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We report for the first time a broad equilibrium model describing the complexation of ionic species in non-aqueous media that explicitly includes ion pairing for one of the components and that relies upon activities rather than molar concentrations. This model directly contradicts existing commonplace equilibrium treatments, which were shown to be incomplete, often invalid, and misleading. Experimental validation of our model was achieved through studies of pseudorotaxane formation between dibenzylammonium salts (DBAm-X) and dibenzo-24-crown-8 (DB24C8) in CDCl3:CD3CN (3:2). In that particular case, we showed that fluctuations in the apparent Ka,exp values as usually reported are attributable to ion pairing, with a dissociation constant Kipd, and that the constant Kassoc for pseudorotaxane complexation is independent of the counterion, a result of the complex existing in solution as a free cation. In accord with this model, we further described a straightforward and simple method to increase the extent of complexation by using either a ditopic cation and anion host, or adding to the charged host/guest solution a molecularly separate host capable of complexing the dissociated counterion. Also in accord with this model, we investigated the influence of the solvent¡¯s dielectric constant on Kipd and Kassoc. On the basis of competing condensation reactions between amines and ketones which were shown to occur within the timescale of host/guest recognition, we also challenged the commonly employed use of acetone in similar complexation studies involving 2o ammonium ions. Because a major goal of this work was to ultimately increase binding efficiency and selectivity, we explored new methods to drive complexation in related pseudorotaxane systems. We noted that addition of di- or tri-topic hydrogen bond accepting anions to solutions of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 or bis(5-carboxy-1,3-phenylene)-32-crown-10 and paraquat di(hexafluorophosphate) served to significantly enhance host/guest interaction. The addition of Et4N+TFA- to an acetone solution of diacid crown and paraquat 2PF6 effectively boosted Ka,exp 40-fold, as estimated by 1H NMR studies. Similar increases in the apparent Ka,exp were observed upon the addition of n-Bu4N+OTs-. Evidenced by crystal structures, the increase in association resulted from chelation of the OH moieties of the crown by the di- or tri-topic anions, forming supramolecular bicyclic macrocycles (pseudocryptands) and stabilizing the complex in a cooperative manner. Significantly, Ka,exp of one of the pseudocryptands was shown to equal that determined in the corresponding cryptand complex. / Ph. D.

Identity based cryptography was first proposed by Shamir in 1984. Rather than deriving a public key from private information, which would be the case in traditional public key encryption schemes, in identity based schemes a user's identity plays the role of the public key. This reduces the amount of computations required for authentication, and simplifies key-management. Efficient and strong implementations of identity based schemes are based around easily computable bilinear mappings of two points on an elliptic curve onto a multiplicative subgroup of a field, also called pairing. The idea of utilizing the identity of the user simplifies the public key infrastructure. However, since pairing computations are expensive for both area and timing, the proposed identity based cryptosystem are hard to implement. In order to be able to efficiently utilize the idea of identity based cryptography, there is a strong need for an efficient pairing implementations. Pairing computations could be realized in multiple fields. Since the main building block and the bottleneck of the algorithm is multiplication, we focused our research on building a fast and small arithmetic core that can work on multiple fields. This would allow a single piece of hardware to realize a wide spectrum of cryptographic algorithms, including pairings, with minimal amount of software coding. We present a novel unified core design which is extended to realize Montgomery multiplication in the fields GF(2^n), GF(3^m), and GF(p). Our unified design supports RSA and elliptic curve schemes, as well as identity based encryption which requires a pairing computation on an elliptic curve. The architecture is pipelined and is highly scalable. The unified core utilizes the redundant signed digit representation to reduce the critical path delay. While the carry-save representation used in classical unified architectures is only good for addition and multiplication operations, the redundant signed digit representation also facilitates efficient computation of comparison and subtraction operations besides addition and multiplication. Thus, there is no need for transformation between the redundant and non-redundant representations of field elements, which would be required in classical unified architectures to realize the subtraction and comparison operations. We also quantify the benefits of unified architectures in terms of area and critical path delay. We provide detailed implementation results. The metric shows that the new unified architecture provides an improvement over a hypothetical non-unified architecture of at least 24.88 % while the improvement over a classical unified architecture is at least 32.07 %. Until recently there has been no work covering the security of pairing based cryptographic hardware in the presence of side-channel attacks, despite their apparent suitability for identity-aware personal security devices, such as smart cards. We present a novel non-linear error coding framework which incorporates strong adversarial fault detection capabilities into identity based encryption schemes built using Tate pairing computations. The presented algorithms provide quantifiable resilience in a well defined strong attacker model. Given the emergence of fault attacks as a serious threat to pairing based cryptography, the proposed technique solves a key problem when incorporated into software and hardware implementations. In this dissertation, we also present an efficient accelerator for computing the Tate Pairing in characteristic 3, based on the Modified Duursma Lee algorithm.

La méthode de la fonctionnelle de la densité d’énergie (Energy Density Functional, EDF) est une approche phénoménologique permettant de calculer les propriétés élémentaires des noyaux atomiques (masses, dimensions et formes) a l’approximation du champ moyen. Elle permet également d’obtenir les spectres correspondant à certains états collectifs (vibrationnels et rotationnels) en mettant en œuvre des calculs ≪ au-delà ≫ du champ moyen (avec la méthode de la coordonnées génératrice (GCM) ou le mécanisme de brisure/restauration de symétries). Cette méthode, applicable sur toute la charte des noyaux hormis les plus légers, connait un regain d’intérêt avec le développement de nouveaux faisceaux radioactifs tels SPIRAL2 au GANIL. Des travaux récents ont montré qu’une description des états collectifs des noyaux nécessitait la modification et la généralisation des formes habituellement utilisées pour la fonctionnelle de la densité d’énergie, notamment avec la suppression de termes dépendants de la densité. Il a également été montre que les fonctionnelles de Skyrme pouvaient conduire à des instabilités et transitions de phases non physiques dans la matière nucléaire et les noyaux, en particulier lorsque le système est autorisé à briser des symétries. Le but de ce travail de thèse a été d’achever la construction de la fonctionnelle de Skyrme généralisée, initiée par J. Sadoudi (Constraints on the nuclear energy density functional and new possible analytical forms., CEA Saclay, 2011), puis d’en ajuster les paramètres. Le terme dépendant de la densité est remplacé par un potentiel d’interaction à 3 et 4 corps et la fonctionnelle associée est utilisée pour décrire le champ moyen et le champ d’appariement. Il a été nécessaire de construire un nouveau protocole d’ajustement afin de contraindre les paramètres de cette fonctionnelle. En particulier, l’ajustement est fait avec des contraintes sur les instabilités précédemment mentionnées. Parallèlement a la construction du protocole d’ajustement, l’utilisation de techniques d’analyse covariante a permis, dans un premier temps, d’estimer les erreurs statistiques associées a chaque paramètre ajuste et les barres d’erreurs des observables calculées. Dans un second temps, nous avons étudié les corrélations existantes entre les différentes contraintes choisies dans le protocole, ce qui a permis de mettre en évidence certains défauts de ces nouvelles interactions généralisées. Enfin, dans un travail annexe, nous avons utilisé des méthodes semiclassiques de type Thomas-Fermi modifiées (MTF) afin de dériver une formule analytique permettant d’estimer la valeur du coefficient d’énergie de surface d’une interaction de Skyrme généralisée. En réajustant les paramètres de la fonctionnelle SLy5 avec une contrainte sur ce coefficient, nous avons montré qu’il était fortement corrèle aux propriétés de fission des actinides. Nous aurons ainsi à notre disposition, grâce à cette estimation du coefficient d’énergie de surface, un outil simple à mettre en œuvre dans des protocoles d’ajustements futurs qui permettra de contraindre les propriétés de fission des noyaux / -

Covariant density functional theory (CDFT) is one of the modern theoretical tools for describing the nuclear structure physics of finite nuclei. Its performance is defined by underlying covariant energy density functionals (CEDFs). In this dissertation and within the framework of the CDFT, different physical properties of the ground and the excited states of rotating and non-rotating nuclei have been investigated. A systematic global investigation of pairing properties based on all available experimental data on pairing indicators has been performed for the first time in the framework of covariant density functional theory. It is based on separable pairing interaction of Ref.\ \cite{TMR.09}. The optimization of the scaling factors of this interaction to experimental data clearly reveals its isospin dependence in the neutron subsystem. However, the situation is less certain in the proton subsystem since similar accuracy of the description of pairing indicators can be achieved both with isospin-dependent and mass-dependent scaling factors. The differences in the functional dependencies of scaling factors lead to the uncertainties in the prediction of proton and neutron pairing properties which are especially pronounced at high isospin and could have a significant impact on some physical observables. Although the present investigation is based on the NL5(E) covariant energy density functional (CEDF), its general conclusions are expected to be valid also for other CEDFs built at the Hartree level. It is shown for the first time that rotational bands which are proton unbound at zero or low spins can be transformed into proton bound ones at high spin by collective rotation of nuclear systems. This is due to strong Coriolis interaction, which acts on high-$N$ or strongly mixed M orbitals and drives the highest in energy occupied single-particle states of nucleonic configurations into the negative energy domain. Proton emission from such proton bound rotational states is suppressed by the disappearance of static pairing correlations at high spins of interest. These physical mechanisms lead to a substantial extension of the nuclear landscape beyond the spin zero proton drip line. In addition, a new phenomenon of the formation of giant proton halos in rotating nuclei emerges: it is triggered by the occupation of strongly mixed M intruder orbitals. Possible experimental fingerprints of the transition from particle bound to particle unbound part of rotational bands are discussed and compared for proton and neutron rich nuclei near and beyond respective drip lines.

L’association de la bière avec les mets apparaît comme une nouvelle tendance en France. Il est donc nécessaire pour les promoteurs de bière et les professionnels de la gastronomie de fournir à leurs clients des conseils de qualité en terme d’accord bière et mets. Au vu de ce contexte, l’objectif de la thèse était d’identifier les principes d’association et de mieux comprendre les mécanismes perceptuels qui les sous-tendent. Les déterminants des accords mets et boissons ont, dans un premier temps, été identifiés à partir du discours d’experts. Les résultats ont montrés que les associations mets et boissons sont régies par des caractéristiques perceptuelles, conceptuelles et affectives, liées à des mécanismes physico-chimiques, perceptuels et cognitifs. Les experts ont souvent mentionné la «similarité aromatique» comme l'un des principaux principes d'association. Ce principe consiste à associer deux produits partageant des arômes similaires. Les mécanismes perceptuels sous-jacents à ce principe ont été investigués. Les résultats ont montrés qu’une similarité aromatique entre un mets et une boisson augmente le niveau d’harmonie et d’homogénéité de leur association et diminue sa complexité. Ces effets peuvent être renforcés en orientant l’attention du dégustateur sur l’arôme partagé. D’un point de vue théorique, cette thèse conclut que l’association bières et mets inclut des dimensions sensorielles avec une recherche d’harmonie, mais aussi des dimensions symboliques et contextuelles. D’un point de vue plus appliqué, cette thèse fournit aux professionnels de la gastronomie, de nouvelles informations concernant les mécanismes perceptifs sous-tendant les principes d’associations. / Pairing between beer and dishes emerges as a new trend in France. Beer promoters or gastronomy professionals need to offer high-quality advices in terms of beer and food pairing to their customers. Within this context, the objective of the research was to identify pairing principles and to better understand the underlying perceptual mechanisms. Determinants of food and beverage pairing were first analysed from experts’ discourses. Results showed that food and beverage pairings are governed by perceptual, conceptual and affective features, related to physio-chemical, perceptual and cognitive processes. Experts often mentioned “Aromatic Similarity” as one of the main pairing principles. This “Aromatic similarity” principle consists in matching two products sharing similar aromas. Underlying perceptual mechanisms were then investigated. Results showed that aromatic similarity in food and beverage generally increases harmony and homogeneity and decreases complexity of the match. These effects can be reinforced by orientating the attentional focus on the shared aroma. From a theoretical point of view, this work concludes that beer and food pairing includes sensory dimensions with the search for harmony, as well as symbolic and contextual dimensions. From an applied point of view, this work provides useful information to gastronomy professionals with recent knowledge on perceptual mechanisms underlying food and beverage pairing principles.

This work explores two methods for practical cryptography on mobile devices. The first method is a quantum-resistant key-exchange protocol proposed by Jao et al.. As the use of mobile devices increases, the deployment of practical cryptographic protocols designed for use on these devices is of increasing importance. Furthermore, we are faced with the possible development of a large-scale quantum computer in the near future and must take steps to prepare for this possibility. We describe the key-exchange protocol of Jao et al. and discuss their original implementation. We then describe our modifications to their scheme that make it suitable for use in mobile devices. Our code is between 18-26% faster (depending on the security level). The second is an highly optimized implementation of Miller's algorithm that efficiently computes the Optimal Ate pairing over Barreto-Naehrig curves proposed by Grewal et al.. We give an introduction to cryptographic pairings and describe the Tate pairing and its variants. We then proceed to describe Grewal et al.'s implementation of Miller's algorithm, along with their optimizations. We describe our use of hand-optimized assembly code to increase the performance of their implementation. For the Optimal Ate pairing over the BN-446 curve, our code is between 7-8% faster depending on whether the pairing uses affine or projective coordinates.

Denna uppsats handlar om Systembolagets dryckesklassifikation. För att hjälpa kunder att matcha mat och dryck har Systembolaget utvecklat ett klassifikationssystem med tre klassifikationsaspekter: smaktypen, som beskriver dryckens karaktär, smakklockorna, som beskriver olika smakupplevelser, och matsymbolerna, bilder som indikerar ett användningsområde. Uppsatsen studerar hur Systembolaget klassificerar drycker och hur butiksanställda använder sig av klassifikationsaspekterna i kundmöten. Denna studie använde sig av genreteori som konstruerad av Jack Andersen och Jens-Erik Mais tankar om klassifikation i kontext. Genreteori inspirerade metoden.  Studien bestod av en intervju med produktinformatörer på Systembolaget och en enkät som skickades till butiksanställda. Intervjun visade att Systembolagets klassifikationssystem är standardiserat och att dryckerna klassificeras metodiskt. Klassifikationsaspekterna tilldelas sensorsikt, där de tilldelade smakklockorna påverkar valet av smaktyper och matsymbolerna bestäms med hjälp av smakklockorna och smaktyperna. Enkäten visade att butiksanställda främst använde sig av smaktyperna och smakklockorna och gjorde detta praktiskt, genom att rekommendera drycker, eller pedagogiskt, där målet var att lära kunderna om dryckerna och klassifikationssystemet. Matsymbolerna var inte användbara för de som har kunskap om mat och dryck men användes av kunder. Anställdas användning av klassifikationssystemet låg i deras genrekunskap. De praktiska och pedagogiska synsätten var genrer av aktivitet som förverkligade klassifikationen till användbara verktyg istället för enbart beskrivande aspekter. / This thesis considers the beverage classification at Systembolaget, the Swedish alcohol monopoly. In order to help customers with the pairing of food and beverages, Systembolaget has developed a classification system with three classification elements: the flavour type, which describes the overall character of the beverage; the flavour graphics, which indicate levels of flavour experiences; and the food symbols, which are pictures that indicate various kinds of food. This thesis studies how Systembolaget classifies their beverages and how Systembolaget employees use classification elements in customer interactions. This study made use of genre theory as conceived by Jack Andersen and the concept of classification in context as conceived by Jens-Erik Mai. Genre theory informed the method. The study consisted of an interview with product informers at Systembolaget and a survey sent out to store employees. The interview revealed that Systembolaget’s classification system is standardised and the classification of beverages is methodological. The classification elements are assigned sensorially. Assigned flavour graphics affect the choice of flavour type. Food symbols are determined through the flavour graphics and flavour type. The survey revealed that store employees primarily use flavour types and flavour graphics and do so practically, by recommending beverages, or pedagogically, with the goal of teaching customer about beverages and Systembolaget's classification. The food symbols are not useful for those with in-depth knowledge of wine and food pairings but are sometimes relied upon by customers. Employees’ use of classification elements was dependent on their genre knowledge. The practical and pedagogical approaches were genres of activity that realised the classification into viable tools rather than just descriptive elements. This is a two years master’s thesis in Archive, Library and Museum studies.

This work sought to enforce aromatic interactions between compatible π-molecular orbital systems with ionic bonding. In this case the interacting partners are oppositely charged discotic triangulene derivatives. The observed properties of the heterodimeric ion-pairs likely arise due to a hypothetical synergy between electrostatics and π-interactions. The work presented here describes investigation of putative covalency arising from this hypothetical synergy in the electrostatics driven π-stacking. In order to probe this, various hypotheses were made and experiments were designed to test their validity. The results from the experiments show existence of contact ion-pairs and complex solvent-separated discotic ions in solution. The formation of complex ion-pairs arise due to the fact that the electrostatic interaction that brings the discotic ions together is strong, but does not neutralize when the contact is made. So, the dipole created by the monopoles in a dimeric contact ion-pair can attract ions at both termini forming oligomers. This process apparently continues towards highly aggregated states and then to nanometric species and at some point the material precipitates. The propensity to aggregate and form complex-ions limited our approach to the measurement of the energetics of the ion-pairing for two reasons: (1) the observables had a complex dependence on temperature, solvent, concentration and ionic strength; and (2) the mass in solution was undergoing kinetic evolution towards solid states. The turbidimetric effects arising due to aggregate formation further complicated the extraction of weak interactions between the ions and hence effects determination of ion-pairing constants.