is not affected by saturation effects, is insensitive to surface contamination layers and provides reliable spectra even for strongly insulating materials. These properties make IPFY a suitable spectroscopic technique for studying XAS in a wide range of materials.

Recently a new x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has been developed that is bulk sensitive and free of saturation effects, which also provides a direct measure of total absorption coefficient. However, IPFY was originally formulated for smooth bulk samples, but XAS is often performed on rough samples. To test the applicability of IPFY on rough surfaces, a model is presented and the calculations based on this model are compared to the experimental results measured on NdGaO3. It is shown that the correspondence between calculated and experimental intensities of IPFY is sufficient to corroborate this model a means of estimating the maximum allowable surface roughness size and the optimal detection geometry.

To fully exploit the capability of NV centers in diamond as magnetic sensors and quantum bits, the optimum production recipe as well as the method to enhance its optical performance has been studied in this work. The NV centers in bulk diamond were prepared by ion implantation and electron irradiation, and the optimum dose and temperature are found by comparing its optical and magnetic performance both experimentally and theoretically. In addition, the enhancement of optical performance and size characterization of NV centers in nanodiamonds will be discussed in this work.

碩士
國立臺灣科技大學
化學工程系
100
In this research, we report the effect of the initial Ag:In stoichiometry, capping ligand concentration, and reaction temperature on the optical properties of AgInS2 quantum dots (QDs). The fabricated QDs exhibit excellent optical characteristics, including PL quantum yields of up to 22 % and the appearance of an excitonic absorption peak. This is the first reported observation of such a well-defined exciton absorption feature in AgInS2 QDs. Its appearance could indicate a relatively narrow size distribution or minimization of nonradiative recombination at the surface sites of the QDs. Moreover, we report one-pot two-step synthesis of highly luminescent AgInS2-ZnS QDs by injection of ZnS precursors directly into the same reactor with existing AgInS2 cores without any purification. In addition, to demonstrate their potential biomedical application, the AgInS2-ZnS QDs were coated with poly(maleic anhydride-alt-1-octadecene) and further conjugated with folic acid for human liver carcinoma (HepG2) tumor cell labeling. The folate-receptor-mediated cellular uptake of the folic-acid-conjugated AgInS2-ZnS QDs was confirmed by confocal imaging characterization. Additionally, the small dimensions and high solubility of the folic-acid-conjugated AgInS2-ZnS QDs were also exploited in prefixed-cell staining; the QDs entered the complex cellular matrix and stained both the nucleoli and cytoplasm of HepG2 cells.

For the last few decades, cancer has been one of the major public health concerns, and the mortality rate has become significant worldwide. However, because of the blessing of science, the early detection of tumors and the survival rate of patients have improved extra 5-years. Therefore, early-stage cancer detection and identification are critical in cancer treatment. Although priority must be given to providing the treatment option, simultaneously, it is also important to design new and improve the existing methods, which are the noble job for the scientist. Recently, gold nanoclusters (Au NCs) have emerged as a promising detection approach in biomedical imaging as it exhibits molecular like properties and good photostability. Metal nanoclusters are a unique class of ultra-small particles consisting of a few to hundreds of atoms. They feature a metal core of size ˂2 nm, which is formed due to controlled aggregation. And because of the confinement of the electrons, it exhibits optoelectronic properties such as fluorescence. In this era, scientists have reported small molecules protected gold nanoclusters, but due to lack of biocompatibility and low quantum yield, it suffers from real applications such as cell imaging etc. So, designing a biocompatible highly fluorescent gold nanocluster is a challenging task to material and synthetic chemistry. Recently, Ying et al. reported protein-protected gold nanoclusters of BSA protein, which exhibit a low quantum yield (QY~6%). To address this problem, Maity et al. have reported a highly fluorescent higher-order assembly of protein-protected gold nanoclusters using supramolecular host-guest chemistry, which exhibits 40% absolute quantum yield. Towards the end, we observed a reversible aggregation-disaggregation in the presence of cucurbit[7]uril (CB7) and adamantly amine (ADA), respectively, which is important from the fundamental point of view, where in general, protein aggregation is irreversible in nature. References: 1. Wan et al. Analyst 2020, 145, 348 2. Pradeep et al. J. Phys. Chem. C 2019, 123, 28969 3. Ying et al. J. Am. Chem. Soc. 2009, 131, 888 4. Maity et al. Nanoscale Adv. 2022, DOI: 10.1039/D2NA00123C
Prime Minister's Research Fellowship (PMRF)

碩士
國立虎尾科技大學
光電工程系光電與材料科技碩士在職專班
104
In the application of the white LED product, if the local LEDs have different hue and brightness, it will cause chromatic aberration. This problem arises in the production process of white light-emitting diode. Because the batch production caused delay time, and spit gum fixture different ways, affect the speed of phosphor deposition rate, resulting in production of products irregularity, so when the feed of each LED dies are hoping to have the same specification, so more easy to color control within a certain range, and maintain a certain production yields, but doing so will result in increased costs. This paper mainly discusses the part after the phosphors was added into the paste, due to the effect of gravity, and the time difference before and after the operation, the device will result in different CIE offset problems. Although shorten the time difference can be reduced, but will result in increased production costs, the problem cannot be mass-produced. In order to solve the problem of CIE offset, that does not affect the status of production operations situation assessment increase plastic material viscosity, in order to achieve the anti-sedimentation, reduce different phosphor particles settling time difference, and does not affect the product luminous efficiency & quality, and expand plastic material viscosity, improve production yield quality.

碩士
逢甲大學
化學工程學系
104
Since the discovery in 2004, fluorescent carbon nanodots (FCNDs) have received wide attention due to their excellent biocompatibility and fluorescence. The fluorescent property enables FCNDs to be applied to bioimaging, biosensing, and photocatalysis. To effectively increase the quantum yield (QY) of FCNDs has been an issue of study. The hydrothermal method is widely used to synthesize FCNDs because of simple operation among other methods such as laser ablation and microwave heating. The basic principle of the hydrothermal method is to put the precursor of carbon dots with additives in water and under high temperature and pressure to induce multiple chemical reactions such as carbonization and polymerization. In this study we prepared high QY FCNDs by the hydrothermal method with sulfuric acid as an additive which promotes carbonization. Through the UV absorbance and fluorescence intensity obtained from the UV-Vis and fluorescence spectra, the QY of FCNDs can be calculated. Results show that QY can be increased by 50–100% by adding a small amount of sulfuric acid. The preferred case in this study is that the highest QY (17.6%) can be reached by adding 0.03 ml sulfuric acid to the HEDTA solution. In addition, result of dynamic light scattering analysis and atomic force microscope imaging, the aforementioned FCNDs has an average particle diameter of 8.47 nm.

碩士
國立臺灣大學
化學研究所
106
This thesis is composed of two major parts. First part, we introduced fluorene core to synthesize three new high photoluminescence (PL) quantum yield red/NIR fluorescent molecules. Second part, we designed a new water-soluble two-photon absorption (TPA) chromophore. 　　Over the last few decades, TADF-type organic light-emitting diodes (OLED) is rapidly expanding, and the internal quantum efficiency (IQE) has already reached to 100%. However, it is difficult to design a red/NIR TADF molecule with high PL quantum yield and good light color purity. In this research, we designed three new high PL quantum yield red/NIR fluorescent molecules NZDFT, NZDSF and BBTDSF, and used as dopants dispensed in the TADF exciplex host. The red/NIR emitting devices were obtained external quantum efficiencies (EQE) of 6.89%、12.44% and 0.99%, respectively. 　　Two-photon absorption (TPA) process is a nonlinear absorption process, which absorbs two photons simultaneously. TPA chromophores have wide applications such as fluorescence microscopy and microfabrication. Therefore, in order to increase molecular TPA cross section and tune the position of the TPA peak wavelength, it is a urgent issue to unveil the structure-property relationship with new TPA molecules. In this research, we designed a new water-soluble TPA molecule BTDFNCOOH (σ = 188 GM at 780 nm) with emission peaked at 597 nm in the water (PLQY<5%).

博士
國立臺灣大學
化學研究所
99
Chapter 1 One-step condensation between Green Fluorescent Protein (GFP) chromophore and 1H-imidazole-5-carbaldehyde catalyzed by ZnCl2 proved to be a facile method to synthesize red Kaede chromophore and its derivatives (1a-d, 2 and 3 > 70%), among which 1a then demonstrated its potential as a dye in solar cell, with a moderate conversion efficiency (

Manipulating light by controlling surface plasmons on metals is being discussed as a means for bridging the size gap between micrometer-sized photonic circuits and nanometer-sized integrated electronics. Plasmonic waveguides based on metal nanoparticles are of particular interest for circumventing the diffraction limit, thereby enabling high-speed communication over short-range distances in miniaturized micro-components. However, scalable, inexpensive fine-tuning of particle assemblies remains a challenge and near-field probing is required to reveal plasmonic interactions. In this thesis, self-assembled waveguides should be produced on DNA scaffolds. DNA origami is an extremely versatile and robust self-assembly method which allows scalable production of nanostructures with a fine control of assemblies at the nanoscale. To form the plasmonic waveguides, six-helix bundle DNA origami nanotubes are used as templates for attachment of highly monodisperse and monocrystalline gold nanoparticles with an inter-particle distance of 1-2 nm. In the first part of this thesis, the effects of parameters which are involved in assembly reactions are systematically investigated. The assembly yield and binding occupancy of the gold nanoparticles are determined by an automated, high-throughput image analysis of electron micrographs of the formed complexes. As a result, unprecedented binding site occupancy and assembly yield are achieved with the optimized synthesis protocol. In addition, waveguides with different sizes of gold nanoparticles and different inter-particle distances, quantum dots attachments to the waveguides and multimerization of the waveguides are successfully realized. In the second part of this thesis, direct observation of energy transport through a self-assembled waveguide towards a fluorescent nanodiamond is demonstrated. High-resolution, near-field mapping of the waveguides are studied by electron energy loss spectroscopy and cathodoluminescence imaging spectroscopy. The experimental and simulation results reveal that energy propagation through the waveguides is enabled by coupled surface plasmon modes. These surface plasmon modes are probed at high spatial and spectral resolutions. The scalable self-assembly approach presented here will enable the construction of complex, sub diffraction plasmonic devices for applications in high-speed optical data transmission, quantum information technology, and sensing.
Die Manipulation des Lichts durch die Kontrolle von Oberflächenplasmonen auf metallischen Oberflächen und Nanopartikeln gilt als vielversprechende Methode zur Überbrückung der Größen-Lücke zwischen Mikrometer-großen photonischen und nanometer-großen elektronischen Schaltkreisen. Plasmonische Wellenleiter basierend auf metallischen Nanopartikeln sind vom besonderen Interesse, da sie die Umgehung des Beugungslimits und somit eine Hochgeschwindigkeitskommunikation über kurze Distanzen in immer kleiner werdenden Schaltkreisen ermöglichen könnten. Allerdings ist die skalierbare und kostengünstige Anordnung von Partikeln eine große Herausforderung und es werden Nahfelduntersuchungen benötigt um plasmonische Interaktionen detektieren zu können. Das Ziel dieser Arbeit ist die Selbstassemblierung von multi-partikel Wellenleitern auf DNA Gerüsten. Die Verwendung von DNA-Origami bietet eine äußerst vielseitige Plattform zur skalierbaren Herstellung von Nanostrukturen mittels Selbstassemblierung und ermöglicht eine präzise Kontrolle der Anordnungen im Nanobereich. Für den Aufbau der plasmonischen Wellenleiter werden DNA-Origami Nanoröhren, bestehend aus sechs Helices als Templat für die Anbindung von monodispersen und monokristallinen Goldnanopartikeln mit einem interpartikulären Abstand von 1-2 nm verwendet. Im ersten Abschnitt dieser Arbeit werden die beeinflussenden Faktoren dieser Assemblierungsreaktion systematisch untersucht. Die Ausbeute der assemblierten Strukturen und die Besetzung der Bindungsstellen werden durch eine automatisierte und effiziente Bildanalyse von Elektronenmikroskopieaufnahmen ausgewertet. Durch die Entwicklung eines optimierten Syntheseprotokolls werden bisher unerreichte Assemblierungsausbeuten ermöglicht. Zusätzlich erfolgen die experimentelle Realisierung von Strukturen mit verschieden großen Goldnanopartikeln und unterschiedlichen interpartikulären Abständen, sowie die Anbindung von Quantenpunkten an die Wellenleiter und eine Verknüpfung der assemblierten Strukturen. Der zweite Abschnitt dieser Dissertation befasst sich mit der Untersuchung des Energietransports in selbstassemblierten Wellenleitern über einen fluoreszierenden Nanodiamanten. Dazu erfolgen hochaufgelöste Nahfeldmessungen der Wellenleiter mittels Elektronenenergieverlustspektroskopie und Kathodolumineszenz-mikroskopie. Die experimentellen Ergebnisse und zusätzlich durchgeführte Simulationen bestätigen eine durch gekoppelte Oberflächenplasmonenmoden induzierte Weitergabe der Energie innerhalb des Wellenleiters. Diese Oberflächenplasmonenmoden werden bei hoher räumlicher und spektraler Auflösung untersucht. Das hier umgesetzte Konzept der Selbstassemblierung wird den Aufbau komplexer plasmonischer Geräte für Anwendungen im Bereich der optischen Hochgeschwindigkeitsdatenübertragung, der Quanteninformations-technolgie und der Sensorik ermöglichen.