Light, when reduced to the level of individual quanta, can possess, besides its familiar properties of wavelength, direction, and polarization, a set of correlations irreducible to classical correlations, among other peculiar behaviour. These correlated states are intrinsically interesting, and are also useful for quantum-enhanced information processing. In this thesis, I use a high-bandwidth, far-off-resonant Raman memory to implement two quantum information primitives -- entanglement generation and light storage -- at room temperature and ambient conditions. Specifically, I show, for the first time, the entanglement of two solid-state objects at room temperature and, also, the storage of light in a hollow-core optical fibre. In the first part, I show that the optical phonon modes of two diamonds can be entangled -- the prototypical non-classical correlation -- at room temperature. The entanglement was generated by spontaneous Raman scattering with projective measurements using single-photon detectors. The degree of entanglement was rigorously quantified by measuring the concurrence -- an entanglement monotone -- of the joint state of the scattered optical fields. In the second part, I store light in the coherent superposition of cesium atoms confined within a kagome-structured hollow-core photonic crystal fibre at room temperature using a far-off-resonant stimulated Raman interaction. The storage efficiency of the memory was 27$pm$1% and the noise level was sufficiently low such that single-photon-level pulses could be stored. Taken together, these results highlight the potential of Raman memories for quantum information tasks in noisy systems with short coherence times.

The development of multimode absorption spectroscopy (MUMAS) for multi-species detec- tion and its potential for process control or environmental monitoring is reported. The simultaneous detection of CO and CO2 is demonstrated in a proof-of-principle experiment for applications in industrially relevant gas species monitoring. The technique of MUMAS is extended to the near infrared in order to detect these and other industrially relevant species. A laser was designed and constructed to emit a multimode spectrum in the region of 1.57um to take advantage of the spectral overlap of the second vibrational overtone of CO and the combination band 3ν1 + ν3 of CO2. The laser consisted of a semi-confocal cavity employing an Er:Yb glass chip as the gain medium. The laser was pumped by a 1W laser diode at 980nm and emitted up to 30mW in a bandwidth of 180GHz. The laser emitted between 6-10 modes depending upon the selective cavity length. Mode spacings varied between 18GHz to 33GHz with an individual mode linewidth of less than 8MHz. The laser modes were simultaneously scanned using a piezo-electric transducer (PZT) in order to modulate the cavity length at frequencies between 1Hz and 10Hz. A system for linearizing the MUMAS spectra with respect to frequency was devised based on a transmission spectra of a confocal Fabry-Perot etalon. Refinements to the MUMAS fitting code were developed to improve the computational efficiency. An initial demonstration of MUMAS on a known gas mixture of CO and CO2 was per- formed. The ratio of CO:CO2 concentrations in the gas mixture was measured with an accuracy of 0.4% which was within the supplier’s quoted uncertainty. MUMAS is then applied to the detection of CO and CO2 concentrations in exhaust gas produced by a 1.3 litre 4-cylinder turbo-charged spark ignition engine. Relative and absolute concentrations were derived from MUMAS signals and values compared to measurements using a 4-gas analyser. Concentrations of CO and CO2 were measured using MUMAS to a precision of 0.17% and 0.23% respectively compared to less than 0.1% for the 4-gas analyser. Ratios of CO and CO2 were determined with a precision of 0.28 using MUMAS compared to 0.11 with the 4-gas analyser. The detection limit of CO was found to be 1486ppm in these circumstances. Finally a discussion is presented of potential improvements arising from wavelength mod- ulation spectroscopy and cavity enhancement techniques.

This work is focused on exploring a unique integration of techniques, Raman micro-spectroscopy and atomic force microscopy (AFM), which when combined offer more than the sum of their respective parts. The non-invasive chemical specificity afforded by Raman spectroscopy, combined with the nanoscale-resolution topographic imaging of AFM offer much individually. The physics underlying the practical application of each technique is very general; Raman spectroscopy detects molecular vibrational shifts using light, and AFM uses a physical probe to interact with a surface to provide topographic (and mechanical) information. As a result, there are few restrictions to the possible samples that can be studied with these techniques, from semiconductors and geological crystals, through to simple organic chemical structures all the way to complex biological molecules and systems such as cells and tissue. In this work, a synthetic biomaterial composed of diphenylalanine (FF) peptide units which self-assemble into strong tubular structures is used as a sample of interest when exploring the different possibilities available from a combined Raman-AFM instrument. First, the combined system was set up in order to perform tip-enhanced Raman spectroscopy (TERS), a technique promising Raman spectroscopic imaging at the resolution of AFM imaging. A relatively young technique, TERS has huge potential in extending the reach of Raman spectroscopic imaging to the nanoscale, at a regime where a great deal of structure exists, but is usually blurred by conventional diffraction-limited Raman microspectroscopy. A major focus in this work is addressing a current problem with TERS: the fabrication of suitable probes. TERS typically utilizes AFM tips modified to have a silver nanoparticle, capable of locally enhancing the Raman signal, attached at the probe apex. A new method is presented here that promises several improvements over existing approaches, as the entire fabrication can be performed in-situ on the instrument. Tips produced in this way are then characterized by electron microscopy and tested on FF nanotubes. Following this, several techniques for the synthesis of silver nanoparticles are explored for use in TERS. Here, the focus is particularly on decahedral nanoparticles, which can be grown into rod shaped particles with well- defined shapes and sizes. These are important considerations for obtaining the desired enhancing properties for TERS probes. Finally, the AFM-Raman instrument is used to investigate the mechanical properties of FF tubes using several methods. AFM force spectroscopy of tubes suspended across a gap can be used in conjunction with a bending beam theory to measure the Young's modulus of individual tubes. A new type of co-localized experiment using polarized Raman spectroscopy on a suspended tube under various forces from the AFM is tested, and subsequently information relating to the hydrogen bonding network is used, in conjunction with existing X-ray data, to determine the molecular contributions to the modulus using a simple model for amyloid fibrils. Each experiment operates at the single fibril level, with the same fibrils being used, such that different methods can be compared for a single FF tube.

In recent years there has been an increasing interest in analysis and identification of complex molecules for the medical diagnostics, pharmaceutical research and homeland security applications. If these molecules are present in high concentration, a technique known as Raman spectroscopy can be utilized. Unfortunately, only one in every 1012 photon incidence on molecule undergoes Raman scattering resulting in weak Raman absorption. An efficient technique to overcome this limitation is to utilize surface-enhanced Raman scattering (SERS) whereby molecules are placed on the surface of nanostructured metallic substrate which performs the function of transducting photons into and out of the molecules. SERS extends the scope of Raman scattering to detect molecules at low concentrations to few/single molecule level. Previously the ‘KlariteTM’ substrate consisting of an inverted array of square based pyramidal nanostructures patterned onto a Silicon substrate has been demonstrated to afford highly reproducible SERS signals with approximately 107 enhancement factor. In this report, the effect of geometrical parameters associated with the inverted pyramidal array on SERS effect for sensing applications was investigated. Geometrical parameters studied include pitch length, pit size, aspect ratio of the base of pyramid and fill factor. 3D computational modelling based on Rigorous Coupled Wave Analysis (RCWA) is used to bridge with theory. From these observations, the geometrical parameters of inverted pyramid nanostructures have been optimized for better sensing ability. A test chip is fabricated for the purpose of performing a matrix experiment, allowing deconvolution of geometrical variables: lattice pitch (1000nm-3000nm), pit size (500nm-2500nm), pit aspect ratio [width to length]. Fabrication steps include electron-beam lithography, anisotropic wet etching and metallization. Computational and experimental reflectometry systems were applied to enable the identification and analysis of a variety of dispersive features including propagating surface plasmons, localized surface plasmons and diffraction dispersion. From the study of inverted pyramid, plasmonic behaviors are observed: 1. the surface plasmon polariton depends strongly on polarization. 2. Highly dispersive features arising from simple surface diffraction effects appear insensitive to polarization state. 3. As the pit size gets bigger, the diffraction efficiency decreases but the wavelength/angular position remain the same. 4. Diffractive features are relatively sharp and clearly defined (narrow bandwidth), and are highly dependent on lattice pitch. Hence they move in wavelength and angle (e.g. highly dispersive) as pitch is varied. These features relate to the coupling of light into or out of the sensor chip. 5. Localized surface plasmons have characteristic of small wavelength shift over wide angular range (low dispersion), and are generally broader in bandwidth. Plasmon features can conclusively be identified over diffractive features by making comparisons between simulations ‘with’ and ‘without’ the top metal coating. In order to derive the optimal geometry for SERS sensor, a highly stable test molecule which is known to form a monolayer coating on gold is required. For this purpose benzenethiol was used as standard in this work. Devices were tested using a Renishaw Invia Raman system. The main wavelength of interest here is 785nm where this laser is readily available and compatible with the end user Raman system. Full details of the optical and Raman measurements are carried out on the silicon test platform. Results show that the averaged SERS enhancement factor was only slightly dependent upon lattice pitch, but was highly dependent on pit size and aspect ratio. Density of the pits plays a further role simply by increasing the number of pits/unit area and so provides extra increase in SERS signal. The experimental data shows this is not simply a surface area dependent effect, but the optimal SERS signal can be obtained by close packing as tightly as possible pits of the optimal size. Minimum spacing (between adjacent pits) of 250nm is found to give the highest SERS enhancement. The optimal aspect ratio was found to be 1:1.2 and the optimal pit size determined to be 1000nm. This new optimized design shows 10-fold improvement in sensitivity compared to current available benchmark Klarite. The study has also explored the possibility of replicating the optimized design to a cost effective and disposable polymer for the purpose of mass production. This was carried out using nanoimprint lithography. The replicated plastic sensor is comparable to the benchmark silicon Klarite. As a proof of principle, the qualitative performance in two demonstrator molecules such as ibuprofen and melamine has been carried out. The disposable plastic sensor was demonstrated for the possibility of dual sensing mechanisms such as surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS). The sensitivity of plastic sensor using SPR mechanism is 225.83nm/RIU on thiol molecule. The work has also been carried out for an alternative SERS sensor design by changing the sidewall profile to 90˚ angle from (100) silicon etched plane. Changing the sidewall profile makes impact on the plasmonic behaviour. The straight sidewalls are favourable to the localized plasmon mode. The structures with slope sidewalls are favourable to both localized and propagating plasmons inside the cavities. This work was conducted as part of the FP7 ‘’PHOTOSENSE’’ consortium project.

This thesis describes the design and operation of a flexible 'optical parametric oscillator based system, which provides a tunable coherent source of near and middle infrared radiation. The system is suitable for use in applications such as high energy spectroscopy and photo-excitation. The system design has concentrated on obtaining a narrow linewidth and high output energy from the Nd:YAG laser pumped LiNbO3 OPO throughout its tuning range, with the ability to extend operation to longer wavelengths by down-conversion. An important consideration has been to make control and tuning of the system as simple as possible for the experimenter; this has been achieved by the use of motorised tuning mechanisms and programmed digital processor based electronics. Several features, including the nonlinear characteristics of the tuning elements, have been incorporated into the processor software, allowing a simplification of the design of the drive mechanisms and interface electronics to be made. Included are measurements of the performance of the system, including those of the output energy, linewidth, beam divergence and the effects of incorrect tracking between tuning elements, With grating tuning alone, the OPO produces millijoule output pulses of ~3cm-1 linewidth from 1.45µm to 4µm, while the down-converter produces microjoule outputs from 4µm to 24µm. The linewidths of the OPO and down-converter are reduced to ~0.1 cm-1 by the addition of an etalon. The results of some demonstration experiments using the source are also presented, these giving indirect indications of the whole system performance.

Understanding the behaviour of polymers which are located in the presence of nuclear materials is important in order to predict the lifespan of the materials. Artificial ageing experiments are undertaken at elevated temperatures to infer how the materials may age. This study was concerned with the monitoring of trace gases (H2O, CO2, CO and acetic acid) within a materials ageing vessel which contained ethylene-vinyl acetate (EVA) polymer and uranium in order to deduce the rate of polymer degradation and/or uptake of the gases by uranium. A novel circular multi-reflective (CMR) cell was designed, developed and deployed in situ in order to extend the optical pathlength within the vessel to improve detection limits of the trace gases. One cell was located at the 6 millimetre solid/solid interfacial region between cylindrical coupons of the EVA polymer and uranium, to enable representative sampling in proximity to where the gases were evolved, adsorbed or reacted. The unique planar star-like beam profile of the CMR cell was crucial in enabling detection within this narrow interfacial region. A second CMR cell was incorporated within the vessel headspace, above the two material coupons, to address a specific research problem which aimed to ascertain whether differences in the gaseous composition existed between the two regions, which would indicate poor gas mixing. Two spectroscopic techniques were employed in conjunction with the CMR cells to monitor the trace gases: these comprised broadband absorption spectroscopy (BBAS) and tunable diode laser absorption spectroscopy (TDLAS). Near-infrared (IR) radiation sources, in the form of diode lasers, a superluminescent light emitting diode (SLED) and supercontinuum (SC) source were utilised in BBAS experiments. TDLAS was used for the detection of CO2, CO and H2O, whilst BBAS was used for the detection of acetic acid, and other potential unknown species. The requirement for using near-IR radiation was a consequence of using flexible silica-based optical fibres to remotely monitor the vessel which was located within a temperature controlled chamber. As a result, this was the first demonstration of CMR cells being used in conjunction with near-IR radiation sources. An optical pathlength of 69 cm was achieved within the materials ageing vessel, which led to the following limits of detection at 75 °C, 150 Torr with a 10 second averaging time: H2O = 3 ppm; acetic acid = 157 ppm; CO2 = 596 ppm and CO = 37500 ppm. Manufacturing issues with the cell optics, coupled with monitoring weak ro-vibrational absorption features led to considerably higher limits of detection than expected. The CMR spectroscopic system was used successfully to observe the outgassing trend of partially cured EVA polymer, which was shown to depend on cure time. A key finding of this research, however, was the observation of a difference between the interfacial gaseous composition versus the headspace gas in a system that contained both a source and sink material (i.e. one that evolved, and one that adsorbed gases). This was only made possible by using the CMR spectroscopic system. This observation was also supported by a computational fluid dynamic (CFD) model.

The purpose of this study is to demonstrate the ability of surface enhanced Raman scattering (SERS) active particles to enable multiplexed immunoassays in a lateral flow format for point of care (POC) testing. The SERS particles used for this study are chemically active glass coated gold particles, containing tracer molecules which in principle can be chosen to provide Raman Spectra with unique features allowing multiple tracers to be simultaneously measured and distinguished without interference between each other. Lateral flow immunoassay technology is the important part of this study and can be conveniently packaged for the use of other than highly skilled technicians outside of the laboratory. A well-known (single channel - simplex) device for the pregnancy test is a typical example of the lateral flow assay. Similar formats have been/are being developed by others for a range of POC applications – but most diagnostic applications require simultaneous determination of a range of biomarkers and multiplexed assays are difficult to achieve without significant interference between the individual assays. This is where SERS particles may provide some advantages over existing techniques. Cardiac markers are the growing market for point of care technology therefore biomarkers of cardiac injury (Troponin, myoglobin and CRP) have been chosen as a model. The object of the study is to establish the proof of concept multiplexing assay using these chosen biomarkers. Thus, initially all different particles were characterised in single and mixture form. Also development of conjugate chemistry between antibodies for each analyte that have been purchased from commercial sources and SERS particles were analysed using different conditions like buffer, pH and antibody loading concentration to get the optimum intensity. The selected SERS particles and their conjugates were tested for size, aggregation and immune quality using a range of techniques: ultraviolet-visible (UV/Vis) absorption spectroscopy, dynamic light scattering (DLS) and lateral flow assay. These characterisations methodologies gave the understanding of optimum conditions of the each conjugates and individual’s behaviour in mixture conditions as well. After the characterisation all conjugates were tested singularly on the lateral flow assay using buffers and serum. The results of this single analyte immunoassay explained the individual’s bioactivity on the lateral flow strip. Further in study, multiplex assay have been demonstrated in serum. These outcomes have described each candidate characteristic in a mixture form on the lateral flow strip. In order to get the optimum Raman intensity from multiplex assay, the detection and capture antibodies loading concentrations were tuned in the assay. Later on different combinations (high, medium and low concentrations) of all three analytes were analysed and has found some interferences in multiplex assay. To investigate these issues various aspect were considered. First of all, different possibilities of non-specific interactions between the co-analytes and antibodies were tested. In addition, steric hindrance and optical interference investigations were performed via several assays and analysis using Scanning electron microscopy. The outcomes have confirmed related optical interferences. Therefore other assay (wound biomarkers) established to eliminate the interferences. In summary, the works reported here have built and test the equipment and necessary reagents for individual assays before moving on the more complicated task. In addition, the entire study has given a deep knowledge of multiplex assay on a single test line including the investigation of the issues for selected cardiac biomarkers and their applications in the future.

Cette thèse présente les premiers travaux réalisés autour d’un nouveau dispositif expérimental de piégeage d’atomes individuels utilisant une unique lentille asphérique de grande ouverture numérique. Au cours de cette thèse, nous avons testé les propriétés optiques de la lentille et démontré la formation d’un col laser de 1 µm ainsi qu’un champ transverse sur lequel la lentille est limitée par diffraction de plus ou moins 25 µm. Après avoir démontré la capacité de ce système à piéger des atomes uniques, les caractérisations usuelles des conditions de piégeage ont été conduites: durée de vie, taux de chauffage, polarisation de la lumière de fluorescence, fréquences d’oscillations. Cette thèse s’est intéressée spécifiquement à la distribution d’énergie des atomes uniques piégés. La technique de lâcher et recapture combinée à une étude spectroscopique de l’occupation du piège par les atomes a conduit à la vérification du caractère thermique de la distribution d’énergie des atomes. Par un refroidissement laser combiné à un refroidissement adiabatique, une température minimale de 1,75 µK sans pertes d’atomes est obtenue avec un niveau vibrationnel moyen occupé égal à 4. Ces résultats sont très encourageants dans le contexte de l’information quantique où la température est souvent la principale limite physique à la durée de vie des cohérences d’un bit quantique. La dernière partie de cette thèse revient sur la problématique de la manipulation spatiale d’atomes uniques. Envisagé dans le cadre de la réalisation d’un calculateur quantique, le transfert d’un bit quantique et son déplacement dans l’espace sur une échelle compatible avec les caractéristiques d’un calculateur sont successivement étudiés. Ces travaux ont montré que ni l’état externe des atomes (au travers de leur température) ni leur état interne (à travers la durée de vie des cohérences d’un bit quantique) sont affectés par ce type de manipulations. / This thesis presents the early work done on a new setup that we have developped for trapping single atoms in an optical tweezer using only one diffraction limited large numerical aperture aspheric lens. Together with an experimental optical measurement of a 1µm laser beam waist created by such an aspheric lens, we showed that the diffraction limited transverse field of the lens is about plus or minus 25 µm. The ability of this new setup to trap single atoms is demonstrated and some crucial parameters are then determined : survival time in the dark, heating rate, fluorescence light polarisation, oscillation frequencies. During this PhD, we did focus our attention especially on determining the energy distribution of the single trapped atoms. A release and recapture technique along with the spectroscopic study of the energy levels occupation helped us show a termal behavior of a succession of single atoms in an optical twezer. By using common laser cooling techniques associated with adiabatic down ramping cooling, we showed that a reduction by a factor 100 of the mean energy corresponding to a mean vibrationnal energy level of about 4 and a minimum temperature of 1,75 µK. Spatial manipulation of single atoms and qubits was also studied. Using a tip-tilt platform, a second trap is set on the experiment and the transfer from one trap to the other, as well as the displacement of one trap with help of the platform, are experimentally studied. Both the temperature of the atoms and the qubit lifetime are showed to be insensitive to these manipulations.

La transplantation pulmonaire est une alternative thérapeutique ultime dans de nombreuses maladies pulmonaires sévères, en particulier chez des patients atteints de mucoviscidose (Cystic Fibrosis) , de fibrose pulmonaire idiopathique (IPF idiopathie pulmonary fibrosis), delymphangioléiomyomatose (LAM) ou d'hypertension pulmonaire. Cependant, les besoins en greffe dépassent largement le nombre de transplantations pratiquées en France. Les causes de ce déséquilibre incluent un trop faible nombre de donneurs potentiels en raison de critères actuels pour l'acceptation du greffon qui sont restreints car les biomarqueurs biologiques de qualité et de viabilité du greffon n'ont pas été décrits à ce jour. L'une des possibilités d'augmenter le nombre de donneurs, est de mettre en évidence des biomarqueurs de la qualité du greffon et d'étendre les critères d'acceptabilité du greffon en permettant les prélèvements à partir de donneurs à coeur arrêté est une possibilité. Les prélèvements pulmonaires après arrêt cardiaque sont effectués, en clinique expérimentale chez l'homme, en Espagne depuis trois ans. Il existe dans ce pays une législation très favorable et surtout une conscience collective qui rend le don d'organes extrêmement facilité. Il est donc essentiel d'optimiser l' utilisation de cette ressource. Pour cela, la mise en place de critères de validation de la qualité du greffon est une donnée clé pour palier à ce manque de transplantation pulmonaire. Les critères d'acceptabilité d'un greffon pulmonaires sont basés sur des données cliniques n'existant pas de biomarqueurs biologiques de qualité et de viabilité du greffon. Nous proposons ici l'utilisation de la métabolomique par spectroscopie en Résonance Magnétique Nucléaire à haute résolution par rotation à angle magique (RMN HRMAS) pour mettre en évidence des biomarqueurs de la qualité du greffon. La métabolomique par la spectroscopie RMN HRMAS, est une technique d'analyse rapide (20 minutes) et originale, caractérisée par l'analyse directe d'un tissu biologique intact sans nécessité d'extraction. Cette technique étudie les profils métaboliques dans le but de mettre en évidence des biomarqueurs métaboliques. La métabolomique a été largement utilisée dans des études en cancérologie pour la détermination de la malignité d'un tissu (Bertini 1. et coll. , Canser Res. 2012/ Griffin JL et coll ., Nat Rev Cancer, 2004/ Li M. et coll. , PLoSOne, 2011/ O'connell TM. Bioanalysis. 2012/ Ma Y. et coll. Mol Biol Rep. 2012). Cependant, très peu de publications dans la littérature s'intéressent au domaine de la transplantation et à la qualité du greffon (Rocha C. et coll. , Journal of Proteome Research, 2011/ RobertR. et coll. J Critical Ca re 2010/ Stenlund H. et coll., Chemometrics and Intelligent Laboratory Systems, 2009/ Du a rte F.L. et coll. , Anal.Chem.2005). Ce projet de thèse avait pour objectifs de :1. Etudier la faisabilité d'utiliser la métabolomique par la spectroscopie RMN HRMAS pour évaluer la qualité du greffon pulmonaire.2. Mettre en évidence de potentiels biomarqueurs de la qualité du greffon pulmonaire.3. Evaluer une éventuelle introduction de cette technique en pratique courante dans un environnement hospitalier. Pour répondre à ces objectifs, il a été entrepris :• Etudier les métabolomes pulmonaires de différentes espèces animales, puis de les comparer au métabolome du poumonhumain afin d'identifier le modèle expérimental le plus adapté à la transplantation pulmonaire.• Evaluer la qualité du greffon chez un modèle animal (porc Large White) pour la transplantation pulmonaire (modèle expérimental de préservation pulmonaire en in situ chez le donneur à coeur arrêté, modèle de perfusion pulmonaire en ex vivo sur machine ocs™).• Evaluer l'effet de la perfusion de deux solutions de conservation sur la qualité du greffon pulmonaire chez le porc. / Lung transplantation is a therapeutic alternative in many severe pulmonary diseases, especially in patients suffering from CF (CysticFibrosis), idiopathie pulmonary fibrosis (IPF), lymphangioleiomyomatosis (LAM) or pulmonary hypertension . However, the need fortransplantation far outweighs the number of transplants performed in France. The causes of this imbalance include an insufficient number of potential donors because of the current criteria for the acceptance of the graft that are restricted as biomarkers of quality and viability of the graft have not been described so far.One of the possibilities to increase the donor pool is to identify biomarkers of the quality of the graft and expand the criteria foracceptability of the graft allowing withdrawals from non-heart-beating donors. The lung taking were performed after cardiac arrest inclinical trials carried out on humans for three years in Spain.lt is therefore essential to optimize the use of this resource. For this, the establishment of criteria for validating the quality of the graft isgiven a key to solve this problem of lung transplantation. The criteria for acceptability of a lung transplant are based on clinical data inabsence of biomarkers of quality and viability for the lung graft.We propose the use of the metabolomics by high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (HRMASNMR) to highlight potential biomarkers for the quality of the graft.The Metabolomics by NMR HRMAS spectroscopy is an original analytical technique characterized by a rapid analysis (20 minutes)performed on intact biopsy samples without extraction prior to analysis. This technique studies the metabolic profiles in arder to identifymetabolic biomarkers. Metabolomics has been widely used in studies in oncology for the determination of malignancy of a tissue (Bertini et al. , Canser Res. 2012/ Griffin JL et al., Nat Rev Cancer, 2004/ Li M. et al. , PLoS One, 2011/ O'connel! TM. Bioanalysis. 2012/ Ma Y. et al. Mol Biol Rep. 2012). However, very few papers in the literature combine the use of the metabolomics NMR HRMAS and the assessment of the quality of the graft (Rocha C. et al. , Journal of Proteome Research, 2011/ Robert R. et al. J Critical Care 2010/ Stenlund H. et al, Chemometrics and Intelligent Laboratory Systems, 2009/ Duarte F.L. et al. , Anal. Chem. 2005).The purposes of this research work were:1. Studying the feasibility of using the metabolomics by NMR HRMAS for the assessment of the quality of the lung graft2. Assess the metabolome of the lung in degradation conditions and highlight potential biomarkers of the quality of the graft3. Assess the possible use of the metabolomics by NMR HRMAS as a tool in clinical practice within a hospital environment.To answer to these purposes we made experimental experiences as follows:- Studying the lung metabolome of various animal species, and compare them to the human metabolome to identify the most suitableexperimental model for lung transplantation.- Assessing the quality of the graft in an animal model (pig Large White) for lung transplantation (experimental model of lung preservation in situ in the case of non-heart-beating donor, lung model for an ex vivo perfusion using OCS ™ Machine)- Evaluating the effect of perfusion with two preservation solutions on the quality of lung graft in pig model.

La présente thèse est constituée par un ensemble d'études expérimentales sur l'effet des hautes pressions sur les nanotubes de carbone mono-parois, individualisées, fermés ou ouvertes, donc vides ou remplis d'eau. Les techniques des hautes pressions et de la spectroscopie Raman ont été combinées afin d'étudier l'effondrement des nanotubes et de sonder les modifications induites par l'effet de la pression. Les coefficients de pression des modes radiaux de respiration (RBM) ont été obtenus avec identification individuelle par chiralité. Les RBM des nanotubes remplis d'eau ont pu être observés à des pressions bien plus élevées que pour des nanotubes vides. Après un cycle à haute pression, les nanotubes vides de diamètre plus important n'étaient pas détectables tandis que les tubes de diamètre sous-nanométrique se sont remplis d'eau. Ces observations suggèrent que les nanotubes de diamètre le plus faible ont une meilleur stabilité sous pression qui est accrue par le remplissage par de l'eau. Une réponse inusuelle du nanotube (7,2) suggère que la chiralité peut avoir aussi un rôle aussi important dans la stabilité structurelle, en tout cas pour les nanotubes de plus faibles diamètres. De son côté, l'évolution des modes de vibration tangentiels suggère l'effondrement radial des nanotubes vides d'un diamètre d'environ de 1.32 nm à une pression proche de 4 GPa, en accord avec les prévisions théoriques les plus récentes. Ces mêmes tubes remplis d'eau, présentent un effondrement à une pression qui se situe au-delà de 16 GPa / The present thesis constitutes a set of experimental studies on the effect of high pressures on single wall carbon nanotubes, individualized, closed or open, therefore empty or filled with water. High-pressure techniques and Raman spectroscopy were combined to study the radial collapse, as well to probe the pressure-induced modifications. Chirality-resolved pressure derivatives were obtained for the radial breathing modes (RBM). The RBM of water-filled could be observed at pressures higher than those of empty. After a high-pressure cycle, empty nanotubes of larger diameters were not detectable anymore, while sub nanometric diameter ones became filled with water. Such observations suggest that thinner nanotubes have better pressure-stability, which is increased upon water filling. An unusual response of the (7,2) nanotube suggests that the chirality may have also an important role on the structural stability for small diameters. The evolution of the tangential modes suggest the onset of radial collapse of empty nanotubes averaging 1.32 nm diameter at about 4 GPa, in agreement with the latest theoretical predictions. These same nanotubes, though water-filled, they collapse at pressures higher than 16 GPa