Informal analysis of authenticated key establishment (ake) protocols was commonly accepted as the valid argument for their security in the past. Although it can provide some confidence in protocol correctness, experience has shown time and again that ake protocols are likely to contain flaws even after an informal analysis is completed. Therefore, it has become increasingly common to expect a formal analysis, and preferably a mathematical proof, of any published ake protocol in order to obtain increased confidence in its security. In this research we use an appropriate model for analysing ake protocols based on its features and properties. The model allows us to design ake protocols modularly and reuse existing protocol components. We provide a detailed description of its formalisation, operations and usage. This description also includes ways of extracting new protocol components from existing ake protocols. Following the description of the model, we propose a new unauthenticated key establishment protocol for two-party communications. By composing this protocol with authentication protocols, we can construct several new secure ake protocols. These new protocols are compared with existing protocols for their computational efficiency. The comparison shows that our new proven secure protocols are as efficient as the existing protocols with an informal security analysis. We then propose a three-party key establishment protocol which involves a trusted server and two users. We also propose a non-interactive authentication protocol and discuss it and a variant of it. These components are used to construct a secure three-party ake protocol that supports a privacy framework. This framework allows users to remain anonymous while conducting electronic transactions with an independent service provider. A new password-based authentication protocol is proposed to address the problem of authentication using passwords. This protocol carries a proof of security and satisfies a slightly relaxed definition of security. We demonstrate its application by composing it with existing key establishment protocols. To maximise its use, we modified a two-party key establishment protocol to become three-party server based. By using the server for authentication, two users within a common network domain can establish a secure session key. Only a small number of ake protocols are demonstrated in this thesis. There exist many more provably secure ake protocols that can be constructed using the protocol components presented by applying the approach of "mix and match". That is, each new component results in a number of new ake protocols depending on the number of existing components.

This report deals with the use of the "Modular Approach", in the simulation of change-over operations, for a continuous multiproduct chemical plant. A dynamic model of the continuous fat hydrolysis process was built, with the DYNSYS framework, with the purpose of evaluating the usefulness of this programme in simulating different change-over operation policies. Operator's activities were simulated making use of an interactive version of DYNSYS, demonstrating its value for studying alternate changeover policies and possible as a training device. Supervisory control was implemented in order to automate the change-over operations, simulating the functions of a small computer controlling the process. Improved operating policies for change-over are proposed and the validity of the simulation is discussed from both a practical and a theoretical point of view. / Thesis / Master of Engineering (ME)

Protein–lipid binding interactions play crucial roles in various physiological and pathological processes, making it very important to study these interactions at the molecular level. However, investigation of these interactions is complicated by several issues, including the inherent complexity of membranes as well as the diverse mechanisms by which proteins interact with the membrane surfaces. As a result, many of these interactions remain poorly characterized. Synthetic probes are useful tools employed for studying protein–lipid binding interactions. This thesis will detail the design and synthesis of metabolically stabilized analogues of various signaling lipids, which mimic the natural species and are not easily modified by enzymes present in biological systems. A modular approach is employed for synthesizing these lipid probes, giving access to a wide range of derivatized lipid probes that can then be used for several studies. Although a wide variety of metabolically stabilized lipid analogues have been synthesized, their activity has not yet been characterized and quantified in detail. So, there is a great need to synthesize biologically active phosphorothioate and phosphonate analogues of various signaling lipids in order to properly characterize and compare the binding affinities and activity of these analogues. Synthesis of metabolically stabilized lipid analogue would take us one step closer towards understanding protein–lipid interactions in biological systems and in trying to find answers to the myriad of questions pertaining to these systems.

Over the past decade, the use of asynchronous video interviews (AVIs) has increased exponentially, largely spurred by ongoing technological progress and shifts to remote work. Although prior research shows interview design can influence applicant reactions, the effect of video interview design factors on interviewee reactions remains unclear. The present study determines the influence of AVI stimulus format (text-based vs. audio-visual questions) on applicant perceptions of social presence, fairness and organisational attractiveness. To this end, a between-subjects posttest-only experimental design was used in two separate samples (South African sample, N = 58; USA sample, N = 169, Combined samples, N = 227). Participants were randomly assigned to either the control or experimental group. Participants completed a mock interview on a commercially available AVI platform and then answered a questionnaire measuring perceptions of social presence, fairness, and organisational attractiveness. Bootstrapped independent sample t-tests and serial mediation were used to test the hypotheses. Within Sample 1, applicant perceptions of social presence, fairness and organisational attractiveness were higher for the audio-visual and text-based AVIs, thereby supporting the proposition that audio-visual stimuli lead to higher perceptions of social presence, fairness and organisational attractiveness. Conversely, Sample 2's findings were non-significant (p > .05). While there were mixed results, the findings of this study provide preliminary evidence which suggests that within the South African context, audio-visual stimuli can be used in AVIs. Organisations in the American context should pay close attention to the effects of AVI stimulus format on applicant reactions as the findings from the American sample were not conclusive. Future research should investigate applicant reactions to different forms of AVI stimulus during a multi-stage selection process

The development of novel, tumor-selective and boron-rich compounds as potential agents for use in boron neutron capture therapy (BNCT) represents a very important field in cancer treatment by radiation therapy. Here, we report the design and synthesis of two promising compounds that combine meta-carborane, a water-soluble monosaccharide and a linking unit, namely glycine or ethylenediamine, for facile coupling with various tumor-selective biomolecules bearing a free amino or carboxylic acid group. In this work, coupling experiments with two selected biomolecules, a coumarin derivative and folic acid, were included. The task of every component in this approach was carefully chosen: the carborane moiety supplies ten boron atoms, which is a tenfold increase in boron content compared to the l-boronophenylalanine (l-BPA) presently used in BNCT; the sugar moiety compensates for the hydrophobic character of the carborane; the linking unit, depending on the chosen biomolecule, acts as the connection between the tumor-selective component and the boron-rich moiety; and the respective tumor-selective biomolecule provides the necessary selectivity. This approach makes it possible to develop a modular and feasible strategy for the synthesis of readily obtainable boron-rich agents with optimized properties for potential applications in BNCT.

Les études de sûreté de fonctionnement (SdF) sont en général basées sur l’hypothèse d’indépendance des événements de défaillance et de réparation ainsi que sur l’analyse des coupes qui décrivent les sous-ensembles de composants entraînant la défaillance du système. Dans le cas des systèmes dynamiques pour lesquels l’ordre d’occurrence des événements a une incidence directe sur le comportement dysfonctionnel du système, il est important de privilégier l’utilisation de séquences d’événements permettant une évaluation des indicateurs de SdF plus précise que les coupes. Ainsi, nous avons proposé, dans une première partie de nos travaux, un cadre formel permettant la détermination des séquences d’événements qui décrivent l’évolution du système ainsi que leur évaluation quantitative, en recourant à la théorie de langages probabilistes et à la théorie des processus markoviens/semi-markoviens. L'évaluation quantitative des séquences intègrent le calcul de leur probabilité d'occurrence ainsi que leur criticité (coût et longueur des séquences). Pour l’évaluation des séquences décrivant l’évolution des systèmes complexes présentant plusieurs modes de fonctionnement ou de défaillance, une approche modulaire basée sur les opérateurs de composition (choix et concaténation) a été proposée. Celle-ci consiste à calculer la probabilité d'une séquence d'événements globale à partir d'évaluations réalisées localement, mode par mode. Les différentes contributions sont appliquées sur deux cas d'étude de taille et complexité croissante. / Dependability studies are often based on the assumption of events (failures and repairs) independence but also on the analyse of cut-set which describes the subsets of components causing a system failure. In the case of dynamic systems where the events occurrence order has a direct impact on the dysfunctional behaviour, it is important to promote using event sequences instead of cut-sets for dependability assessment. In the first part, a formal framework is proposed. It helps in determining sequences of events that describe the evolution of the system and their assessment, using the theory of probabilistic languages and the theory of Markov/semi-Markov processes. The assessment integrates the calculation of the probability occurrence of the event sequences and their criticality (cost and length). For the assessment of complex systems with multiple operating/failure modes, a modular approach based on composition operators (choice and concatenation) is proposed. Evaluation of the probability of a global sequence of events is performed from local Markov/semi-Markov models for each mode of the system. The different contributions are applied on two case studies with a growing complexity.

This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis. Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated. Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems. A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands. Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved. <b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.

<p>This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.</p><p>Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.</p><p>Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.</p><p>A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.</p><p>Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.</p><p><b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.</p>

Les systèmes complexes ferroviaires étant de plus en plus contraints par des autorités de décision placées à un haut niveau d'abstraction, il devient problématique d'imposer des critères à une autre échelle que fonctionnelle. Ainsi, dès lors que l'on descend plus bas, nous sommes confrontés à des spécificités des systèmes nationaux qui font perdre la généralité du travail des décisionnaires Européens. Le problème est qu'à chaque niveau d'abstraction, des méthodes d'évaluation du risque existent, mais sans être compatibles entre elles. Par ailleurs, la combinaison des couches et la vision fonctionnelle du système ne prennent pas en compte l'impact des fonctions les unes sur les autres, ni le lien entre le niveau global et les composants afin d'allouer la sécurité.Nous proposons donc une démarche harmonisée d'évaluation du risque, capable de répartir les contraintes définies au niveau fonctionnel abstrait sur les entités qui implémentent les systèmes avec leurs spécificités.Notre contribution est méthodologique. Elle part d'un modèle fonctionnel du système ferroviaire constitué en couches. Le but étant de représenter ce système sans dépendance entre les fonctions, il a fallu les traduire indépendamment des autres en faisant apparaître les entrées/sorties comme des places/transitions d'un réseau de Petri. A chaque couche de la décomposition correspond une classe de réseau de Petri. Ainsi, à la couche structurelle, nous associons les réseaux de Petri Temporels; à la couche fonctionnelle les réseaux de Petri stochastiques et à la couche logique les réseaux de Petri Prédicats Transitions / The railway systems are being more and more forced by decision authorities. As they are placed at a high level of abstraction, it becomes problematic to impose another criterion or scale. In fact, since we come down lower, we are confronted with specificities of the national systems which make lose the majority of the work of the European decision-makers. The issue is that, at every level of abstraction, risk assessment methods exist, but without being compatible. Besides, the combination of layers and the functional vision of the railway system do not take into account the impact of some functions on the others, nor the link between the global level of risk and the components to assign the safety.Thus, we propose a harmonized approach for risk assessment. This approach allows us to distribute the constraints defined at the abstract functional level on the entities which implement both the systems and their specificities.Our contribution is methodological. It leaves a functional model of the layered railway system. The purpose is to represent this system without any dependencies between the functions. For instance, it was necessary to translate them independently by creating entrances/exits as places/transitions of a Petri net. A Petri net class corresponds to each layer. To the structural layer, we associate the time Petri net; to the functional layer, the stochastic Petri nets and to the logical layer, the predicate transitions nets

Des résultats récents ont montré les premières preuves d’un effet multivalent puissant des iminosucres sur l’inhibition des glycosidases, avec des gains d’affinité allant jusqu’à 10000. Afin de comprendre les différentes caractéristiques de cet « effet de cluster » et d’en poursuivre l’optimisation, de nouvelles charpentes doivent être conçues. Le premier axe de recherche a donc consisté en la mise au point d’un ensemble de techniques d’ingénierie « click » pour la synthèse de systèmes multivalents, avec le développement d’une stratégie Sweet LEGO®. Cette approche permettrait un accès simple à une grande variété de néocyclodextrines préfonctionnalisées. Le second axe a consisté en une étude de relation structure-activité autour de charpentes moléculaires polyalcynes utilisées pour préparer de nouveaux clusters par chimie « click ». Une partie des clusters a été préparée en utilisant de nouvelles charpentes cyclopeptoïdes. Ils ont permis de poursuivre l’optimisation de l’effet multivalent des iminosucres sur l’inhibition de glycosidases. En particulier, un composé portant 30 ligands a montré le meilleur effet multivalent connu sur une enzyme modèle. / Recent reports have demonstrated the first pieces of evidence of a strong multivalent effect in glycosidase inhibition by iminosugars, with affinity enhancements close to 10000. In order to understand the different parameters of this “cluster effect” and to continue its optimization, new scaffolds must be designed. The first research topic was thus to develop a set of « Click » Chemistry engineering techniques for the synthesis of multivalent systems, with the development of a Sweet LEGO® strategy. In the end, it would allow an easy access to a broad range of prefunctionalized neocyclodextrins. The second research topic consisted in a structure-activity relationship study by varying the molecular polyalkyne scaffold used for the preparation of new clusters by way of « Click » Chemistry. They allowed to investigate the specific features of the iminosugar cluster effect in the inhibition of glycosidases. In particular, a compound of unprecedented valency bearing 30 iminosugar units demonstrated an unprecedented dramatic affinity enhancement for the inhibition of a model enzyme (Jack bean alpha-mannosidase).