Stereoselective synthesis of vinyl germanes and silanes. Applications of tris(trimethyl)germanes and silanes in Pd-catalyzed cross -coupling reactions

Although group 14 organometallic compounds (Si, Sn) have been well developed as transmetallation reagents in cross-coupling reactions, the application of organogermanium compounds as cross-coupling reagents is still a relatively new area with few papers published. This study aimed to develop methods for the synthesis of new classes of vinyl germane and vinyl silane compounds, mainly Z and E tris(trimethylsilyl)germanes and silanes, which were then applied to Pd-catalyzed cross-couplings with aryl and alkenyl halides. The stereoselective radical-mediated desulfonylation of vinyl sulfones with tris(trimethyl)germanium or silane hydrides provided access to the synthesis of trans vinyl germanes or silanes. Alternatively hydrogermylation or hydrosilylation of terminal alkynes gave cis vinyl germanes or silanes. The application of these new classes of organometallic compounds in cross-coupling reactions with various aryl and alkenyl halides under aqueous [NaOH/H2O2/Pd(PPh 3)4] and anhydrous [KH/t-BuOOH/Pd(PPh 3)4] oxidative conditions were investigated. ^ It was found that the vinyl tris(trimethylsilyl)germanes successfully underwent Pd-catalyzed cross-couplings with aryl and alkenyl halides and aryl triflates under aqueous and anhydrous oxidative conditions. These procedures provided examples of "ligand-free" Pd-catalyzed coupling of organogermanes with aryl and alkenyl halides. Interestingly, couplings with fluorinated vinyl germanes appeared to occur more easily than with the corresponding (α-fluoro)vinyl stannanes and silanes since neither addition of an extra ligand nor activation with fluoride was necessary. The vinyl tris(trimethyl)silanes were found to be alternative substrates for the Hiyama reaction. The coupling of TTMS-silanes with various aryl, heteroaryl as well as alkenyl halides proceeded smoothly upon treatment with hydrogen peroxide in the presence of sodium hydroxide and fluoride ion. ^

The current and potential applications of Ambient Mass Spectrometry in detecting food fraud

The adulteration of food has received substantial amounts of media attention in the last few years, with events such as the European horsemeat scandal in 2013 sending shockwaves through society. Almost all cases are motivated by the pursuit of profits and are often aided by long and complex supply chains. In the past few years, the rapid growth of ambient mass spectrometry (AMS) has been remarkable, with over thirty different ambient ionisation techniques available. Due to the increasing concerns of the food industry and regulators worldwide, AMS is now being utilised to investigate whether or not it can generate results which are faster yet comparable to those of conventional techniques. This article reviews some aspects of the adulteration of food and its impact on the economy and the public's health, the background to ambient mass spectrometry and the studies that have been undertaken to detect food adulteration using this technology.

Fabrication, Optical Analysis and Photonic Applications of Certain Metallic Nanostructure-Integrated Dye Doped Polymer Optical Fibers” submitted by Ms. Suneetha Sebastian

Polymer Optical Fibers have occupied historically a place for large core flexible fibers operating in short distances. In addition to their practical passive application in short-haul communication they constitute a potential research field as active devices with organic dopants. Organic dyes are preferred as dopants over organic semiconductors due to their higher optical cross section. Thus organic dyes as gain media in a polymer fiber is used to develop efficient and narrow laser sources with a tunability throughout the visible region or optical amplifier with high gain. Dyes incorporated in fiber form has added advantage over other solid state forms such as films since the pump power required to excite the molecules in the core of the fiber is less thereby utilising the pump power effectively. In 1987, Muto et.al investigated a dye doped step index polymer fiber laser. Afterwards, numerous researches have been carried out in this area demonstrating laser emission from step index, graded index and hollow optical fibers incorporating various dyes. Among various dyes, Rhodamine6G is the most widely and commonly used laser dye for the last four decades. Rhodamine6G has many desirable optical properties which make it preferable over other organic dyes such as Coumarin, Nile Blue, Curcumin etc. The research focus on the implementation of efficient fiber lasers and amplifiers for short fiber distances. Developing efficient plastic lasers with electrical pumping can be a new proposal in this field which demands lowest possible threshold pump energy of the gain medium in the cavity as an important parameter. One way of improving the efficiency of the lasers, through low threshold pump energy, is by modifying the gain of the amplifiers in the resonator/cavity. Success in the field of Radiative Decay Engineering can pave way to this problem. Laser gain media consisting of dye-nanoparticle composites can improve the efficiency by lowering the lasing threshold and enhancing the photostability. The electric field confined near the surface of metal nanoparticles due to Localized Surface Plasmon Resonance can be very effective for the excitation of active centers to impart high optical gain for lasing. Since the Surface Plasmon Resonance of nanoparticles of gold and silver lies in the visible range, it can affect the spectral emission characteristics of organic dyes such as Rhodamine6G through plasmon field generated by the particles. The change in emission of the dye placed near metal nanoparticles depend on plasmon field strength which in turn depends on the type of metal, size of nanoparticle, surface modification of the particle and the wavelength of incident light. Progress in fabrication of different types of nanostructures lead to the advent of nanospheres, nanoalloys, core-shell and nanowires to name a few. The thesis deals with the fabrication and characterisation of polymer optical fibers with various metallic and bimetallic nanostructures incorporated in the gain media for efficient fiber lasers with low threshold and improved photostability.

Applications of Microwave Antenna Array for Wireless Power Transmission and Radar Imaging in Complex Environment

Thesis (Ph.D.)--University of Washington, 2016-08

Optimization and Applications of Large-Scale Biomedical Event Networks

The overwhelming amount and unprecedented speed of publication in the biomedical domain make it difficult for life science researchers to acquire and maintain a broad view of the field and gather all information that would be relevant for their research. As a response to this problem, the BioNLP (Biomedical Natural Language Processing) community of researches has emerged and strives to assist life science researchers by developing modern natural language processing (NLP), information extraction (IE) and information retrieval (IR) methods that can be applied at large-scale, to scan the whole publicly available biomedical literature and extract and aggregate the information found within, while automatically normalizing the variability of natural language statements. Among different tasks, biomedical event extraction has received much attention within BioNLP community recently. Biomedical event extraction constitutes the identification of biological processes and interactions described in biomedical literature, and their representation as a set of recursive event structures. The 2009–2013 series of BioNLP Shared Tasks on Event Extraction have given raise to a number of event extraction systems, several of which have been applied at a large scale (the full set of PubMed abstracts and PubMed Central Open Access full text articles), leading to creation of massive biomedical event databases, each of which containing millions of events. Sinece top-ranking event extraction systems are based on machine-learning approach and are trained on the narrow-domain, carefully selected Shared Task training data, their performance drops when being faced with the topically highly varied PubMed and PubMed Central documents. Specifically, false-positive predictions by these systems lead to generation of incorrect biomolecular events which are spotted by the end-users. This thesis proposes a novel post-processing approach, utilizing a combination of supervised and unsupervised learning techniques, that can automatically identify and filter out a considerable proportion of incorrect events from large-scale event databases, thus increasing the general credibility of those databases. The second part of this thesis is dedicated to a system we developed for hypothesis generation from large-scale event databases, which is able to discover novel biomolecular interactions among genes/gene-products. We cast the hypothesis generation problem as a supervised network topology prediction, i.e predicting new edges in the network, as well as types and directions for these edges, utilizing a set of features that can be extracted from large biomedical event networks. Routine machine learning evaluation results, as well as manual evaluation results suggest that the problem is indeed learnable. This work won the Best Paper Award in The 5th International Symposium on Languages in Biology and Medicine (LBM 2013).

Performance analysis in soccer: applications of player tracking technology

The aim of this thesis was threefold, firstly, to compare current player tracking technology in a single game of soccer. Secondly, to investigate the running requirements of elite women’s soccer, in particular the use and application of athlete tracking devices. Finally, how can game style be quantified and defined. Study One compared four different match analysis systems commonly used in both research and applied settings: video-based time-motion analysis, a semi-automated multiple camera based system, and two commercially available Global Positioning System (GPS) based player tracking systems at 1 Hertz (Hz) and 5 Hz respectively. A comparison was made between each of the systems when recording the same game. Total distance covered during the match for the four systems ranged from 10 830 ± 770 m (semi-automated multiple camera based system) to 9 510 ± 740m (video-based time-motion analysis). At running speeds categorised as high-intensity running (>15 km⋅h-1), the semi-automated multiple camera based system reported the highest distance of 2 650 ± 530 m with video-based time-motion analysis reporting the least amount of distance covered with 1 610 ± 370 m. At speeds considered to be sprinting (>20 km⋅h-1), the video-based time-motion analysis reported the highest value (420 ± 170 m) and 1 Hz GPS units the lowest value (230 ± 160 m). These results demonstrate there are differences in the determination of the absolute distances, and that comparison of results between match analysis systems should be made with caution. Currently, there is no criterion measure for these match analysis methods and as such it was not possible to determine if one system was more accurate than another. Study Two provided an opportunity to apply player-tracking technology (GPS) to measure activity profiles and determine the physical demands of Australian international level women soccer players. In four international women’s soccer games, data was collected on a total of 15 Australian women soccer players using a 5 Hz GPS based athlete tracking device. Results indicated that Australian women soccer players covered 9 140 ± 1 030 m during 90 min of play. The total distance covered by Australian women was less than the 10 300 m reportedly covered by female soccer players in the Danish First Division. However, there was no apparent difference in the estimated "#$%&', as measured by multi-stage shuttle tests, between these studies. This study suggests that contextual information, including the “game style” of both the team and opposition may influence physical performance in games. Study Three examined the effect the level of the opposition had on the physical output of Australian women soccer players. In total, 58 game files from 5 Hz athlete-tracking devices from 13 international matches were collected. These files were analysed to examine relationships between physical demands, represented by total distance covered, high intensity running (HIR) and distances covered sprinting, and the level of the opposition, as represented by the Fédération Internationale de Football Association (FIFA) ranking at the time of the match. Higher-ranking opponents elicited less high-speed running and greater low-speed activity compared to playing teams of similar or lower ranking. The results are important to coaches and practitioners in the preparation of players for international competition, and showed that the differing physical demands required were dependent on the level of the opponents. The results also highlighted the need for continued research in the area of integrating contextual information in team sports and demonstrated that soccer can be described as having dynamic and interactive systems. The influence of playing strategy, tactics and subsequently the overall game style was highlighted as playing a significant part in the physical demands of the players. Study Four explored the concept of game style in field sports such as soccer. The aim of this study was to provide an applied framework with suggested metrics for use by coaches, media, practitioners and sports scientists. Based on the findings of Studies 1- 3 and a systematic review of the relevant literature, a theoretical framework was developed to better understand how a team’s game style could be quantified. Soccer games can be broken into key moments of play, and for each of these moments we categorised metrics that provide insight to success or otherwise, to help quantify and measure different methods of playing styles. This study highlights that to date, there had been no clear definition of game style in team sports and as such a novel definition of game style is proposed that can be used by coaches, sport scientists, performance analysts, media and general public. Studies 1-3 outline four common methods of measuring the physical demands in soccer: video based time motion analysis, GPS at 1 Hz and at 5 Hz and semiautomated multiple camera based systems. As there are no semi-automated multiple camera based systems available in Australia, primarily due to cost and logistical reasons, GPS is widely accepted for use in team sports in tracking player movements in training and competition environments. This research identified that, although there are some limitations, GPS player-tracking technology may be a valuable tool in assessing running demands in soccer players and subsequently contribute to our understanding of game style. The results of the research undertaken also reinforce the differences between methods used to analyse player movement patterns in field sports such as soccer and demonstrate that the results from different systems such as GPS based athlete tracking devices and semi-automated multiple camera based systems cannot be used interchangeably. Indeed, the magnitude of measurement differences between methods suggests that significant measurement error is evident. This was apparent even when the same technologies are used which measure at different sampling rates, such as GPS systems using either 1 Hz or 5 Hz frequencies of measurement. It was also recognised that other factors influence how team sport athletes behave within an interactive system. These factors included the strength of the opposition and their style of play. In turn, these can impact the physical demands of players that change from game to game, and even within games depending on these contextual features. Finally, the concept of what is game style and how it might be measured was examined. Game style was defined as "the characteristic playing pattern demonstrated by a team during games. It will be regularly repeated in specific situational contexts such that measurement of variables reflecting game style will be relatively stable. Variables of importance are player and ball movements, interaction of players, and will generally involve elements of speed, time and space (location)".

PICTOAPRENDE: Design and evaluation of a tool that contributes to the personal autonomy of children and youth diagnosed with autism spectrum disorder in Ecuador

This paper presents the development and evaluation of PICTOAPRENDE, which is an interactive software designed to improve oral communication. Additionally, it contributes to the development of children and youth who are diagnosed with autism spectrum disorder (ASD) in Ecuador. To fulfill this purpose initially analyzes the intervention area where the general characteristics of people with ASD and their status in Ecuador is described. Statistical techniques used for this evaluation constitutes the basis of this study. A section that presents the development of research-based cognitive and social parameters of the area of intervention is also shown. Finally, the algorithms to obtain the measurements and experimental results along with the analysis of them are presented.

Applications of functional nucleic acids in imaging, sensing and drug delivery and investigations of DNAzyme-metal interactions

Functional nucleic acids (FNA), including nucleic acids catalysts (ribozymes and DNAzymes) and ligands (aptamers), have been discovered in nature or isolated in a laboratory through a process called in vitro selection. They are nucleic acids with functions similar to protein enzymes or antibodies. They have been developed into sensors with high sensitivity and selectivity; it is realized by converting the reaction catalyzed by a DNAzyme/ribozyme or the binding event of an aptamer to a fluorescent, colorimetric or electrochemical signal. While a number of studies have been reported for in vitro sensing using DNAzymes or aptamers, there are few reports on in vivo sensing or imaging. MRI is a non-invasive imaging technique; smart MRI contrast agents were synthesized for molecular imaging purposes. However, their rational design remains a challenge due to the difficulty to predict molecular interactions. Chapter 2 focuses on rational design of smart T1-weighted MRI contrast agents with high specificity based on DNAzymes and aptamers. It was realized by changing the molecular weight of the gadolinium conjugated DNA strand with the analytes, which lead to analyte-specific water proton relaxation responses and contrast changes on an MRI image. The designs are general; the high selectivity of FNA was retained. Most FNA-based fluorescent sensors require covalent labeling of fluorophore/quencher to FNAs, which incurrs extra expenses and could interfere the function of FNAs. Chapter 3 describes a new sensor design avoiding the covalent labeling of fluorophore and quencher. The fluorescence of malachite green (MG) was regulated by the presence of adenosine. Conjugate of aptamers of MG and adenosine and a bridge strand were annealed in a solution containing MG. The MG aptamer did not bind MG because of its hybridization to the bridge strand, resulting in low fluorescence signal of MG. The hybridization was weakened in the presence of adenosine, leading to the binding of MG to its aptamer and a fluorescence increase. The sensor has comparable detection limit (20 micromolar) and specificity to its labeled derivatives. Enzymatic activity of most DNAzymes requires metal cations. The research on the metal-DNAzyme interaction is of interest and challenge to scientists because of the lack of structural information. Chapters 4 presents the research on the characterization of the interaction between a Cu2+-dependent DNAzyme and Cu2+. Electron paramagnetic resonance (EPR) and UV-Vis spectroscopy were used to probe the binding of Cu2+ to the DNAzyme; circular dichroism was used to probe the conformational change of the DNAzyme induced by Cu2+. It was proposed that the conformational change by the Cu2+ binding is important for the activity of the DNAzyme. Chapter 5 reports the dependence of the activity of 8-17 DNAzyme on the presence of both Pb2+ and other metal cations including Zn2+, Cd2+ and Mg2+. It was discovered that presence of those metal cations can be cooperative or inhibitive to 8-17 activity. It is hypothesized that the 8-17 DNAzyme had multiple binding sites for metal cations based on the results. Cisplatin is effective killing tumor cells, but with significant side effects, which can be minimized by its targeted delivery. Chapter 6 focuses on the effort to functionalize liposomes encapsulating cisplatin by an aptamer that selectively bind nucleolin, an overexpressed protein by breast cancer cells. The study proved the selective cytotoxicity to breast cancer cells of the aptamer-functionalized liposome.

Preparation, Characterization, and Photocatalytic Applications of MWCNTs/TiO2 Composite

The multiwall carbon nanotubes (MWCNTs)/titanium dioxide (P25) composite in different ratios was prepared using simple evaporation and drying process. The composite was characterized by Raman spectroscopy, X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy, and scanning electron microscopy (SEM). The photocatalytic activity of this composite was investigated using degradation of the Bismarck brown R dye (BBR). An optimal MWCNTs/TiO2 ratio of 0.5% (w/w) was found to achieve the maximum rate of BBR degradation. It was observed that the composite exhibits enhanced photocatalytic activity compared with TiO2. The enhancement in photocatalytic activity performance of the MWCNTs/P25 composite is explained in terms of recombination of photogenerated electron-hole pairs. In addition, MWCNTs act as a dispersing support to control the morphology of TiO2 particles in the MWCNTs/TiO2 composite.

Applications of synchrotron x-ray powder diffraction in hydrated cements: high-resolution and high-pressure studies

The main aim of this study is to apply synchrotron radiation techniques for the study of hydrated cement pastes. In particular, the tetracalcium aluminoferrite phase, C4AF in cement nomenclature, is the major iron-containing phase in Ordinary Portland Cement (OPC) and in iron rich belite calcium sulfoaluminate cements. In a first study, the hydration mechanism of pure tetracalcium aluminoferrite phase with water-to-solid ratio of 1.0 has been investigated by HR-SXRPD (high resolution synchrotron X-ray powder diffraction). C4AF in the presence of water hydrates to form mainly an iron-containing hydrogarnet-type (katoite) phase, C3A0.84F0.16H6, as single crystalline phase. Its crystal structure and stoichiometry were determined by the Rietveld method and the final disagreement factors were RWP=8.1% and RF=4.8% [1]. As the iron content in the product is lower than that in C4AF, it is assumed that part of the iron also goes to an amorphous iron rich gel, like the hydrated alumina-type gel, as hydration proceeds. Further results from the high-resolution study will be discussed. In a second study, the behavior of pure and iron-containing katoites (C3AH6 and C3A0.84F0.16H6) under pressure have been analyzed by SXRPD using a diamond anvil cell (DAC) and then their bulk moduli were determined. The role of the pressure transmitting medium (PTM) has also been studied. In this case, silicone oil as well as methanol/ethanol mixtures have been used as PTM. Some “new peaks” were detected in the pattern for C3A0.84F0.16H6 as pressure increases, when using ethanol/methanol as PTM. These new peaks were still present at ambient pressure after releasing the applied pressure. They may correspond to crystalline nordstrandite or doyleite from the crystallization of amorphous aluminium hydroxide. The results from the high-pressure study will also be discussed.

Design and Applications of a Decade-Spanning Terahertz Frequency Comb Spectrometer: Doppler-limited Rotational Spectroscopy of Methanol and Methanol-OD

This thesis details the design and applications of a terahertz (THz) frequency comb spectrometer. The spectrometer employs two offset locked Ti:Sapphire femtosecond oscillators with repetition rates of approximately 80 MHz, offset locked at 100 Hz to continuously sample a time delay of 12.5 ns at a maximum time delay resolution of 15.6 fs. These oscillators emit continuous pulse trains, allowing the generation of a THz pulse train by the master, or pump, oscillator and the sampling of this THz pulse train by the slave, or probe, oscillator via the electro-optic effect. Collecting a train of 16 consecutive THz pulses and taking the Fourier transform of this pulse train produces a decade-spanning frequency comb, from 0.25 to 2.5 THz, with a comb tooth width of 5 MHz and a comb tooth spacing of ~80 MHz. This frequency comb is suitable for Doppler-limited rotational spectroscopy of small molecules. Here, the data from 68 individual scans at slightly different pump oscillator repetition rates were combined, producing an interleaved THz frequency comb spectrum, with a maximum interval between comb teeth of 1.4 MHz, enabling THz frequency comb spectroscopy.

The accuracy of the THz frequency comb spectrometer was tested, achieving a root mean square error of 92 kHz measuring selected absorption center frequencies of water vapor at 10 mTorr, and a root mean square error of 150 kHz in measurements of a K-stack of acetonitrile. This accuracy is sufficient for fitting of measured transitions to a model Hamiltonian to generate a predicted spectrum for molecules of interest in the fields of astronomy and physical chemistry. As such, the rotational spectra of methanol and methanol-OD were acquired by the spectrometer. Absorptions from 1.3 THz to 2.0 THz were compared to JPL catalog data for methanol and the spectrometer achieved an RMS error of 402 kHz, improving to 303 kHz when excluding low signal-to-noise absorptions. This level of accuracy compares favorably with the ~100 kHz accuracy achieved by JPL frequency multiplier submillimeter spectrometers. Additionally, the relative intensity performance of the THz frequency comb spectrometer is linear across the entire decade-spanning bandwidth, making it the preferred instrument for recovering lineshapes and taking absolute intensity measurements in the THz region. The data acquired by the Terahertz Frequency Comb Spectrometer for methanol-OD is of comparable accuracy to the methanol data and may be used to refine the fit parameters for the predicted spectrum of methanol-OD.

Applications of advanced and dual energy computed tomography in proton therapy

This thesis focuses on advanced reconstruction methods and Dual Energy (DE) Computed Tomography (CT) applications for proton therapy, aiming at improving patient positioning and investigating approaches to deal with metal artifacts. To tackle the first goal, an algorithm for post-processing input DE images has been developed. The outputs are tumor- and bone-canceled images, which help in recognising structures in patient body. We proved that positioning error is substantially reduced using contrast enhanced images, thus suggesting the potential of such application. If positioning plays a key role in the delivery, even more important is the quality of planning CT. For that, modern CT scanners offer possibility to tackle challenging cases, like treatment of tumors close to metal implants. Possible approaches for dealing with artifacts introduced by such rods have been investigated experimentally at Paul Scherrer Institut (Switzerland), simulating several treatment plans on an anthropomorphic phantom. In particular, we examined the cases in which none, manual or Iterative Metal Artifact Reduction (iMAR) algorithm were used to correct the artifacts, using both Filtered Back Projection and Sinogram Affirmed Iterative Reconstruction as image reconstruction techniques. Moreover, direct stopping power calculation from DE images with iMAR has also been considered as alternative approach. Delivered dose measured with Gafchromic EBT3 films was compared with the one calculated in Treatment Planning System. Residual positioning errors, daily machine dependent uncertainties and film quenching have been taken into account in the analyses. Although plans with multiple fields seemed more robust than single field, results showed in general better agreement between prescribed and delivered dose when using iMAR, especially if combined with DE approach. Thus, we proved the potential of these advanced algorithms in improving dosimetry for plans in presence of metal implants.

Student’s Perception on the Personal Impact of a Social Education Degree Internship

The functional profile of the social educator is based on the development of theoretical, technical and personal/relational skills, which should guide training courses organization. Assuming the shortcomings of a merely theoretical approach, besides a consistent preparation in theoretical and essential technical contents for socio-educational intervention, practice in context should be favoured as an opportunity to develop professional skills, together with a critical reflection on the functional profile. This study emerges from the need to reflect and rethink the internship, as well as how the respective supervision is developed, of the degree in social education at the School of Education of the Polytechnic Institute of Viseu, and it is based on the students’ perceptions about the impact of the internship on personal development. This is a qualitative and exploratory study, using the documentary analysis of 50 final internship reports. From the content analysis, four categories emerged referring to gains in terms of acquiring and managing knowledge, development of technical skills, personal and relational development and reinforcement of professional identity. The importance given to personal and relational development should be noted (41.4% of mentions) taking into account its relevance in constructing a professional identity. Findings on the technical skills and on the increase of profession knowledge, also by mobilising theoretical training, positively reinforce the internship model that is based on a proximity supervision approach and on a dialogical perspective of the professional learning.

Applications of perceptual sparse representation (Spikegram) for copyright protection of audio signals

Chaque année, le piratage mondial de la musique coûte plusieurs milliards de dollars en pertes économiques, pertes d’emplois et pertes de gains des travailleurs ainsi que la perte de millions de dollars en recettes fiscales. La plupart du piratage de la musique est dû à la croissance rapide et à la facilité des technologies actuelles pour la copie, le partage, la manipulation et la distribution de données musicales [Domingo, 2015], [Siwek, 2007]. Le tatouage des signaux sonores a été proposé pour protéger les droit des auteurs et pour permettre la localisation des instants où le signal sonore a été falsifié. Dans cette thèse, nous proposons d’utiliser la représentation parcimonieuse bio-inspirée par graphe de décharges (spikegramme), pour concevoir une nouvelle méthode permettant la localisation de la falsification dans les signaux sonores. Aussi, une nouvelle méthode de protection du droit d’auteur. Finalement, une nouvelle attaque perceptuelle, en utilisant le spikegramme, pour attaquer des systèmes de tatouage sonore. Nous proposons tout d’abord une technique de localisation des falsifications (‘tampering’) des signaux sonores. Pour cela nous combinons une méthode à spectre étendu modifié (‘modified spread spectrum’, MSS) avec une représentation parcimonieuse. Nous utilisons une technique de poursuite perceptive adaptée (perceptual marching pursuit, PMP [Hossein Najaf-Zadeh, 2008]) pour générer une représentation parcimonieuse (spikegramme) du signal sonore d’entrée qui est invariante au décalage temporel [E. C. Smith, 2006] et qui prend en compte les phénomènes de masquage tels qu’ils sont observés en audition. Un code d’authentification est inséré à l’intérieur des coefficients de la représentation en spikegramme. Puis ceux-ci sont combinés aux seuils de masquage. Le signal tatoué est resynthétisé à partir des coefficients modifiés, et le signal ainsi obtenu est transmis au décodeur. Au décodeur, pour identifier un segment falsifié du signal sonore, les codes d’authentification de tous les segments intacts sont analysés. Si les codes ne peuvent être détectés correctement, on sait qu’alors le segment aura été falsifié. Nous proposons de tatouer selon le principe à spectre étendu (appelé MSS) afin d’obtenir une grande capacité en nombre de bits de tatouage introduits. Dans les situations où il y a désynchronisation entre le codeur et le décodeur, notre méthode permet quand même de détecter des pièces falsifiées. Par rapport à l’état de l’art, notre approche a le taux d’erreur le plus bas pour ce qui est de détecter les pièces falsifiées. Nous avons utilisé le test de l’opinion moyenne (‘MOS’) pour mesurer la qualité des systèmes tatoués. Nous évaluons la méthode de tatouage semi-fragile par le taux d’erreur (nombre de bits erronés divisé par tous les bits soumis) suite à plusieurs attaques. Les résultats confirment la supériorité de notre approche pour la localisation des pièces falsifiées dans les signaux sonores tout en préservant la qualité des signaux. Ensuite nous proposons une nouvelle technique pour la protection des signaux sonores. Cette technique est basée sur la représentation par spikegrammes des signaux sonores et utilise deux dictionnaires (TDA pour Two-Dictionary Approach). Le spikegramme est utilisé pour coder le signal hôte en utilisant un dictionnaire de filtres gammatones. Pour le tatouage, nous utilisons deux dictionnaires différents qui sont sélectionnés en fonction du bit d’entrée à tatouer et du contenu du signal. Notre approche trouve les gammatones appropriés (appelés noyaux de tatouage) sur la base de la valeur du bit à tatouer, et incorpore les bits de tatouage dans la phase des gammatones du tatouage. De plus, il est montré que la TDA est libre d’erreur dans le cas d’aucune situation d’attaque. Il est démontré que la décorrélation des noyaux de tatouage permet la conception d’une méthode de tatouage sonore très robuste. Les expériences ont montré la meilleure robustesse pour la méthode proposée lorsque le signal tatoué est corrompu par une compression MP3 à 32 kbits par seconde avec une charge utile de 56.5 bps par rapport à plusieurs techniques récentes. De plus nous avons étudié la robustesse du tatouage lorsque les nouveaux codec USAC (Unified Audion and Speech Coding) à 24kbps sont utilisés. La charge utile est alors comprise entre 5 et 15 bps. Finalement, nous utilisons les spikegrammes pour proposer trois nouvelles méthodes d’attaques. Nous les comparons aux méthodes récentes d’attaques telles que 32 kbps MP3 et 24 kbps USAC. Ces attaques comprennent l’attaque par PMP, l’attaque par bruit inaudible et l’attaque de remplacement parcimonieuse. Dans le cas de l’attaque par PMP, le signal de tatouage est représenté et resynthétisé avec un spikegramme. Dans le cas de l’attaque par bruit inaudible, celui-ci est généré et ajouté aux coefficients du spikegramme. Dans le cas de l’attaque de remplacement parcimonieuse, dans chaque segment du signal, les caractéristiques spectro-temporelles du signal (les décharges temporelles ;‘time spikes’) se trouvent en utilisant le spikegramme et les spikes temporelles et similaires sont remplacés par une autre. Pour comparer l’efficacité des attaques proposées, nous les comparons au décodeur du tatouage à spectre étendu. Il est démontré que l’attaque par remplacement parcimonieux réduit la corrélation normalisée du décodeur de spectre étendu avec un plus grand facteur par rapport à la situation où le décodeur de spectre étendu est attaqué par la transformation MP3 (32 kbps) et 24 kbps USAC.