<p>This thesis concerns the study of reaction mechanisms by means of kinetic isotope effects (KIEs). Studies of the nucleophilic bimolecular substitution (S_N2) reaction had the dual purpose of improving our fundamental understanding of molecular reactivity and assessing the ability of kinetic isotope effects to serve as mechanistic tools. The transition state of the S_N2 reaction between a cyanide ion and ethyl chloride in tetrahydrofuran was found to be reactant like and only slightly tighter than has been found previously for the same reaction in dimethyl sulphoxide. One conclusion was that the transition-state structure in this reaction was predicted fairly well by the theoretical calculations, even without solvent modelling. The S_N2 reactions between cyanide ions and <i>para</i>-substituted benzyl chlorides were found to have reactant-like transition states, of which the C_α-Cl bond was most influenced by the <i>para</i>-substitution. Theoretical calculations indicated that the chlorine KIEs could be used as probes of the substituent effect on the C_α-Cl bond if bond fission was not too advanced in the transition state. Furthermore, the nucleophile carbon ¹¹C/¹⁴C KIEs were determined for the reactions between cyanide ions and various ethyl substrates in dimethyl sulphoxide.</p><p>Precision conductometry was employed to estimate the aggregation status of tetrabutylammonium cyanide in tetrahydrofuran and in dimethyl sulphoxide, which is of interest as tetrabutylammonium cyanide is frequently used as the nucleophilic reagent in mechanistic investigations and synthetic reactions. The tendency for ion-pair formation was found to be very slight, significant, and very strong in dimethyl sulphoxide, water, and tetrahydrofuran, respectively. </p><p>The nitrogen kinetic isotope effect on monoamine oxidase B catalysed deamination of benzylamine was determined in an attempt to obtain conclusive evidence regarding the mechanism of the oxidation. Monoamine oxidase is an important drug target in connection with the treatment of, for example, depression and Parkinson’s disease, and knowledge on how the enzyme effects catalysis would facilitate the design of highly selective and efficient inhibitors.</p>

This thesis concerns the study of reaction mechanisms by means of kinetic isotope effects (KIEs). Studies of the nucleophilic bimolecular substitution (SN2) reaction had the dual purpose of improving our fundamental understanding of molecular reactivity and assessing the ability of kinetic isotope effects to serve as mechanistic tools. The transition state of the SN2 reaction between a cyanide ion and ethyl chloride in tetrahydrofuran was found to be reactant like and only slightly tighter than has been found previously for the same reaction in dimethyl sulphoxide. One conclusion was that the transition-state structure in this reaction was predicted fairly well by the theoretical calculations, even without solvent modelling. The SN2 reactions between cyanide ions and para-substituted benzyl chlorides were found to have reactant-like transition states, of which the Cα-Cl bond was most influenced by the para-substitution. Theoretical calculations indicated that the chlorine KIEs could be used as probes of the substituent effect on the Cα-Cl bond if bond fission was not too advanced in the transition state. Furthermore, the nucleophile carbon 11C/14C KIEs were determined for the reactions between cyanide ions and various ethyl substrates in dimethyl sulphoxide. Precision conductometry was employed to estimate the aggregation status of tetrabutylammonium cyanide in tetrahydrofuran and in dimethyl sulphoxide, which is of interest as tetrabutylammonium cyanide is frequently used as the nucleophilic reagent in mechanistic investigations and synthetic reactions. The tendency for ion-pair formation was found to be very slight, significant, and very strong in dimethyl sulphoxide, water, and tetrahydrofuran, respectively. The nitrogen kinetic isotope effect on monoamine oxidase B catalysed deamination of benzylamine was determined in an attempt to obtain conclusive evidence regarding the mechanism of the oxidation. Monoamine oxidase is an important drug target in connection with the treatment of, for example, depression and Parkinson’s disease, and knowledge on how the enzyme effects catalysis would facilitate the design of highly selective and efficient inhibitors.

Meiosis is a specialized type of cell division essential for the production of four normal haploid gametes. In early prophase I of meiosis, the intimate synapsis between homologous chromosomes, and the formation of chiasmata, is facilitated by a proteinaceous structure known as the synaptonemal complex (SC). Ultrastructural analysis of germ cells of a number of organisms has disclosed that SC is a specialized tripartite structure composed of two lateral elements, one on each homolog, and a central element, which, in turn, are linked by transverse elements. Genetic studies have revealed that defects in meiotic chromosome alignment and/or segregation result in aneuploidy, which is the leading cause of spontaneous miscarriages in humans, hereditary birth defects such as Down syndrome, and are also, associated with the development and progression of certain forms of cancer. The mechanism(s) underlying the alignment/pairing of chromosomes at meiosis I differ among organisms. These can be divided into at least two broad pathways: one is independent of DNA double-strand breaks (DSB) and other is mediated by DSBs. In the DSB-dependent pathway, SC plays crucial roles in promoting homolog pairing and disjunction. On the other hand, the DSB-independent pathway involves the participation of telomeres, centromeres and non-coding RNAs in the pre-synaptic alignment, pre-meiotic pairing as well as pairing of homologous chromosomes. Although a large body of literature highlights the central role of SC in meiotic recombination, the possible role of SC components in homolog recognition and alignment is poorly understood. Genetic screens for Saccharomyces cerevisiae mutants defective in meiosis and sporulation lead to the isolation of genes required for interhomolog recombination, including those that encode SC components. In S. cerevisiae, ten meiosis-specific proteins viz., Hop1, Red1, Mek1, Hop2, Pch2, Zip1, Zip2, Zip3, Zip4 and Rec8 have been recognized as bona fide constituents of SC or associated with SC function. Mutations in any of these genes result in defective SC formation, thus leading to reduction in the rate of recombination. HOP1 (Homolog Pairing) encodes a ̴ 70 kDa structural protein, which localizes to the lateral elements of SC. It was found to be essential for the progression of meiotic recombination. In hop1Δ mutants, meiosis specific DSBs are reduced to 10% of that of wild type level and it fails to produce viable spores. It also displays relatively high frequency of inter-sister recombination over inter-homolog recombination. Bioinformatics analysis suggests that Hop1 comprises of an N-terminal HORMA domain (Hop1, Rev7 and Mad2), which is conserved among Hop1 homologs from diverse organisms. This domain is also known to be present in proteins involved in processes like chromosome synapsis, repair and sex chromosome inactivation. Additionally, Hop1 harbors a 36-amino acid long zinc finger 348374 motif (CX2CX19CX2C) which is critical for DNA binding and meiotic progression, and a putative nuclear localization signal corresponding to amino acid residues from 588-594. Previous studies suggested that purified Hop1 protein exists in multiple oligomeric states in solution and displays structure specific DNA binding activity. Importantly, Hop1 exhibited higher binding affinity for the Holliday junction (HJ), over other early recombination intermediates. Binding of Hop1 to the HJ at the core resulted in branch migration of the junction, albeit weakly. Intriguingly, Hop1 showed a high binding affinity for G4 DNA, a non-B DNA structure, implicated in homolog synapsis and promotes robust synapsis between double-stranded DNA molecules. Hop1 protein used in the foregoing biochemical studies was purified from mitotically dividing S. cerevisiae cells containing the recombinant plasmid over-expressing the protein where the yields were often found to be in the low-microgram quantities. Therefore, one of the major limitations to the application of high resolution biophysical techniques, such as X-crystallography and spectroscopic analyses for structure-function studies of S. cerevisiae Hop1 has been the non-availability of sufficient quantities of functionally active pure protein. In this study, we have performed expression screening in Escherichia coli host strains, capable of high level expression of soluble S. cerevisiae Hop1 protein. A new protocol has been developed +2 for expression and purification of S. cerevisiae Hop1 protein, using Ni-NTA and double-stranded DNA-cellulose chromatography. Recombinant S. cerevisiae Hop1 protein thus obtained was >98% pure and exhibited DNA binding activity with high-affinity for Holliday junction. The availability of the bacterial HOP1 expression vector and functionally active Hop1 protein has enabled us to glean and understand several vital biological insights into the structure-function relationships of Hop1 as well as the generation of appropriate truncated mutant proteins. Mutational analyses in S. cerevisiae has shown that sister chromatid cohesion is required for proper chromosome condensation, including the formation of axial elements, SC assembly and recombination. Consistent with these findings, homolog alignment is impaired in red1hop1 strains and associations between homologs are less stable. red1 mutants fail to make any discernible axial elements or SC structures but exhibit normal chromosome condensation, while hop1 mutants form long fragments of axial elements but without any SCs, are defective in chromosome condensation, and produce in-viable spores. Using single molecule and ensemble assays, we found that S. cerevisiae Hop1 organizes DNA into at least four major distinct DNA conformations: (i) a rigid protein filament along DNA that blocks access to nucleases; (ii) bridging of non-contiguous segments of DNA to form stem-loop structures; (iii) intra-and intermolecular long range synapsis between double-stranded DNA molecules; and (iv) folding of DNA into higher order nucleoprotein structures. Consistent with B. McClintock’s proposal that “there is a tendency for chromosomes to associate 2-by-2 in the prophase of meiosis involving long distance recognition of homologs”, these results to our knowledge provide the first evidence that Hop1 mediates the formation of tight DNA-protein-DNA nucleofilaments independent of homology which might help in the synapsis of homologous chromosomes during meiosis. Although the DNA binding properties of Hop1 are relatively well established, comparable knowledge about the protein is lacking. The purification of Hop1 from E. coli, which was functionally indistinguishable from the protein obtained from mitotically dividing S. cerevisiae cells has enabled us to investigate the structure-function relationships of Hop1, which has provided important insights into its role in meiotic recombination. We present several lines of evidence suggesting that Hop1 is a modular protein, consisting of an intrinsically unstructured N-terminal domain and a core C-terminal domain (Hop1CTD), the latter being functionally equivalent to the full-length Hop1 in terms of its in vitro activities. Importantly, however, Hop1CTD was unable to rescue the meiotic recombination defects of hop1null strain, indicating that synergy between the N-terminal and C-terminal domains of Hop1 protein is essential for meiosis and spore formation. Taken together, our findings provide novel insights into the molecular functions of Hop1, which has profound implications for the assembly of mature SC, homolog synapsis and recombination. Several lines of investigations suggest that HORMA domain containing proteins are involved in chromatin binding and, consequently, have been shown to play key roles in processes such as meiotic cell cycle checkpoint, DNA replication, double-strand break repair and chromosome synapsis. S. cerevisiae encodes three HORMA domain containing proteins: Hop1, Rev7 and Mad2 (HORMA) which interact with chromatin during diverse chromosomal processes. The data presented above suggest that Hop1 is a modular protein containing a distinct N-terminal and C-terminal (Hop1CTD) domains. The N-terminal domain of Hop1, which corresponds to the evolutionarily conserved HORMA domain, although, discovered first in Hop1, its precise biochemical functions remain unknown. In this section, we show that Hop1-HORMA domain expressed in and purified from E. coli exhibits preferential binding to the HJ and G4 DNA, over other early recombination intermediates. Detailed functional analyses of Hop1-HORMA domain, using mobility shift assays, DNase I footprinting and FRET, have revealed that HORMA binds at the core of Holliday junction and induces marked changes in its global conformation. Further experimental evidence also suggested that it causes DNA stiffening and condensation. However, like Hop1CTD, HORMA domain alone failed to rescue the meiotic recombination defects of hop1 null strain, indicating that synergy between the N-and C-terminal domains of Hop1 is essential for meiosis as well as for the formation of haploid gametes. Moreover, these results strongly implicate that Hop1 protein harbours a second DNA binding motif, which resides in the HORMA domain at its N-terminal region. To our knowledge, these findings also provide the first insights into the biochemical mechanism underlying HORMA domain activity. In summary, it appears that the C-terminal (CTD) and N-terminal (HORMA) domains of Hop1 may perform biochemical functions similar (albeit less efficiently) to that of the full-length Hop1. However, further research is required to uncover the functional differences between these domains, their respective interacting partners and modulation of the activity of these domains.

Soit R un anneau de valuation discrète de corps de fractions K. Soit X_K un K- schéma propre géométriquement normal. On montre que X_K possède des modèles X sur R, propres, plats, normaux et tels que tout faisceau inversible sur X_K se prolonge en un faisceau inversible sur X. On peut alors reconstruire le modèle de Néron de la variété de Picard de X_K, à partir du foncteur de Picard de X/R.Lorsque R est hensélien à corps résiduel algébriquement clos, on en tire des informations sur le prolongement de l’équivalence algébrique de X_K à X. En particulier, on peut décrire le symbole de Néron entre 0-cycles de degré zéro et diviseurs algébriquement équivalents à zéro sur X_K, en termes de multiplicités d’intersection sur le modèle X. Ceci nous permet de reformuler la conjecture de dualité de Grothendieck pour les modèles de Néron des variétés abéliennes, en termes d’équivalence algébrique relative. / Let R be a discrete valuation ring with fraction field K. Let X_K be proper geometrically normal scheme over K. One shows that X_K admits models X over R which are proper, flat, normal an such that any invertible sheaf on X_K can be extended to an invertible sheaf on X. Then, one can recover the Néron model of the Picard variety of X_K from the Picard functor of X/R.When R is henselian with algebraically closed residue field, one obtains some consequences about the extension of algebraic equivalence from X_K to X. In particular, one can describe the Néron symbol between 0-cycles of degree zero and divisors which are algebraically equivalent to zero on X_K, in terms of intersection multiplicities on the model X. This allows us to reformulate Grothendieck’s duality conjecture for Néron models of abelian varieties, in terms of relative algebraic equivalence.

The presented thesis investigates the transfer of drug molecules across interfaces that mimic biological membrane barriers. The permeability of drug molecules across biological membrane mimics has been investigated in a novel artificial membrane permeation assay configuration using an in situ time-dependent approach and reproducible rotation of the membrane. A method to determine the membrane permeability from the knowledge of measured permeability and the applied stirring rate is presented. The initial transient of the permeation response, previously not observed in situ, is investigated and its importance in data evaluation is discussed. The permeability coefficients of 31 drugs are optimised for the conditions found in vivo and a correlation with the fraction absorbed in humans is presented. The evidence for ionic and/or ion-pair flux across the artificial membrane obtained from measurement of permeability at different pH is supported by the investigation of the permeation assay with external membrane polarisation. The permeability coefficient of the solute's anionic form is determined. Liquid/liquid electrochemistry has been used to study the transfer of ionized species across the interface between water and 1,2-dichloroethane. An alternative method to study the transfer of partially ionised drug molecules employing a rotating liquid/liquid interface is presented. In addition, a bipolar electrochemical cell with a rotating-disc electrode is developed and its properties investigated in order to verify the hydrodynamics of the rotating artificial membrane configuration. Finally, in support of the electrochemical techniques used is this thesis, a detailed preparation and evaluation of the silver/silver sulphate reference electrode is presented.

The phenomenon of pairing in atomic and nuclear many-body systems gives rise to a great number of different physical properties of matter, from areas as seemingly diverse as the shape of stable nuclei to superconductivity in metals and superfluidity in neutron stars. With the experimental realisation of the long sought BCS-BEC crossover observed in trapped atomic gases - where it is possible to fine tune the s-wave scattering length a of a many-fermion system between a dilute, correlated BCS-like superfluid of Cooper pairs and a densely packed BEC of composite bosons - pairing problems in atomic physics have found renewed interest in recent years. Given the high precision techniques involved in producing these trapped gas condensates, we would like to employ a suitably accurate many-body method to study such systems, preferably one which goes beyond the simple mean-field picture.The Coupled Cluster Method (CCM) is a widely applied and highly successful ab initio method in the realm of quantum many-body physics and quantum chemistry, known to be capable of producing extremely accurate results for a wide variety of different many-body systems. It has not found many applications in pairing problems however, at least not in a general sense. Our aim, therefore, is to study various models of pairing using a variety of CCM techniques - we are interested in studying the generic features of pairing problems and in particular, we are especially interested in probing the collective modes of a system which exhibits the BCS-BEC crossover, in either the BCS or BEC limit. The CCM seems a rather good candidate for the job, given the high precision results it can produce.

Protocolos de autenticação e de estabelecimento de chaves são peças fundamentais em implementações de segurança para comunicação de dispositivos eletrônicos. Em aplicações que envolvam dispositivos com poder computacional restrito (tais como smartphones ou tablets) comunicando-se com um servidor, é primordial a escolha de protocolos eficientes e que necessitem de uma infraestrutura mais simples. Neste trabalho selecionamos e implementamos protocolos de acordo de chave seguros nos modelos de criptografia de chave pública baseado em identidade (ID-based) e sem certificado (Certificateless) em plataformas com processadores ARM. Comparamos tempos de execução, utilização de memória e uso do canal de comunicação. / Protocols for authentication and key establishment are fundamental parts in security implementations for electronic devices communication. In applications involving devices with limited computational power (such as smartphones and tablets) communicating with a server, the choice of efficient protocols that require a simpler infrastructure is essential. In this work we select and implement secure key agreement protocols in ID-based and Certificateless public key cryptography models on ARM processor platforms. We also compare running times, memory and network usage.

L’aléatoire est un ingrédient clé en cryptographie. Par exemple, les nombres aléatoires sont utilisés pour générer des clés, pour le chiffrement et pour produire des nonces. Ces nombres sont générés par des générateurs pseudo-aléatoires et des fonctions pseudo-aléatoires dont les constructions sont basées sur des problèmes qui sont supposés difficiles. Dans cette thèse, nous étudions certaines mesures de complexité des fonctions pseudo-aléatoires de Naor-Reingold et Dodis-Yampolskiy et étudions la sécurité de certains générateurs pseudo-aléatoires (le générateur linéaire congruentiel et le générateur puissance basés sur les courbes elliptiques) et de certaines signatures à base de couplage basées sur le paradigme d’inversion. Nous montrons que la fonction pseudo-aléatoire de Dodis-Yampolskiy est uniformément distribué et qu’un polynôme multivarié de petit dégré ou de petit poids ne peut pas interpoler les fonctions pseudo-aléatoires de Naor-Reingold et de Dodis-Yampolskiy définies sur un corps fini ou une courbe elliptique. Le contraire serait désastreux car un tel polynôme casserait la sécurité de ces fonctions et des problèmes sur lesquels elles sont basées. Nous montrons aussi que le générateur linéaire congruentiel et le générateur puissance basés sur les courbes elliptiques sont prédictibles si trop de bits sont sortis à chaque itération. Les implémentations pratiques de cryptosystèmes souffrent souvent de fuites critiques d’informations à travers des attaques par canaux cachés. Ceci peut être le cas lors du calcul de l’exponentiation afin de calculer la sortie de la fonction pseudo-aléatoire de Dodis-Yampolskiy et plus généralement le calcul des signatures dans certains schémas de signatures bien connus à base de couplage (signatures de Sakai-Kasahara, Boneh-Boyen et Gentry) basées sur le paradigme d’inversion. Nous présentons des algorithmes (heuristiques) en temps polynomial à base des réseaux qui retrouvent le secret de celui qui signe le message dans ces trois schémas de signatures lorsque plusieurs messages sont signés sous l’hypothèse que des blocs consécutifs de bits des exposants sont connus de l’adversaire. / Randomness is a key ingredient in cryptography. For instance, random numbers are used to generate keys, for encryption and to produce nonces. They are generated by pseudo-random generators and pseudorandom functions whose constructions are based on problems which are assumed to be difficult. In this thesis, we study some complexity measures of the Naor-Reingold and Dodis-Yampolskiy pseudorandom functions and study the security of some pseudo-random generators (the linear congruential generator and the power generator on elliptic curves) and some pairing-based signatures based on exponentinversion framework. We show that the Dodis-Yampolskiy pseudo-random functions is uniformly distributed and that a lowdegree or low-weight multivariate polynomial cannot interpolate the Naor-Reingold and Dodis-Yampolskiy pseudo-random functions over finite fields and over elliptic curves. The contrary would be disastrous since it would break the security of these functions and of problems on which they are based. We also show that the linear congruential generator and the power generator on elliptic curves are insecure if too many bits are output at each iteration. Practical implementations of cryptosystems often suffer from critical information leakage through sidechannels. This can be the case when computing the exponentiation in order to compute the output of the Dodis-Yampolskiy pseudo-random function and more generally in well-known pairing-based signatures (Sakai-Kasahara signatures, Boneh-Boyen signatures and Gentry signatures) based on the exponent-inversion framework. We present lattice based polynomial-time (heuristic) algorithms that recover the signer’s secret in the pairing-based signatures when used to sign several messages under the assumption that blocks of consecutive bits of the exponents are known by the attacker.

La théorie covariance de la fonctionnelle de la densité (CDF), basée sur un petit nombre de paramètres ajustables, a été utilisée avec succès pour décrire l’état fondamental et les états excités des noyaux de la carte nucléaire, pour A>12. Cette approche permet de décrire les systèmes nucléaires finis avec un Lagrangien hadronique universel résolu dans le cadre de l'approche Relativiste-Hartree-Fock-Bologuibov (RHFB). Ce modèle est également utilisé pour l'étude des étoiles compactes, car il peut être étendu à des densités élevées où la relativité restreinte ne peut pas être ignoré. Ce modèle peut également être étendu pour inclure la contribution des hypérons et ainsi que d'autres particules exotiques. Dans ce travail, la description et des prédictions basées sur l'approche RHFB pour les noyaux dans des conditions extrêmes de la masse, d'isospin et de température sont présentés.Dans la première partie de cette thèse, nous explorons l'apparition de nouvelles fermetures de couches sphériques pour des noyaux super-lourds, où les fermetures de couches sont caractérisées en termes de gap à deux nucléons. Les résultats dépendent légèrement des Lagrangians effectifs utilisés, mais les nombres magiques au-delà de ^{208} Pb sont prédit pour un nombre de protons Z=120 et 138, et pour un nombre de neutrons N=172, 184, 228, et 258. Les effets de couche sont sensibles à différents termes de champ de moyen, tels que le couplage spin-orbite, la masse scalaire et la masses effective, ainsi que l'interaction de tensorielle de Lorentz. Ces termes ont des poids différents dans les Lagrangians effectifs employées, expliquant les variations, somme toute petites, dans leurs prédictions. Employant le modèle RHFB le plus avancé, nous avons trouvé que le nucléide ^{304} 120 est favorisée comme étant le prochain noyau sphérique doublement magique au-delà de ^{208} Pb.Dans la deuxième partie de cette thèse, nous étudions l'apparition de nouveaux nombres magiques pour les noyaux de masse intermédiaire riches en neutrons, et nous analysons le rôle des interactions pseudo-vecteur et de tensorielle de Lorentz. Basé sur la transformation de Foldy-Wouthuysen, nous discutons en détail le rôle joué par les différents termes des interactions pseudo-vecteur et de tensorielle de Lorentz. Dans l'apparition des nouveaux nombres magiques N=16 , 32 et 34. Les noyaux ^{24} O ^{48} Si et ^{52,54} Ca sont prédits avec un grand gap au niveau de Fermi et un gap d'appariement zéro (^{24} O,^{54}Ca ) ou quasi-nul (^{48} Si,^{54} Ca), les rendant candidats pour de nouveaux nombres magiques des noyaux riches en neutrons. Nous constatons que les interactions de Lorentz pseudo-vecteur et tensorielle induisent des évolutions très spécifiques des énergies à une particule, ce qui pourrait signer la présence et la nécessité d'approches relativistes avec des interactions d'échanges de mésons.Dans la dernière partie de cette thèse, nous étudions les transitions de phase et excitations thermiques des deux noyaux stables et faiblement liés. Les prédictions de divers Lagrangiens relativistes et des différentes interactions d'appariement sont discutées. La température critique de la transition d'appariement dépend linéairement du gap d'appariement à température nulle, et cette dépendance est similaire pour une interaction de portée nulle ou bien finie. Les calculs présentés montrent des caractéristiques intéressantes des corrélations d'appariement à température finie, comme la persistance d'appariement et les phénomènes de re-entrance superfluide. En outre, nous analysons la réponse thermique de certains noyaux.En conclusion, le travail présenté dans cette thèse montre des résultats très intéressants et nouveaux pour trois des questions les plus importantes en physique nucléaire: la quête d'un nouvel îlot de stabilité dans la région des super-lourds, l'apparition de nouveaux nombres magiques dans les noyaux exotiques, et la réponse d'un système finis aux excitations thermiques. / The covariant density functional (CDF) theory with a few number of parameters has been successfully employed to describe ground-state and excited-states of nuclei over the entire nuclear landscape for A > 12. It describes finite nuclear systems with a universal hadronic Lagrangian, which is solved considering the relativistic-Hartree-Fock-Bologuibov approach (RHFB). This model is also employed for the study of compact stars, since it can be extended to high densities where special relativity cannot be ignore. This model can also be extended to include the contribution of hyperons and as well as other exotic particles. In this work, the description and some predictions based on RHFB approach for nuclei under extreme conditions of mass, isospin and temperature are presented.In the first part, we explore the occurrence of spherical shell closures for superheavy nuclei, where shell closures are characterized in terms of two-nucleon gaps. The results depend slightly on the effective Lagrangians used, but the magic numbers beyond ^{208}Pb are generally predicted to be Z = 120 and 138 for protons, and N = 172, 184, 228, and 258 for neutrons. Shell effects are sensitive to various terms of the mean-field, such as the spin-orbit coupling, the scalar and the effective masses, as well as the Lorentz-tensor interaction. These terms have different weights in the effective Lagrangians employed, explaining the (relatively small) variations in the predictions. Employing the most advanced RHFB model, we founded that the nuclide ^{304}120 is favored as being the next spherical doubly-magic nucleus beyond ^{208}Pb.In the second part, we investigate the formation of new shell gaps in intermediate mass neutron-rich nuclei, and analyze the role of the Lorentz pseudo-vector and tensor interactions. Based on the Foldy-Wouthuysen transformation, we discuss in detail the role played by the different terms of the Lorentz pseudo-vector and tensor interactions in the appearance of the N=16, 32 and 34 shell gaps. The nuclei ^{24}O, ^{48}Si and ^{52,54}Ca are predicted with a large shell gap and zero (^{24}O, ^{52}Ca) or almost zero (^{48}Si, ^{54}Ca) pairing gap, making them candidates for new magic numbers in neutron rich nuclei. We find that the Lorentz pseudo-vector and tensor interactions induce very specific evolutions of single-particle energies, which could clearly sign their presence and reveal the need for relativistic approaches with exchange interactions.In the last part, we study the phase transitions and thermal excitations of both stable and weakly-bound nuclei. The predictions of various relativistic Lagrangians and different pairing interactions are discussed. The critical temperature of the pairing transition is found to depend linearly on the zero-temperature pairing gap, and this dependence is similar for a zero-range or a finite-range pairing interaction. The present calculations show interesting features of the pairing correlations at finite temperature, such as the pairing persistence and pairing re-entrance phenomena. Also, we analyze the thermal response of some nuclei.In conclusion, the work presented in this thesis shown interesting and new results for three of the most important questions in nuclear physics: the quest for a new island of stability in the superheavy region, the appearance of new magic numbers in exotic nuclei, and the response of finite-systems to thermal excitations.

Dizertační práce se zabývá kryptografickými schématy zvyšující ochranu soukromí uživatelů v systémech řízení přístupu a sběru dat. V současnosti jsou systémy fyzického řízení přístupu na bázi čipových karet využívány téměř dennodenně většinou z nás, například v zaměstnání, ve veřejné dopravě a v hotelech. Tyto systémy však stále neposkytují dostatečnou kryptografickou ochranu a tedy bezpečnost. Uživatelské identifikátory a klíče lze snadno odposlechnout a padělat. Funkce, které by zajišťovaly ochranu soukromí uživatele, téměř vždy chybí. Proto je zde reálné riziko možného sledovaní lidí, jejich pohybu a chovaní. Poskytovatelé služeb nebo případní útočníci, kteří odposlouchávají komunikaci, mohou vytvářet profily uživatelů, ví, co dělají, kde se pohybují a o co se zajímají. Za účelem zlepšení tohoto stavu jsme navrhli čtyři nová kryptografická schémata založená na efektivních důkazech s nulovou znalostí a kryptografii eliptických křivek. Konkrétně dizertační práce prezentuje tři nová autentizační schémata pro využití v systémech řízení přístupu a jedno nové schéma pro využití v systémech sběru dat. První schéma využívá distribuovaný autentizační přístup vyžadující spolupráci více RFID prvků v autentizačním procesu. Tato vlastnost je výhodná zvláště v případech řízení přístupu do nebezpečných prostor, kdy pro povolení přístupu uživatele je nezbytné, aby byl uživatel vybaven ochrannými pomůckami (se zabudovanými RFID prvky). Další dvě schémata jsou založena na atributovém způsobu ověření, tj. schémata umožňují anonymně prokázat vlastnictví atributů uživatele, jako je věk, občanství a pohlaví. Zatím co jedno schéma implementuje efektivní revokační a identifikační mechanismy, druhé schéma poskytuje nejrychlejší verifikaci držení uživatelských atributů ze všech současných řešení. Poslední, čtvrté schéma reprezentuje schéma krátkého skupinového podpisu pro scénář sběru dat. Schémata sběru dat se používají pro bezpečný a spolehlivý přenos dat ze vzdálených uzlů do řídící jednotky. S rostoucím významem chytrých měřičů v energetice, inteligentních zařízení v domácnostech a rozličných senzorových sítí, se potřeba bezpečných systémů sběru dat stává velmi naléhavou. Tato schémata musí podporovat nejen standardní bezpečnostní funkce, jako je důvěrnost a autentičnost přenášených dat, ale také funkce nové, jako je silná ochrana soukromí a identity uživatele či identifikace škodlivých uživatelů. Navržená schémata jsou prokazatelně bezpečná a nabízí celou řadu funkcí rozšiřující ochranu soukromí a identity uživatele, jmenovitě se pak jedná o zajištění anonymity, nesledovatelnosti a nespojitelnosti jednotlivých relací uživatele. Kromě úplné kryptografické specifikace a bezpečnostní analýzy navržených schémat, obsahuje tato práce také výsledky měření implementací jednotlivých schémat na v současnosti nejpoužívanějších zařízeních v oblasti řízení přístupu a sběru dat.