Fluorescence Spectroscopy in Structural Studies of Plant Cell Walls

Plant cell walls represent the most abundant, renewable and biodegradable composite on Earth. Its highly complex structure consists mainly of three organic compounds: cellulose, hemicelluloses, and lignin. Cell walls have wide applications in different industries, especially for biofuels and biomaterials. Fluorescence spectroscopy is the method allowing investigation of cell wall structure thought monitoring of lignin autoflorescence and thus interactions of lignin with the other cell wall constituents. Deconvolution of fluorescence spectra reveals the number and location of spectral component peaks by calculation of the approximation of the probability density (APD) of component positions. A characteristic of complex CW fluorescence is that the emission spectrum contains multiple log–normal components originating from different fluorophores, shorter wavelengths corresponding to phenolic structures and longer wavelengths to conjugated structures in lignin. Fluorescence spectroscopy has been used for fast screening of the cell wall properties from plants of different origin (hardwood, softwood and herbaceous plant), that may be important for selection of plants for possible applications. Fluorescence spectroscopy may be applicable in the investigation of the effect of stress on the cell wall. Lignin fluorescence emission spectra, peak intensities and shifts in the positions of the long-wavelength spectral components may be indicators of changes in cell wall structure during the stress. There is an increasing application of quantum dots (QDs) in plant science, as fluorescent markers. The isolated cell wall is an appropriate object for study of the interactions with nanoparticles. The results of different physico-chemical techniques including fluorescence spectroscopy combined with spectral deconvolution, show that in the cell walls, CdSe QDs predominantly bind to cellulose, via OH groups, and to lignin, via the conjugated C=C/C–C chains. Variability of bond types in lignin is related to the involvement of this polymer in plant response to various types of stress, by introducing local structural modifications in the cell wall. Different lignin model compounds have been used in order to reveal spectroscopic properties of lignin. Lignin model polymers were synthesized from three monomers, coniferyl alcohol, ferulic acid and p-coumaric acid mixed in various ratios, simulating lignin synthesis in the real cell walls. Further, by using fluorescence spectroscopy and appropriate mathematical methods, it is possible to get deeper insight into the structural characteristics of the molecule. Future investigations will be based on synthetic cell walls and on variation in a portion of all three main components: cellulose, hemicelluloses and lignin, also having in mind results of fine structural modifications in lignin model compounds

Imagerie thermique et thermoélastique de circuits intégrés : application à l'analyse de défaillances

Ce travail décrit le développement d’une instrumentation en mesures thermiques et thermoélastiques pour l’analyse de défaillance sur circuits intégrés, il comporte trois parties : La première partie concerne des mesures interférométriques effectuées avec deux interféromètres, homodyne et hétérodyne. Ces interféromètres seront appliqués pour la détection de points chauds sur des circuits défaillants. La deuxième partie concerne des mesures thermiques effectuées en thermoréflectance. Deux bancs de mesure ont été développés : - le premier s’applique pour l’imagerie face avant. - le deuxième entièrement original, concerne l’imagerie large champ face arrière qui utilise une porte optique temporelle. La dernière partie concerne le développement d’une nouvelle approche pour les mesures de température et déplacement en utilisant la microscopie à balayage laser, avec une étude de résolution et sensibilité.This work describes the development of instrumentation in thermal and thermoelastic measurements for failure localisation and test diagnostic. It is divided in three parts: The first part is about interferometric measurements done with homodyne and heterodyne interferometers. Those interferometers were applied for defects localisation in failures ICs. The second part is about thermal measurements done with thermoreflectance. Two experimental benches were developed: - the first is applied for front side imaging - the second is a new technique applied for back side imaging, which is based on time gating. The last part of this work is about the development of a new approach for thermal and thermelastic measurements with the use of light scanning microscopy. It includes a study of the resolution and the sensitivity

Quantitative measurement using scanning thermal microscopy

This thesis reports on the development of quantitative measurement using micromachined scanning thermal microscopy (SThM) probes. These thermal probes employ a resistive element at their end, which can be used in passive or active modes. With the help of a review of SThM, the current issues and potentials associated with this technique are revealed. As a consequence of this understanding, several experimental and theoretical methods are discussed, which expand our understanding of these probes. The whole thesis can be summarized into three parts, one focusing on the thermal probe, one on probe-sample thermal interactions, and the third on heat transfer within the sample. In the first part, a series of experiments are demonstrated, aimed at characterizing the probe in its electrical and thermal properties, benefiting advanced probe design, and laying a fundamental base for quantifying the temperature of the probe. The second part focuses on two artifacts observed during the thermal scans – one induced by topography and the other by air conduction. Correspondingly, two devices, probing these artifacts, are developed. A topography-free sample, utilizing a pattern transfer technique, minimises topography-related artifacts that limited the reliability of SThM data; a controlled temperature ‘Johnson noise device’, with multiple-heater design, offers a uniform, accurate, temperature distribution. Analyzing results of scan from these samples provides data for studying the thermal interactions within the probe and the tip-sample interface. In the final part, the observation is presented that quantification of measurements depends not only on an accurate measurement tool, but also on a deep understanding of the heat transfer within the sample resulting from the nanoscopic contact. It is believed that work in this thesis contributes to SThM gaining wider application in the scientific community

Feature Papers in Electronic Materials Section

This book entitled "Feature Papers in Electronic Materials Section" is a collection of selected papers recently published on the journal Materials, focusing on the latest advances in electronic materials and devices in different fields (e.g., power- and high-frequency electronics, optoelectronic devices, detectors, etc.). In the first part of the book, many articles are dedicated to wide band gap semiconductors (e.g., SiC, GaN, Ga2O3, diamond), focusing on the current relevant materials and devices technology issues. The second part of the book is a miscellaneous of other electronics materials for various applications, including two-dimensional materials for optoelectronic and high-frequency devices. Finally, some recent advances in materials and flexible sensors for bioelectronics and medical applications are presented at the end of the book

Development of new materials and techniques for luminescence nanothermometry and photothermal conversion

Hem estudiat la dependència amb la temperatura de la luminescència generada per nanopartícules dielèctriques dopades amb ions lantànids que poden ser utilitzades en nanotermometria luminescent. Hem analitzat nous materials amb emissió en el rang del visible de l’espectre electromagnètic, incloent Ho,Yb:KLu(WO4)2 i Ho,Tm,Yb:KLu(WO4)2, així com nanopartícules core-shell de Er,Yb:GdVO4@SiO2. També hem desenvolupat un nou mètode de síntesi solvotermal assistit per microones per nanopartícules de Er,Yb:NaYF4, que opera a temperatures més baixes i temps de reacció més curts que els mètodes convencionals. Hem utilitzat nanotermometria basada en la mesura dels temps de vida mitjana radiativa en nanopartícules up-conversores de Er,Yb:NaY2F5O per la determinació de temperatura en sistemes biològics, així com la determinació de temperatura pel canvi de color de l’emissió de nanopartícules de Tm,Yb:GdVO4@SiO2. Finalment, hem desenvolupat un sistema de nanotermometria luminescent simple i compacte que permetrà atansar la nanotermometria luminescent a l’entorn mèdic i industrial. Hem analitzat també la nanotermometria luminescent en la regió de l’infraroig proper. El Nd:KGd(WO4)2 mostra potencial com nanotermòmetre luminescent en aquesta regió per sistemes biològics, amb una profunditat de penetració d’1 cm en teixits biològics. Els ions Er3+ i Tm3+ mostren bandes d’emissió eficients en aquesta regió que poden utilitzar-se per nanotermometria luminescent en sistemes biològics. Les nanopartícules de Tm,Yb:GdVO4@SiO2, amb emissions localitzades en la primera finestra biològica, presenten una elevada sensitivitat tèrmica i s’han internalitzat en cèl·lules HeLa. Finalment, hem mostrat la multifuncionalitat de les nanopartícules de Ho,Tm:KLu(WO4)2 que actuen com nanotermòmetres, agents fototèrmics i marcadors biològics. També hem determinat l’eficiència de conversió fototèrmica del grafè i derivats, escalfadors eficients pel tractament de diverses malalties inclòs el càncer, i hem desenvolupat un nou mètode per determinar aquesta eficiència de conversió utilitzant una esfera integradora, un mètode que es pot estendre a altres agents fototèrmics.Hemos estudiado la dependencia con la temperatura de la luminiscencia generada por nanopartículas dieléctricas dopadas con iones lantánido que pueden ser usadas en nanotermometría luminiscente. Hemos analizado nuevos materiales con emisión en el rango del visible del espectro electromagnético, incluyendo Ho,Yb:KLu(WO4)2 y Ho,Tm,Yb:KLu(WO4)2, así como nanopartículas core-shell de Er,Yb:GdVO4@SiO2. También hemos desarrollado un nuevo método de síntesis solvotermal asistido por microondas para nanopartículas de Er,Yb:NaYF4, que opera a temperaturas más bajas y tiempos de reacción más cortos que los métodos convencionales. Hemos utilizado nanotermometría basada en la medida de tiempos de vida media radiativa en nanoparticulas up-conversoras de Er,Yb:NaY2F5O para la determinación de temperatura en sistemas biológicos, así como la determinación de temperatura por el cambio de color de la emisión de nanopartículas de Tm,Yb:GdVO4@SiO2. Finalmente, hemos desarrollado un sistema de nanotermometría luminiscente simple y compacto que va a permitir acercar la nanotermometría luminiscente al entorno médico e industrial. Hemos analizado también la nanotermometría luminiscente en la región del infrarojo cercano. El Nd:KGd(WO4)2 muestra potencial como nanotermómetro luminiscentes en esta región para sistemas biológicos, con una profundidad de penetración de 1 cm en tejidos biológicos. Los iones Er3+ y Tm3+ muestran bandas de emisión eficientes en esta región que pueden utilizarse para nanotermometría luminiscente en sistemas biológicos. Las nanopartículas de Tm,Yb:GdVO4@SiO2, con emisiones localizadas en la primera ventana biológica, presentan una elevada sensitividad térmica y se han internalizado en células HeLa. Finalmente, hemos mostrado la multifuncionalidad de las nanopartículas de Ho,Tm:KLu(WO4)2 que actúan como nanotermómetros, agentes fototérmicos y marcadores biológicos. También hemos determinado la eficiencia de conversión fototérmica del grafeno y derivados, calentadores eficientes para el tratamiento de diversas enfermedades incluido el cáncer, y hemos desarrollado un nuevo método para determinar esta eficiencia de conversión utilizando una esfera integradora, un método que puede extenderse a otros agentes fototérmicos.We studied the temperature dependence of the luminescence generated by dielectric nanoparticles doped with lanthanide ions to be used in luminescence nanothermometry. New materials emitting in the visible range of the electromagnetic spectrum, including Ho,Yb:KLu(WO4)2 and Ho,Tm,Yb:KLu(WO4)2 and Er,Yb:GdVO4@SiO2 core-shell nanoparticles have been analyzed for these purposes. Moreover, we developed a new and greener microwave-assisted solvothermal synthesis method for Er,Yb:NaYF4 nanoparticles that operates at lower temperatures and shorter reaction times than conventional methods. We used lifetime-based nanothermometry in upconversion Er,Yb:NaY2F5O nanoparticles for temperature determination in biological systems, and the change of color of the emission generated in Tm,Yb:GdVO4@SiO2 core-shell nanoparticles as a function of temperature. Furthermore, we developed a simple and compact setup that would approach luminescence nanothermometry to the real practical applications in medical and industrial environments. We also explored luminescence nanothermometry in the near infrared region of the electromagnetic spectrum. Nd3+-doped KGd(WO4)2 nanoparticles show potentiality as a luminescent nanothermometer in this region for biological systems, with a penetration depth of 1 cm in biological tissues. Er3+ and Tm3+ ions doped in different matrices have shown also efficient emission bands lying in the short-wavelength infrared region that can be used for luminescence thermometry in biological systems. Also, Tm3+,Yb3+:GdVO4@SiO2 core-shell nanoparticles with emissions located in the first biological window are presented as highly thermal sensitive nanothermometers and have been efficiently internalized in the HeLa cells. Finally, the multifunctionality of Ho3+ and Tm3+ co-doped KLu(WO4)2 nanoparticles has been shown, acting as nanothermometers, photothermal agents and biolabels for bioimaging. Also, we determined the photothermal conversion efficiency of graphene and graphene oxide, efficient heaters for the treatment of several diseases including cancer, and developed a new method for determining their photothermal conversion efficiency by using an integrating sphere, a method that can be extended to other photothermal agents

Thermal parameters identification of micrometric layers of microelectronic devices by thermoreflectance microscopy

The objective of this paper is the determination of the thermal properties of micrometric layers of electronic devices using a thermoreflectance probe. Unlike classical thermoreflectance methods, the main point of the method presented in this paper is to be able to quantify the heating energy (by Joule effect) and the effective temperature response (by calibration). It is then possible to estimate the thermal conductivity (in W m−1 K−1) instead of the thermal diffusivity (in m2 s−1). A semi-analytical thermal 3D-periodic model then enables to identify a few thermal properties of the layers of the device, and in particular the thermal conductivity of the passivation layer. This methodology has been applied to the study of an industrial device containing interconnect test structures made of copper lines on a silicon wafer with a few micrometers BCB (BenzoCycloButene) polymer passivation layer. The BCB thermal conductivity and the metal heat capacity are obtained using this method

Estimation sur des bases orthogonales des propriétés thermiques de matériaux hétérogènes à propriétés constantes par morceaux

Ce travail se propose de caractériser thermiquement des composites à microstructures complexes. Il s agit de développer des méthodes d estimation permettant d identifier les propriétés thermiques des différentes phases en présence, ainsi que celles associées à leurs interfaces, à partir de mesures issues de la thermographie infrarouge. Cette estimation paramétrique nécessite la connaissance au préalable de la structure géométrique de l échantillon. Le premier objectif concerne donc l identification de la structure de l échantillon testé par la discrimination des différentes phases et interfaces. Une fois la structure de l échantillon connue, le second objectif est l identification des paramètres thermiques des différents constituants ainsi que ceux de leurs interfaces. On se propose d exploiter deux tests spécifiques utilisant le même dispositif expérimental. Deux méthodes mathématiques différentes ont été développées et utilisées pour exploiter les mesures de champ issues du premier test et permettre de retrouver la microstructure de l échantillon. La première est fondée sur la décomposition en valeurs singulières des données de températures recueillies. Il est montré que cette méthode permet d obtenir des représentations de la microstructure de très bonne qualité à partir de mesures même fortement bruitées. La seconde méthode permet de raffiner les résultats obtenus à l aide de la méthode précédente. Elle repose sur la résolution d un problème d optimisation sous contraintes en exploitant la technique dite Level-Set pour identifier les frontières des différents constituants de l échantillon. L étape d identification des propriétés thermiques des constituants et des interfaces exploite les mesures de champs issues du second test expérimental. La méthode développée, la SVD-FT combine des techniques de décompositions en valeurs singulières avec desfonctions tests particulières pour dériver des estimateurs linéaires des propriétés recherchées.Cette méthode permet de limiter les effets du bruit de mesure sur la qualité de l estimation et de s affranchir des opérations de filtrage des données.This work reports on the thermal characterization of composites with a complex microstructure. It aims at developping mathematical methods to identify the thermal properties of the constituants and thoses associate at their interfaces. The first step consistsin discriminating the microstructure of the sample to be tested. Then, when the sample structure is known, the second step consists in estimating the thermal parameters of the different phases and those at their interfaces. One experimental device has been set up to realize those two steps. Two mathematical methods have been developped and used to discriminate the microstructure based on the images of the sample recorded bu an infrared camera. The first method is based on the singular value decomposition of the temperature data. It has been shown that this method gives a very good representation of the microstructure even with very noisy data. The second method allows to refine the results obtained by the first one. This method is based on the resolution of an optimization problem under constraints and use a Level-Set technic to identify the boundary of each phase. To estimate the thermal properties of each phase and its interface, the infrared images of the second experiment have been used. The SVD-FT method developed in this work combines the singular values decomposition technic with particular tests functions to derive linear estimat or for the thermal properties. As a result, a significant amplification of the signal/noise ratios is reached.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF