The application of ICP-MS to the fields of proteomics and genomics has arisen in part due to its ability to detect and quantify trace levels of S and P, which are major constituents in proteins and nucleic acids respectively. The development of collision/reaction cell technology and high resolution instruments has enabled these biologically important elements to be measured and quantified at the pg - ng ml-1 level. Despite these advances, the detection limits of P and S are still inferior compared to other elements. Oligonucleotides containing biotin functionality were labelled with Au nano-particles attached to a streptavidin protein to achieve site specific labelling, with 100% labelling efficiency. Each nano-particle contained ~86 Au atoms, resulting in an 882 fold signal enhancement for 24 base length oligonucleotides. However, this enhancement factor was only observed when one oligonucleotide bound to one nano-particle in a 1:1 ratio. Much lower Au labelling efficiencies and signal enhancements were observed when thiolated oligonucleotides were labelled with maleimide functionalised gold nano-particles. This was attributed to the extensive and difficult sample preparation steps that were required prior to labelling. The detection and quantification of adducts formed between DNA and the Pt anti-cancer drugs cisplatin and oxaliplatin were also investigated with ICP-MS. Acid digestion of the carbon based DNA matrix enabled Pt adducts to be quantified at low dose rates of 1 Pt atom per 1 500 000 nucleotides in ~12 μg DNA. Such sensitive mass spectrometric determinations could be employed in clinical tests to detect and quantify low level adducts formed in patients in-vivo. To complement ICP-MS analysis, electrospray ionisation linear ion trap mass spectrometry was employed to study the interaction of oxaliplatin with the four DNA nucleobases. Multiple stage mass spectrometry enabled detailed Pt-nucleobase adduct fragmentation pathways to be established. The method of DNA detection using P in conjunction with the collision cell, or cool plasma to form PO+ was also demonstrated and the limitations of the method, namely, polyatomic interferences and severe matrix effects were highlighted.

Transportation-related collisions are ubiquitous and often traumatic. Identifying post-collision psychological distress and the characteristics of the collision survivor that lead to distress are vital to the development of early and appropriate interventions. The goals of this study were: 1) to use a questionnaire as opposed to a typical diagnostic interview, 2) to confirm that psychological distress is present in currently hospitalized transportation-related collision survivors, 3) to confirm that different types of distress co-occur, 4) to determine if distress is more likely to occur in those who have had prior distress, and 5) to explore the relationship between symptoms of distress and perception of control by self, others, and God/Higher Power of past, present, and future collision-related events. Subjects were 100 English speaking adult inpatients, 16 years and older, who were less than 3 weeks post-injury, and receiving some rehabilitation. Participants completed a questionnaire which included the Center for Epidemiologic Studies Depression Scale (CES-D), Beck Anxiety Inventory (BAI), and Davidson Trauma Scale (DTS) as well as questions regarding demographics, details of the collision/injury, alcohol/drug use, pain, past and present stressors, social support, and perceptions of life change. Information about head injury and collision-concurrent alcohol and/or drug use was collected from the patient's medical chart. Compared to other traumatic experiences (e.g., physical/sexual abuse, war combat), transportation-related collisions share the characteristics of being sudden, unexpected, relatively brief in duration, and potentially lethal. Prior studies used diagnostic interviews to identify psychological distress in post hospitalized collision survivors. This study used questionnaire-based depression, anxiety, and trauma symptom inventories in a currently hospitalized sample and included head injured patients. As hypothesized there was a significant correlation between the CES-D total score and the BAI total score [Hypothesis 1], the DTS total score [Hypothesis 2], and collision concurrent alcohol and/or drug use (as indicated by medical chart records or score on the CAGE) [Hypothesis 3]. Further, there was a significant correlation between the patient's self-reported history of depression, anxiety, or stress reaction and CES-D, BAI, and DTS total scores, respectively [Hypothesis 4]. Also as hypothesized, perceived personal control of the past "events that caused the collision" was significantly correlated with the CES-D total score [Hypothesis 5] while perceived control of the present "life in general right now" was negatively correlated to the CES-D total score [Hypothesis 6]. Contrary to hypothesis, perceived control of the present "recovery process right now" was not correlated to the CES-D total score [Hypothesis 6] nor was perceived control of the future "preventing a collision like this from happening...again" [Hypothesis 7]. Perception of control by "others" of the present "recovery process right now" was negatively correlated to the CES-D total score. Results support the theory that perceived personal control of past traumatic events increases the likelihood of psychological distress. Some evidence of post traumatic growth was found.

This thesis presents an evaluation of the performance, in terms of throughput and latency, of two Media Access Control (MAC) mechanisms in Underwater Acoustic Networks (UANs), using a model designed in the COTS simulation tool OPNET 10.5. The carrier sense multiple access with collision avoidance is the predominant approach for implementing the MAC mechanism in UANs. However, the underwater acoustic environment is characterized by extreme propagation delays and limited bandwidth, which suggests that an Aloha-like scheme may merit consideration. The performance of these two schemes was compared with respect to two topologies: tree and grid. The results showed that an Aloha-like scheme that does not segment messages outperforms the contention-based scheme under all load conditions, in terms of both throughput and latency, for the two topologies. This thesis is the first to establish that Aloha-like MAC mechanisms can be more than a limited alternative for lightly loaded networks; more specifically, they can be the preferred choice for an environment with large propagation delays. / Lieutenant Commander, Portuguese Navy

Les recherches en sécurité routière suscitent largement l'intérêt des chercheurs. Indépendamment des techniques de modélisation, un facteur important d'imprécision -qui caractérise les études dans ce domaine- concerne le niveau d'agrégation des données. Aujourd'hui, la plupart des autoroutes sont équipées de systèmes permanents de surveillance qui fournissent des données désagrégées. Dans ce contexte, l'objectif de la thèse est d'exploiter les données trafic recueillies en temps réel au moment des accidents, afin d'élargir le champ des travaux précédents et de mettre en évidence un potentiel d'applications innovantes. À cette fin, nous examinons les effets du trafic sur le type d'accident ainsi que sur la gravité subie par les occupants des véhicules, tout en tenant compte des facteurs environnementaux et géométriques. Des modèles Probit sont appliqués aux données de trafic et d'accidents enregistrés pendant quatre années sur le tronc commun aux autoroutes A4 et A86 en Ile-de-France. Les résultats empiriques indiquent que le type d'accident peut être presque exclusivement défini par les conditions de trafic prévalant peu avant son occurrence. En outre, l'augmentation du débit s'avère exercer un effet constamment positif sur la gravité, alors que la vitesse exerce un effet différentiel sur la gravité en fonction des conditions d'écoulement. Nous établissons ensuite un cadre conceptuel pour des applications de gestion des incidents qui s'appuie sur les données trafic recueillies en temps réel. Nous utilisons les résultats de la thèse afin d'explorer des implications qui ont trait à la propension et à la détection des incidents, ainsi qu'à l'amélioration de leur gestion / Research on road safety has been of great interest to engineers and planners for decades. Regardless of modeling techniques, a serious factor of inaccuracy - in most past studies - has been data aggregation. Nowadays, most freeways are equipped with continuous surveillance systems making disaggregate traffic data readily available ; these have been used in few studies. In this context, the main objective of this dissertation is to capitalize highway traffic data collected on a real-time basis at the moment of accident occurrence in order to expand previous road safety work and to highlight potential further applications. To this end, we first examine the effects of various traffic parameters on type of road crash as well as on the injury level sustained by vehicle occupants involved in accidents, while controlling for environmental and geometric factors. Probit models are specified on 4-years of data from the A4-A86 highway section in the Ile-de -France region, France. Empirical findings indicate that crash type can almost exclusively be defined by the prevailing traffic conditions shortly before its occurrence. Increased traffic volume is found to have a consistently positive effect on severity, while speed has a differential effect on severity depending on flow conditions. We then establish a conceptual framework for incident management applications using real-time traffic data on urban freeways. We use dissertation previous findings to explore potential implications towards incident propensity detection and enhanced management

Les objectifs de cette thèse visent le développement d’un traitement inédit dans un repère spatiale tridimensionnel, pour le problème de la dynamique de collisions diffusives d’objets macromoléculaires en solution en écoulement hydrodynamique à l'intérieur des pores de largeur variable, soumis aux forces hydrodynamiques, du mouvement brownien et des collisions diffusifs aux parois des pores, en utilisant la modélisation théorique et les simulations numériques. L’approche par simulation numérique est nécessaire car il est extrêmement complexe d’utiliser des outils analytiques à présent pour traiter le problème de ces collisions diffusives aux parois solides. Les algorithmes que nous avons développés et les simulations correspondantes sont suffisamment généraux et avancés pour être directement appliquée à l'étude de la dynamique d'une grande variété de polymère et des particules biologiques dans des solutions diluées sous diverses conditions physiques et hydrodynamiques à l'intérieur des pores. Par ailleurs, les mécanismes conduisant à l'adhésion de nano particules et de particules macromoléculaires sous conditions de non-équilibre, en raison de l'influence contradictoire des collisions mécaniques diffusifs et les forces attractives de Hamaker aux parois solides, sont d'un intérêt majeur. Nous avons donc développé un modèle théorique pour calculer le coefficient de restitution. L'objectif est de quantifier le bilan énergétique pendant le processus de collision diffusive de ces particules aux parois, sous l'influence des forces de répulsion d'une part et les forces attractives de Hamaker. Cela se fait par l'élaboration d'un modèle, basé sur le JKR et les théories d’Hertz, pour tenir compte des pertes d'énergie lors des collisions et des gains d'énergie en raison des interactions Hamaker. L’adhésion arrive si le bilan énergétique le permet. Notre modèle théorique est développé en proposant une approche particulière basée sur le potentiel Hamaker. Nous démontrons ce bilan par le biais d'une équation caractéristique non linéaire pour le coefficient de restitution, et analysons ses propriétés qui déterminent l'adhésion ou non pour diverses conditions physiques initiales. / The purpose of this thesis is to develop a comprehensive model analysis in a three-dimensional spatial frame for the dynamics of molecular particles in dilute colloidal suspensions in solutions flowing inside pores of variable width, subject to hydrodynamic forces, Brownian motion and diffusive collisions at the rough pore boundaries, by using numerical simulations. The approach by simulations is necessary because it is extremely complex to use analytical tools at present to deal with the problem of diffusive collisions of the particles at the solid pore boundaries. The algorithms which we have developed and the corresponding simulations are sufficiently general and refined to be directly applied to the study of the dynamics of a wide variety of polymer and biological particles in dilute solutions under diverse physical and applicable hydrodynamic conditions inside pores. Moreover, the mechanisms leading to the adhesion of particles of nano sizes under what would be non-equilibrium conditions, due to the conflicting influence of the mechanical diffusive collisions and the attractive Hamaker forces at the boundaries, are of major interest. We have hence investigated a theoretical model to calculate the restitution coefficient from basic physical principles. The objective is to quantify the energy balance during the process of a diffusive collision of a nano particle under the influence of the repulsive forces on one hand, and the attractive Hamaker forces acting on the nano particle on the other. This is done by developing a model, based on the JKR and Hertz theories, to account for the energy losses during collisions, and for the energy gains due to the Hamaker interactions. Adhesion becomes an outcome if the energy balance permits this. Our theoretical model is developed by proposing a special analytic approach based on the Hamaker potential. We derive from the theoretical analysis a characteristic nonlinear equation for the restitution coefficient, and analyze its properties which determine under given physical conditions the outcome for adhesion or not.

The present thesis analyses the proposal of CubeHash with spe- cial emphasis on the following papers: "Inside the Hypercube" [1], "Sym- metric States and Their Improved Structure" [7] and "Linearisation Frame- work for Collision Attacks" [6]. The CubeHash algorithm is presented in a concise manner together with a proof that the CubeHash round function R : ({0, 1}32 )32 → ({0, 1}32 )32 is a permutation. The results of [1] and [7] con- cerning the CubeHash symmetric states are reviewed, corrected and substan- tiated by proofs. More precisely, working with a definition of D-symmetric state, based on [7], the thesis proves both that for V = Z4 2 and its linear subspace D, there are 22 |V | |D| D-symmetric states and an internal state x is D-symmetric if and only if the state R(x) is D-symmetric. In response to [1], the thesis presents a step-by-step computation of a lower bound for the num- ber of distinct symmetric states, explains why the improved preimage attack does not work as stated and gives a mathematical background for a search for fixed points in R. The thesis further points out that the linearisation method from [6] fails to consider the equation (A ⊕ α) + β = (A + β) ⊕ α (∗), present during the CubeHash iteration phase. Necessary and sufficient conditions for A being a solution to (∗) are...

The development of the IEEE 802.22 standard is aimed at providing broadband access in rural areas by effectively utilizing the unused TV band, provided no harmful interference is caused to the incumbent operation. This thesis presents the analytical framework to evaluate the number of active customer premise equipments (CPEs) in a wireless regional area network. Initial ranging is the primary process in IEEE 802.22 networks for CPEs to access the network and establish their connections with the base station (BS). A comprehensive analysis of initial ranging mechanism is provided in this work and initial ranging request success probability is derived based on the number of contended CPEs and the initial contention window size. Further, the average ranging success delay is derived for the maximum backoff stages. The collision probability is highly dependent on the size of the initial contention window and the number of contended CPEs. To keep it at a specific level, it is necessary for the BS to schedule the required size of the initial contention window to facilitate the maximum number of CPEs to establish their connections with reasonable delay. Therefore, the optimized initial window size is proposed that meets the collision probability constraint for a particular number of contended CPEs. An analytical model is also developed to estimate the ranging request collision probability depending upon the size of initial contention window and the number of contended CPEs. Moreover, this approximation provides the threshold size for contention window to start the initial ranging process in the IEEE 802.22 network.

The problem of aircraft conflict detection and resolution (CDR) in uncertainty is addressed in this thesis. The main goal in CDR is to provide safety for the aircraft while minimizing their fuel consumption and flight delays. In reality, a high degree of uncertainty can exist in certain aircraft-aircraft encounters especially in cases where aircraft do not have the capabilities to communicate with each other. Through the use of a probabilistic approach and a multiple model (MM) trajectory information processing framework, this uncertainty can be effectively handled. For conflict detection, a randomized Monte Carlo (MC) algorithm is used to accurately detect conflicts, and, if a conflict is detected, a conflict resolution algorithm is run that utilizes a sequential list Viterbi algorithm. This thesis presents the MM CDR method and a comprehensive MC simulation and performance evaluation study that demonstrates its capabilities and efficiency.

Cette thèse étudie les premiers instants d'une collision d'ions lourds. Juste après cette collision, il a été démontré que la matière produite -- appelée Plasma de Quarks et de Gluons (PQG) -- est très loin de l'équilibre thermique. On voudrait donc savoir si le PQG thermalise, et quelle est l'échelle de temps caractéristique pour cela. Le manuscrit expose l'étude de ces questions dans deux sortes de théories.Dans un premier temps, on étudie une théorie scalaire. En initialisant cette dernière dans un état hors équilibre, on peut étudier l'approche de l'équilibre pour un système de volume fixe ou un système en expansion unidimensionnelle. Dans les deux cas, des preuves d'une possible thermalisation peuvent être observées : une équation d'état se forme, le tenseur des pressions devient isotrope et le nombre d'occupation tend vers une distribution d'équilibre thermique classique. Ces résultats sont obtenus à l'aide de l'approximation classique statistique (ACS), qui permet d'inclure des contributions au-delà de l'ordre dominant de la théorie des perturbations.Dans un second temps, le "Color Glass Condensate", une théorie effective basée sur la Chromodynamique quantique adaptée à l'étude des premiers instants suivant la formation du PQG, est utilisé pour étudier de manière plus réaliste l'approche de l'équilibre thermique dans les collisions d'ions lourds. Après avoir établi quelques prérequis pour l'utilisation de l'ACS, les simulations numériques effectuées avec les équations de Yang-Mills semblent indiquer que le PQG devient rapidement isotrope, tandis que son rapport viscosité sur entropie est très petit, ce qui est la caractéristique d'un fluide quasi idéal. / This thesis deals with the theory of the early stages of a heavy ion collision. Just after such a collision, the matter produced – called the Quark-Gluon-Plasma (QGP) – has been shown to be far out of thermal equilibrium. One would like to know whether the QGP thermalizes, and what is the typical time scale for this. Proving that the QGP thermalizes would also justify from first principles the hydrodynamical treatment of the subsequent evolution of a heavy ion collision. After having recalled some essential theoretical concepts, the manuscript addresses these questions in two different theories In a first part, we study a scalar field theory. Starting from an out of equilibrium initial condition, one studies the approach to equilibrium in a fixed volume or in a one-dimensional expanding system. In both cases, clear signs of thermalization are obtained: an equation of state is formed, the pressure tensor becomes isotropic and the occupation number approaches a classical thermal distribution. These results are obtained thanks to the classical statistical approximation (CSA), that includes contributions beyond the Leading Order perturbative calculation. In a second part, the Color Glass Condensate – a quantum chromdynamics (QCD) effective theory well suited to describe the early life of the QGP – is used to treat more realistically the approach to thermalization in heavy ion collisions. After having derived some analytical prerequisites for the application of the CSA, the numerical simulations performed with the Yang-Mills equations show evidences of an early onset of hydrodynamical behavior of the QGP: the system becomes isotropic on short time scales, while the shear viscosity over entropy ratio is very small, which is characteristic of a quasi perfect fluid.

Diese Arbeit stellt eine Messung des W+W- Produktionswirkungsquerschnitts in pp Kollisionen bei einer Schwerpunktenergie von √s = 13 TeV vor. Der verwendete Datensatz wurde mit dem ATLAS Detektor im Jahr 2015 aufgezeichnet und entspricht einer integrierten Luminosität von 3,16 fb-1. Die W+W- Ereignisse werden über leptonische Zerfälle der W-Bosonen selektiert, wobei jeweils eines der W Bosonen in ein Elektron und ein Elektronneutrino und das andere in ein Myon und ein Myonneutrino zerfällt. Der gemessene Wirkungsquerschnitt in einem Referenzphasenraum, der nahe der Detektorakzeptanz definiert ist, beträgt σ (fiducial, W+W-) = 529 ± 20 (stat.) ± 50 (syst.) ± 11 (lumi.) fb. Das Ergebnis stimmt innerhalb der Fehlergrenzen mit der besten verfügbaren Standardmodell-Vorhersage von 478 ± 17 fb überein. Die kinematischen Verteilungen der im Zerfall der beiden W Bosonen produzierten Leptonen wurden genauer untersucht, um die drei- Eichbosonenkopplung bei den WWγ und WWZ Vertizes zu messen. Abweichungen dieser Kopplungen vom Standardmodell können ein Hinweis auf neue Physik sein. Für die Größen, welche diese anomalen Kopplungen parametrisieren, wurden Konfidenzintervalle berechnet. Die beobachteten Kopplungen stimmen mit dem Standardmodell überein. / This thesis presents a measurement of W+W- production cross section with the pp collision data collected at the ATLAS detector in the year of 2015. The dataset corresponds to a centre-of-mass collision energy of √s = 13 TeV with a total integrated luminosity of 3.16 fb-1. The W+W- signal events are selected using a signature where one of the W bosons decays into an electron and an electron neutrino while the other produces a muon with an associated muon neutrino. The measured cross section in the chosen fiducial phase space close to detector acceptance is σ (fiducial, W+W-) = 529 ± 20 (stat.) ± 50 (syst.) ± 11 (lumi.) fb. The result within the assigned uncertainties is compatible with the best available Standard Model prediction of 478 ± 17 fb. The observed kinematic spectrums of the produced leptons from the decay of the two W bosons are further investigated to study the triple gauge boson couplings at the WWγ und WWZ vertices. The deviation of these couplings from the Standard Model can probe the existence of new physics. The confidence intervals have been calculated for the parameters representing these anomalous couplings. The observations are consistent with the Standard Model expectations.