The ultimate goal in the rapidly burgeoning field of spintronics is to realize semiconductor-based devices that utilize the spin degree of freedom of a single charge carrier (electron or hole) or an ensemble of such carriers to achieve novel and/or enhanced device functionalities such as spin based light emitting devices, spin transistors and femto-Tesla magnetic field sensors. These devices share a common feature: they all rely on controlled transport of spins in semiconductors. A prototypical spintronic device has a transistor-like configuration in which a semiconducting channel is sandwiched between two contacts (source and drain) with a gate electrode sitting on top of the channel. Unlike conventional charge-based transistors, the source electrode of a spin transistor is a ferromagnetic (or half-metallic) material which injects spin polarized electrons in the channel. During transit, the spin polarizations of the electrons are controllably rotated by a gate electric field mediated spin-orbit coupling effect. The drain contact is ferromagnetic (or half-metallic) as well and the transmission probability of an electron through this drain electrode depends on the relative orientation of electron spin polarization and the (fixed) magnetization of the drain. When the spins of the electrons are parallel to the drain magnetization, they are transmitted by the drain resulting in a large device current (ON state of spin FET). However, these electrons will be completely blocked if their spins are antiparallel to the drain magnetization, and ideally, in this situation device current will be zero (OFF state of spinFET). Thus, if we vary the gate voltage, we can modulate the channel current by controlling the spin orientations of the electrons with respect to the drain magnetization. This is how transistor action is realized (Datta-Das model). However, during transport, electrons' velocities change randomly with time due to scattering and hence different electrons experience different spin-orbit magnetic fields. As a result, even though all electrons start their journey with identical spin orientations, soon after injection spins of different electrons point along different directions in space. This randomization of initial spin polarization is referred to as spin relaxation and this is detrimental to the spintronic devices. In particular, for Datta-Das transistor, this will lead to inefficient gate control and large leakage current in the OFF state of the spinFET. The aim of this work is to understand various spin relaxation processes that are operative in semiconductor nanostructures and to indicate possible ways of minimizing them. The theoretical aspect of this work (Chapters 2-5) focuses on the D'yakonov-Perel' process of spin relaxation in a semiconductor quantum wire. This process of spin relaxation occurs because during transport electron spin precesses like a spinning top about the spin-orbit magnetic field. We show that the conventional drift-diffusion model of spin transport, which has been used extensively in literature, completely breaks down in case of a quantum confined system (e.g. a quantum wire). Our approach employs a semi-classical model which couples the spin density matrix evolution with the Boltzmann transport equation. Using this model we have thoroughly studied spin relaxation in a semiconductor quantum wire and identified several inconsistencies of the drift-diffusion formalism.The experimental side of this work (Chapters 6-8) deals with two different issues: (a) performing spin transport experiments in order to extract spin relaxation length and time in various materials (e.g. Cu, Alq3) under one-dimensional confinement, and (b) measurement of the ensemble spin dephasing time in self-assembled cadmium sulfide quantum dots using electron spin resonance technique. The spin transport experiment, as described in Chapter 7 of this dissertation, shows that the spin relaxation time in organic semiconductor (Alq3) is extremely long, approaching a few seconds at low temperatures. Alq3 is the chemical formula of tris- 8 hydroxy-quinoline aluminum, which is a small molecular weight organic semiconductor. This material is extensively used in organic display industry as the electron transport and emission layer in green organic light emitting diodes. The long spin relaxation time in Alq3 makes it an ideal platform for spintronics. This also indicates that it may be possible to realize spin based organic light emitting diodes which will have much higher internal quantum efficiency than their conventional non-spin counterparts. From spin transport experiments mentioned above we have also identified Elliott-Yafet mode as the dominant spin relaxation mechanism operative in organic semiconductors. Electron spin resonance experiment performed on self-assembled quantum dots (Chapter 8) allows us to determine the ensemble spin dephasing time (or transverse spin relaxation time) of electrons confined in these systems. In quantum dots electrons are strongly localized in space. Surprisingly, the ensemble spin dephasing time shows an increasing trend as we increase temperature. The most likely explanation for this phenomenon is that spin dephasing in quantum dots (unlike quantum wells and wires) is dominated by nuclear hyperfine interaction, which weakens progressively with temperature. We hope that our work, which elaborates on all of the above mentioned topics in great detail, will be a significant contribution towards the current state of knowledge of subtle spin-based issues operative in nanoscale device structures, and will ultimately lead to realization of novel nano-spintronic devices.

O câncer de próstata é um problema de saúde pública no Brasil, sendo a segunda causa de óbitos por câncer em homens, superado apenas pelo câncer de pulmão. Entre os possíveis tratamentos disponíveis para o câncer de próstata encontra-se a braquiterapia, onde, pequenas sementes contendo o radioisótopo 125I são implantadas na próstata. A semente consiste de uma cápsula de titânio selada de 0,8 mm de diâmetro externo e 4,5 mm de comprimento, contendo um fio de prata com 125I adsorvido. A soldagem por arco plasma é uma das técnicas viáveis para selagem, o equipamento tem um custo menor que o de outros processos. Constituem os objetivos deste trabalho o desenvolvimento e a validação do procedimento de selagem utilizando processo de soldagem plasma e a elaboração de rotinas para selagem segundo as Boas Práticas de Fabricação. O desenvolvimento do trabalho apresentou as seguintes fases: corte e limpeza do material, determinação dos parâmetros de soldagem, desenvolvimento de dispositivos para fixação do tubo de titânio durante o processo de soldagem, ensaios de validação de fontes seladas conforme norma ISO 2919 Sealed Radioactive Sources General Requirements and Classification, ensaios de estanqueidade conforme norma ISO 9978 Sealed Radioactive Sources Leakage Test Methods e ensaio metalográfico. O procedimento desenvolvido para a selagem das sementes de 125I mostrou-se eficiente, atendendo a todos os requisitos estabelecidos na norma ISO 2919. Os resultados apresentados neste trabalho possibilitaram a elaboração de rotinas de fabricação segundo as orientações apresentadas na resolução RDC nº 59 Boas Práticas de Fabricação de Produtos Médicos da ANVISA - Agência Nacional de Vigilância Sanitária. / The prostate cancer, which is the second cause of death by cancer in men, overcome only by lung cancer, is a problem of public health in Brazil. Brachytherapy is among the possible available treatments for prostate cancer, in which small seeds containing 125I radioisotope are implanted in the prostate. The seed consists of a titanium sealed capsule with 0.8 mm external diameter and 4.5 mm length, containing a central silver wire with adsorbed 125I. The plasma arc welding is one of the viable techniques for the sealing process. The equipment used in this technique is less costly than in other processes. The main objective of this work was the development and the validation of the welding procedure using plasma welding process and the elaboration of a sealing routine according to Good Manufacturing Practices. The development of this work has presented the following phases: cut and cleaning of the titanium material, determination of the welding parameters, development of a device for holding the titanium tube during the welding process, validation of sealed sources according to ISO 2919 Sealed Radioactive Sources - General Requirements and Classification, leakage test according to ISO 9978 Sealed Radioactive Sources - Leakage Test Methods and metallographics assays. The developed procedure, to seal 125I seeds using plasma welding process, has shown to be efficient, satisfying all the established requirements of ISO 2919. The results obtained in this work have given the possibility to establish a routine production process according to the orientations presented in resolution RDC nº 59 - Good Manufacturing Practices to Medical Products of the ANVISA - National Agency of Sanitary Surveillance.

O objetivo deste trabalho foi estudar os efeitos dos lacebacks ativos e passivos na biomecânica da fase de nivelamento, utilizando-se a técnica MBT. A amostra foi constituída de 29 sujeitos de pesquisa (22 do gênero feminino e 7 do gênero masculino), brasileiros, leucodermas e pardos, portadores de má oclusão de Classe I e com idade média de 15 anos e 5 meses. O tratamento ortodôntico foi planejado com as extrações dos primeiros pré-molares e, durante a fase estudada, foram empregados apenas fios de aço inoxidável (0.014", 0.016", 0.018", 0.020" e 0.019" x 0.025"). Os recursos de ancoragem utilizados para os arcos dentários superior e inferior foram, respectivamente, o aparelho extrabucal tipo IHG e o arco lingual fixo. De acordo com a indicação dos lacebacks, a amostra foi dividida em quatro grupos: grupo I – 14 sujeitos que utilizaram lacebacks ativos no arco dentário superior; grupo II – 9 sujeitos que utilizaram lacebacks passivos no arco dentário superior; grupo III – 19 sujeitos que utilizaram lacebacks ativos no arco dentário inferior e grupo IV – 10 sujeitos que utilizaram lacebacks passivos no arco dentário inferior. Para cada indivíduo da amostra foram tomadas duas telerradiografias laterais, uma ao início e outra ao término da fase de nivelamento, com um intervalo médio de 21 meses. Os dados foram coletados utilizando-se o método cefalométrico computadorizado. Para a análise de erros, o método cefalométrico foi repetido em todos os sujeitos da amostra, pelo mesmo operador, com um intervalo mínimo de 15 dias entre as medidas. Os resultados indicaram que as variações observadas foram compatíveis com as estimativas de erros operacionais em estudos cefalométricos. Após a análise estatística e a interpretação dos resultados, verificou-se que, no grupo I, apenas a coroa do primeiro molar superior sofreu um movimento mesial e que tanto a coroa como a raiz do incisivo central superior apresentaram um movimento em direção lingual. No entanto, as inclinações destes dentes não foram alteradas. No grupo II, o primeiro molar superior se manteve estável e somente a coroa do incisivo central superior se movimentou em direção lingual, produzindo uma rotação horária deste dente. No grupo III, observou-se uma mesialização, tanto da coroa como da raiz, e extrusão do primeiro molar inferior, enquanto a posição do incisivo central inferior permaneceu inalterada. As inclinações destes dentes também não foram alteradas. No grupo IV, verificou-se que nem o primeiro molar inferior nem o incisivo central inferior apresentaram variações no sentido ântero-posterior. Verticalmente, houve extrusão apenas do primeiro molar inferior. / The purpose of this study was to evaluate the effects of active and passive lacebacks in the biomechanics of the leveling phase, using the MBT technique. The sample was composed of 29 Brazilian subjects (22 female and 7 male), Caucasian, with Class I malocclusion and mean age of 15 years and 5 months. The orthodontic treatment was planned with the extraction of the first premolars, and the leveling phase was performed with stainless steel wire only (0.014", 0.016", 0.018", 0.020" e 0.019" x 0.025"). The anchorage control devices used in the upper and lower arches were, respectively, the IHG extraoral appliance and the fixed lingual arch. According to the type of laceback prescription, the sample was divided into four groups: group I – 14 subjects in which active lacebacks were used in the upper arch; group II – 9 subjects in which passive lacebacks were used in the upper arch; group III – 19 subjects in which active lacebacks were used in the lower arch; group IV – 10 subjects in which passive lacebacks were used in the lower arch. For each subject of the sample two lateral cephalometric radiographs were taken: one at the beginning and another at the end of the leveling phase, with a mean interval of 21 months. The data were collected using the resources of computerized cephalometry. To perform the analysis of errors, the cephalometric method was repeated in all subjects of the sample, by the same operator, with a minimum interval of 15 days between the measurements. The results revealed that the observed variations were compatible with the estimates of operational errors in cephalometric studies. After statistical analysis and interpretation of the results, it was observed that in group I, only the crown of the upper first molar presented a mesial movement. As to the upper central incisor, both the crown and the root presented a lingual movement. However, the inclination of these teeth was not affected. In group II, the upper first molar remained stable and only the crown of the upper central incisor moved lingually, leading to a clockwise rotation of this tooth. In group III, a mesial movement of both the crown and the root of the lower first molar was observed, along with its extrusion, whereas the position of the lower central incisor remained unchanged. The inclination of these teeth was not affected either. In group IV, it was observed that neither the lower first molar nor the lower central incisor experienced variations in the anteroposterior sense. Vertically, there only was extrusion of the lower first molar.

No presente estudo foi analisada a distribuição de tensões, na região anterior de modelo fotoelástico, gerada por arcos de intrusão de incisivos inferiores. Compararam-se as tensões entre diferentes arcos. E ainda, em cada tipo de arco, compararam-se as tensões entre terços radiculares e entre incisivos. O modelo fotoelástico foi construído simulando a extrusão dos incisivos. Foram confeccionados sessenta arcos de intrusão, sendo quinze de cada tipo de mecânica: arco contínuo de Burstone, arco utilitário de Ricketts, arco com dobra de ancoragem usado na mecânica de Begg e arco com curva de Spee reversa usado na mecânica de Tweed. A força de ativação foi mensurada em 50gf na região da linha média. O modelo fotoelástico foi observado em polariscópio circular, na configuração de campo escuro, e fotografado. As fotografias frontais foram analisadas, e as ordens de franjas em cada região registradas. A repetibilidade do método foi identificada pela análise de kappa. A comparação entre as tensões foi realizada pelo teste de Kruskall-Wallis complementado com teste de Dunn. Os resultados obtidos permitiram concluir que na região apical, as maiores magnitudes de tensões foram geradas pelo arco utilitário de Ricketts, seguido pelo arco contínuo de Burstone. Na região média, as maiores magnitudes de tensões foram geradas pelo arco utilitário de Ricketts, seguida por arco contínuo de Burstone, arco com dobra de ancoragem e arco com curva de Spee reversa. Na região cervical, as maiores magnitudes de tensões foram decorrentes do arco utilitário de Ricketts, seguido por arco com curva de Spee reversa e arco com dobra de ancoragem. Os arcos contínuos de Burstone apresentaram as menores tensões na região cervical. Ao se comparar as ordens de franjas entre os terços radiculares, de cada dente, em todos os arcos analisados, as maiores magnitudes de tensões foram observadas nas regiões cervicais. Ao se comparar as ordens de franjas entre os dentes, em cada terço radicular, no arco contínuo de Burstone, as maiores magnitudes de tensões foram observadas nos incisivos laterais. Entretanto, no arco utilitário de Ricketts e no arco com dobra de ancoragem, as maiores magnitudes de tensões foram observadas nos incisivos centrais. No arco com curva de Spee reversa, as maiores magnitudes de tensões foram identificadas nos incisivos esquerdos. Portanto, os resultados do presente estudo permitiram a visualização e compreensão dos efeitos dos diversos arcos de intrusão. Entretanto, estes resultados devem ser observados com cautela, requerendo mais pesquisas que confirmem a reprodutibilidade do método e dos resultados. / In the present study, the distribution of stresses caused by intrusion arches on lower incisors, in the anterior region of photoelastic model, was analyzed. The stresses were compared among the different arches. Additionally, stresses were also compared among the root thirds, as well as among the incisors for each arch type. The photoelastic model was constructed simulating the extrusion of incisors. Sixty intrusion arches were made up, corresponding to fifteen of each type: Burstone continuous arches, Ricketts utility arches, anchorage bend arches used in Begg mechanics and reverse Spee curved arches used in Tweed mechanics. Activation force was measured at 50gf in the midline. The photoelastic model was observed under circular polariscope, in dark-field configuration, and photographed. Frontal photographs were analyzed, and fringe order in each region was recorded. Method repeatability was identified by kappa analysis. A comparison among stresses was carried out using Kruskall-Wallis test and complemented by the Dunn test. Results obtained led to the conclusion that in the apical region, the major stress magnitudes were generated by the Ricketts utility arch, followed by the Burstone continuous arch. In mid-region, the major stress magnitudes were generated by Ricketts utility arch, followed by the Burstone continuous arch, anchorage bend arch, and arch wire with a reverse curve of Spee. In the cervical region, the major stress magnitudes stemmed from Ricketts utility arch, followed by arch with reverse curve of Spee and the anchorage bend arch. The Burstone continuous arches presented the least stresses in the cervical region. On comparing fringe orders among root thirds, of each tooth, in all arches analyzed, major magnitudes of stresses were observed in the cervical regions. On comparing fringe orders among teeth, in each root third, the major magnitudes of stresses were observed in lateral incisors in Burstone continuous arches. However, in both Ricketts utility arches and anchorage bend arches the major stresses magnitudes were observed in central incisors. In arch with a reverse curve of Spee the major magnitudes of stresses were identified in left incisors. Consequently the results in the present study allowed a visualization and understanding of the effects of the diverse intrusion arches. However, such results should be observed with caution, requiring further study to confirm method reproducibility as well as results.

Diese Arbeit stellt eine gründliche Analyse der Schwerpunktsbewegung von Exzitonen in Halbleiter-Quantengräben und -Quantendrähten dar. Dabei wurde die k.p-Kopplung der schweren und leichten Löcher im Valenzband sowie das Coulomb-Potential voll berücksichtigt. Die Optimierung der Schwerpunktstransformation auf der Basis eines Ansatzes für die Abhängigkeit des Grundzustands des Exzitons vom Schwerpunktsimpuls Q ermöglichte numerische Ergebnisse hoher Qualität. Es zeigt sich nämlich, daß in einer Subbandentwicklung die Enveloppe des Grundzustands des Exzitons in guter Näherung unabhängig vom Schwerpunktsimpuls ist. So konnten erstmalig Multiband-Exziton-Berechnungen in Quantendrähten mit voller Berücksichtigung der Coulomb-Wechselwirkung durchgeführt werden. Die in dieser Arbeit dargestellten Untersuchungen zeigen interessante physikalische Effekte auf, wie beispielsweise eine nichtmonotone Zunahme der Bindungsenergie des exzitonischen Grundzustands mit wachsendem Q und einen zur entsprechenden Kontinuumskante weitestgehend parallelen Verlauf der Dispersion des exzitonischen Grundzustands. Die Optimierung der Schwerpunktstransformation führt außerdem zu einem analytischen Ausdruck für eine mittlere Masse, die relevant für den exzitonischen Grundzustand ist. / This thesis presents a thorough investigation of the center-of-mass dispersion properties of excitons in semiconductor quantum wells and quantum wires. The k.p coupling of heavy and light holes as well as the Coulomb coupling are taken fully into account. High-quality numerical calculations of the exciton center-of-mass dispersion are achieved by optimizing the center-of-mass transformation, making use of an Ansatz for the dependence of the groundstate exciton upon the center-of-mass momentum Q. Indeed, the envelope in the subband expansion of the groundstate exciton is to a good approximation independent of Q. This technique made possible for the first time multiband calculations in quantum wires that take the Coulomb coupling fully into account. Various physically interesting effects are found and investigated, like, e.g., the non-monotonous increase of the exciton groundstate binding energy with Q or the fact that the exciton groundstate energy follows the exciton continuum edge rather closely. The center-of-mass optimization leads also to an analytical expression for an estimate of the exciton groundstate center-of-mass mass.

A condutância de fios quânticos definidos em uma geometria de \"split gate\" varia em platôs quantizados de 2e2/h em relação à ocupação dos seus modos transversais [van Wees et al. Phys. Rev. Lett. 60, 848 (1988) & Wharam et al. J. Phys. C: solid state phys. 21, L209 (1988)]. Em gráficos da condutância esta ocupação é dada pelo potencial aplicado aos eletrodos que formam o fio. Em 1996 observou-se experimentalmente nestes gráficos [Thomas et al. Phys. Rev. Lett. 77, 135 (1996)] que quando apenas um modo transversal é ocupado a condutância exibe um platô anômalo adicional em 0.7X2e2/h. Desde então, a origem desta anomalia 0.7 é associada a fenômenos dependentes de spin, porém sua descrição teórica permanece como importante objeto de pesquisa. Recentemente, observou-se que na presença de altos campos magnéticos, cruzamentos de modos transversais de spins opostos também geram estruturas anômalas no gráfico da condutância [Graham etal. Phys. Rev. Lett. 91, 136404 (2003)]. Os análogos 0.7, assim chamados devido à semelhança com a anomalia 0.7, são usualmente relacionados ou como anti-crossings ou como transições de fase magnética. Motivado pela concordância quantitativa com experimentos de um trabalho anterior em magnetotransporte em 2DEGs e transições de fase de ferromagnetismo de efeito Hall quântico via teoria do funcional da densidade dependente de spin (SDFT) [Freire e Egues, Phys. Rev. Lett. 99, 026801 (2007) & Ferreira et al. Phys. Stat. Sol. (c) 3, 4364 (2006)], propomos aqui um modelo similar para estudar na magnetocondutância de fios quânticos. Utilizamos (i) a SDFT resolvendo as equações de Kohn-Sham autoconsistentemente dentro da aproximação de densidade local de spin para obter a estrutura eletrônica do fio quântico e (ii) o formalismo de Landauer-Büttiker para calcular a condutância do fio no regime de resposta linear. Em nosso modelo, a anomalia e os análogos 0.7 aparecem devido a transições ferromagnéticas que rearranjam de forma abrupta os modos transversais do fio quântico próximos ao nível de Fermi. Nossos resultados teóricos apresentam boa concordância com os dados de Graham et al. / At low temperatures the conductance of a quantum wires exhibits plateaus at integer multiples of 2e2/h due to the quantization of the transverse modes [van Wees et al. Phys. Rev. Lett. 60, 848 (1988) & Wharam et al. J. Phys. C: solid state phys. 21, L209 (1988)]. This conductance behavior is understood within an independent particles model. In 1996 Thomas et al.[Phys. Rev. Lett. 77, 135 (1996)] showed experimentally that when only one transverse mode is occupied, the conductance displays an additional plateau at 0.7 X 2e2/h the so-called 0.7 anomaly. Further experiments have shown that in the presence of high in-plane magnetic fields, similar structures also appear in the conductance near the crossings of spin-split transverse modes [Graham et al. Phys. Rev. Lett. 91, 136404 (2003)]. These so-called 0.7 analogs, due to their similarity to the 0.7 anomaly, are usually related to either anti-crossings or magnetic phase transitions. Motivated by the quantitative agreement with experiments of a previous theoretical work on magnetotransport in 2DEGs and quantum Hall ferromagnetic phase transitions via the Spin Density Functional Theory (SDFT) [Freire and Egues, Phys. Rev. Lett. 99, 026801 (2007) & Ferreira et al. Phys. Stat. Sol. (c) 3, 4364 (2006)], here we propose a similar model to investigate the magnetoconductance of interacting quantum wires. We use (i) the SDFT via the Kohn-Sham self-consistent scheme within the local spin density approximation to obtain the quantum wire electronic structure and (ii) the Landauer-Büttiker formalism to calculate the conductance of a quantum wire in the linear response regime. Our results show good agreement with the data of Graham et al.

The study of synthetic peptides aid in improving our current understanding of the fundamental principles for the de novo design of functional proteins. The investigation of designed peptides has been instrumental in providing answers to many questions ranging from the conformational preferences of amino acids to the compact folded structures and also in developing tools for understanding the growth and formation of the protein secondary structures (helices, sheets and turns). In addition, the self-assembly of peptides through non-covalent interactions is also an emerging area of growing interest. The design of peptides which can mimic the protein secondary structures relies on the use of stereochemically constrained amino acid residues at select positions in the linear peptide sequences, leading to the construction of protein secondary structural modules like helices, hairpins and turns. The use of non-coded amino acid residues with strict preferences for adopting particular conformations in the conformational space becomes the most crucial step in peptide design strategies. In addition the crystallographic characterization and analysis of the sequences provides the necessary optimization of the design strategies. The crystallographic characterization of designed peptides provides a definitive and conclusive proof of the success of a design strategy. Furthermore, the X-ray structures provide an atomic view of the interactions, both strong and weak, which govern the growth of the crystal. The information on the geometric parameters and stereochemical properties of a series of peptides, through a systematic study, provides the necessary basis for further scientific investigation, like the molecular dynamics and can also aid in improving the force field parameters meant for carrying out molecular simulations. This can be further complemented by constructing biologically active peptide sequences. The focus of this thesis is to characterize crystallographically the conformational and structural aspects of peptide nanotubes and encapsulated water wires and the β-hairpin peptide models of β-sheets. The systematic study of a series of pentapeptide and octapeptide sequences, containing Aib and D-amino acid residues incorporated at strategic positions, establish the conformation and structural properties of designed peptides as mimics of protein secondary structures and hydrophobic tubular peptide channels and close-packed forms. The structures reported in this thesis are given below: 1 Boc-DPro-Aib-Leu-Aib-Val-OMe (DPUL5) C30H53N5O8 2 Boc-DPro-Aib-Val-Aib-Val-OMe (DPUV5a) C29H51N5O8 .(0.5) H2O 3 Boc-DPro-Aib-Val-Aib-Val-OMe (DPUV5b) C27H51N5O8 .(0.17) H2O 4 Boc-DPro-Aib-Ala-Aib-Val-OMe (DPUA5) C27H47N5O8 5 Boc-DPro-Aib-Phe-Aib-Val-OMe (DPUF5) C33H48N5O8 6 Boc-Pro-Aib-DLeu-Aib-DVal-OMe (PUDL5) C30H53N5O8 7 Boc-Pro-Aib-DVal-Aib-DVal-OMe (PUDV5a) C27H51N5O8 .(0.17) H2O 8 Boc-Pro-Aib-DVal-Aib-DVal-OMe (PUDV5b) C27H51N5O8 . 2H2O 9 Boc-Pro-Aib-DAla-Aib-DVal-OMe (PUDA5) C27H47N5O8 10 Boc-Pro-Aib-DPhe-Aib-DVal-OMe (PUDF5) C33H48N5O8 11 Ac-Phe-Pro-Trp-OMe (FPW) C28H32N4O5.(0.33)H2O 12 Boc-Leu-Phe-Val-DPro-Pro-Leu-Phe-Val-OMe (DPLP8) C56H84N8O1 1 .(0.5) H2O 13 Boc-Leu-Phe-Val-DPro-Pro-Leu-Phe-Val-OMe (YDPP8) C56H83N8O12 .(1.5) H2O 14 Boc-Leu-Val-Val-DPro-ψPro-Leu-Val-Val-OMe (PSIP8) C56H84N8O11S1 .(1.5) H2O 15 Boc-Leu-Phe-Val-DPro-Pro-Leu-Phe-Val-OMe (DPPV8) C48H84N8O11 16 Boc-Leu-Phe-Val-DPro-Aib-Leu-Phe-Val-OMe (DPUF8) C57H88N8O11.(1.5) H2O 17 Piv-Pro-ψH,CH3Pro-NHMe (PSPL3) C22H37N3O5S1 18 Boc-Leu-Val-Val-Aib-DPro-Leu-Val-Val-OMe (UDPV8) C47H84N8O11.2(C3H7NO) 19 Boc-Leu-Phe-Val-DPro-Ala-Leu-Phe-Val-OMe (BH1P8) C54H78N8O11.H2O 20 Boc-Leu-Phe-Val-DPro-Aib-Leu-Phe-Val-OMe (DPUFP8) C55H84N8O11. (0.5) H2O 21 Boc-Leu-Phe-Val-DPro-Pro-Leu-Phe-Val-OMe (YDPPP8) C56H83N8O12. (1.5) H2O The crystal structure determination of the peptides presented in this thesis provides a wealth of information on the folding patterns of the sequences, in addition to the characterization of many structural and geometric properties. In particular, the study sheds light on the growth and formation of peptide nanotubes and the structure of encapsulated water wires, and also the structural details of Type I′ and Type II′β-turn nucleated hairpins. The study provides the backbone and side chain conformational parameters of the sequences, highlighting the varied conformational excursions possible in the peptide molecules. The thesis is divided into 6 chapters and one appendix. Chapter 1 gives a general introduction to the stereochemistry of the polypeptide chain, description of backbone torsion angles of α-amino acid residues and the major secondary structures of α-peptides, namely α-helix, β-sheet and β-turns. The basic structural features of helices and sheets are given. A brief introduction to polymorphism and weak interactions is also presented, followed by a discussion on X-ray diffraction and solution to the phase problem. Chapter 2 is divided into two parts. PART 1 describes the crystal structures of a series of eight related enantiomeric peptide sequences (Raghavender et al., 2009; Raghavender et al., 2010). The crystal structures of four sequences with the general formula Boc-DPro-Aib-Xxx-Aib-Val-OMe (Xxx = Ala/Val/Leu/Phe) and the enantiomeric sequences provided a set of crystal structures withdifferent packing arrangements. The structure of the peptide with Xxx = Leu revealed a nanotube formation with the Leu lining the inner walls of channel. The channels were found to be empty. The sequence with Xxx = Val revealed a solvent-filled water channel.Investigation of the water wire structures on the diffraction data collected on the same crystal over a period of time revealed the existence of two different kinds of water wires in thechannels. Comparison with the peptide tubular structures available in the literature and the water structure inside the aquaporin channels are contrasted. Close-packed structures are observed in the case of Xxx=Ala and Phe. The backbone conformations are essentially identical. Enantiomeric sequences also revealed similar structures. Polymorphic forms were observed in the case of DVal(3) containing sequence. One form is observed to have water-filled channels forming a nanotube, as opposed to the close-packed structure in the polymorphic form. Crystal parameters DPUL5: C30H53N5O8; P65; a = b = 24.3673 (9) Å, c = 10.6844 (13) Å; α = β = 90°, γ = 120°; Z = 6; R = 0.0671, wR2 = 0.1446. DPUV5a: C29H51N5O8 .(0.5) H2O; P65; a = b = 24.2920 (13) Å, c = 10.4838 (11) Å; α = β = 90°, γ = 120°; Z = 6; R = 0.0554, wR2 = 0.1546. DPUV5b: C29H51N5O8 .(0.17) H2O; P65; a = b = 24.3161 (3) Å, c = 10.1805 (1) Å; α = β = 90°, γ = 120°; Z = 6; R = 0.0617, wR2 = 0.1844. DPUA5: C27H47N5O8; P212121; a = 12.2403 (8), b = 15.7531 (11) Å, c = 16.6894 (11) Å; Z =4; R = 0.0439, wR2 = 0.1249. DPUF5: C33H48N5O8; P212121; a = 10.3268 (8), b = 18.7549 (15) Å, c = 18.9682 (16) Å; Z = 4; R = 0.0472, wR2 = 0.1325. PUDL5: C30H53N5O8; P61; a = b = 24.4102 (8) Å, c = 10.6627 (7) Å; α = β = 90°, γ = 120°; Z = 6; R = 0.0543, wR2 = 0.1495. PUDV5a: C29H51N5O8 .(0.17)H2O; P61; a = b = 24.3645 (14) Å, c = 10.4875 (14) Å; α = β = 90°, γ = 120°; Z = 6; R = 0.0745, wR2 = 0.1810. PUDV5b: C29H51N5O8. 2H2O; C2; a = 20.7278 (35), b = 9.1079 (15) Å, c = 19.5728 (33) Å; α = γ = 90°, β = 94.207°; Z = 6; R = 0.0659, wR2 = 0.1755. PUDA5: C27H47N5O8; P212121; a = 12.2528 (12), b = 15.7498 (16) Å, c = 16.6866 (16) Å; Z = 4; R = 0.0473, wR2 = 0.1278. PUDF5: C33H48N5O8; P212121; a = 10.3354 (8), b = 18.7733 (10) Å, c = 18.9820 (10) Å; Z = 4; R = 0.0510, wR2 = 0.1526. PART 2 describes the crystallographic characterization of the tubular structure in a tripeptide Ac-Phe-Pro-Trp-OMe (FPW) sequence. The arrangement of the single-file water moleculesin the peptide nanotubes of FPW could be established by X-ray diffraction. In addition, the energetically favoured arrangement of the water wire inside the peptide channels could be modeled by understanding the construction of the peptide nanotube. In particular, the helicalmacrodipole of the peptide nanotube and the water wire dipoles prefer an antiparallel arrangement inside the peptide channels as opposed to parallel arrangements, is established by the classical dipole-dipole interaction energy calculation. In addition, the growth of thenanotubes and the arrangement of the water wires inside the channels could be correlated to the macroscopic dimensions of the crystal by the indexing of the crystal faces and contrasted with the structure of DPUV5. Crystal parameters FPW: C28H32N4O5.(0.33)H2O; P65; a = b = 21.5674 (3) Å, c = 10.1035 (2) Å; α = β = 90°, γ = 120 °; Z = 6; R = 0.0786, wR2 = 0.1771 Chapter 3 provides the crystal structures of five octapeptide β-hairpin forming sequences and a tripeptide containing a modified amino acid, with modification in the side chain (pseudo-proline, ψH,CH3Pro). The parent peptide, Boc-Leu-Phe-Val-DPro-Pro-Leu-Phe-Val-OMe (DPLP8), was observed to form a strong Type II′β-turn at the DPro-Pro segment, and the strand segments adopting a β-sheet conformation. Two molecules were observed in the asymmetric unit, inclined to each other at approximately 70°. Modification in the strand sequence Phe(2) to Tyr(2) also resulted in a hairpin with identical conformation and similar packing arrangement. The difference was in the solvent content. In both the cases the molecules were packed orthogonal with respect to each other, resulting in the formation of ribbon-like structures in three dimensions. The replacement of Phe(2) and Phe(7) with Valine residues, with the retention of DPro-Pro β-turn segment, results in an entiely different packing arrangement (parallel). Modification of Pro(5) residue of the turn segment to Aib(5) and ψPro, also results in the molecules packing orthogonally to each other. The tripeptide with a modified form of ψPro, namely ψH,CH3Pro, resulted in a folded structure with a Type VIa β-turn, with the amide bond between the Pro-ψH,CH3Pro segment adopting a cis configuration (Kantharaju et al., 2009). Crystal parameters DPLP8: C56H84N8O11 .(0.5) H2O; P21; a = 14.4028 (8), b = 18.9623 (11) Å, c = 25.4903 (17) Å, β = 105.674 ° (4); Z = 4; R = 0.0959, wR2 = 0.2251. YDPP8: C56H84N8O12 .(1.5) H2O; P212121; a = 14.4028 (8), b = 18.9623 (11) Å, c = 25.4903 (17) Å, Z = 8; R = 0.0989, wR2 = 0.2064. PSIP8: C57H86N8O11S1.(1.5) H2O; C2; a = 34.6080 (2), b = 15.3179 (10) Å, c = 25.6025 (15) Å, β = 103.593 ° (3); Z = 4; R = 0.0931, wR2 = 0.2259. DPPV8: C48H84N8O11; P1; a = 9.922 (3), b = 11.229 (4) Å, c = 26.423 (9) Å, α = 87.146 (6), β = 89.440° (6), γ = 73.282 (7); Z = 2; R = 0.1058, wR2 = 0.2354. DPUF8: C57H88N8O11 .(1.5) H2O; P21; a = 18.410 (2), b = 23.220 (3) Å, c = 19.240 (3) Å, β = 118.036 ° (4); Z = 4; R = 0.1012, wR2 = 0.2061. PSPL3: C22H37N3O5S1; P31; a = b = 14.6323 (22), c = 10.4359 (22) Å, α = β = 90°, γ = 120°; Z = 3; R = 0.0597, wR2 = 0.1590. Chapter 4 describes the crystal structure and molecular conformation of Type I′β-turn nucleated hairpin. The incorporation of Aib-DPro segment in the middle of Leu-Val-Val strands in the peptide sequence Boc-Leu-Val-Val-Aib-DPro-Leu-Val-Val-OMe results in an obligatory Type I′ turn containing hairpin. The molecular conformation and the packing arrangement of the molecules in the crystal are contrasted with the only Type I′β-hairpin reported in the literature and with a sequence where the turn residues are flipped and strand residues replaced with Phe(2) and Phe(7). Crystal parameters UDPV8: C47H84N8O11.2(C3H7NO); P21; a = 11.0623 (53), b = 18.7635 (89) Å, c = 16.6426 (80) Å, β = 102.369 (8); Z = 2; R = 0.0947, wR2 = 0.1730. Chapter 5 provides the crystal structures of three polymorphic forms of β-hairpins. The structure of BH1P8 provides new insights into the packing of hairpins inclined orthogonally to each other. The two polymorphic forms differ not only in their modes of packing in crystals but also in the strong and weak interactions stabilizing the packing arrangements. The polymorphic forms of DPUFP8 differ only in the content of the solvent in the asymmetric unit and the role it plays in bridging the symmetry related pairs of molecules. The polymorphic form YDPPP8 crystallized in a completely different space group, revealing a completely different mode of packing and also the cocrystallized solvent participating in a different set of interactions. Crystal parameters BH1P8: C54H78N8O11.H2O; P212121; a = 18.7511 (9), b = 23.3396 (11) Å, c = 28.1926 (13)Å; Z = 8; R = 0.1208, wR2 = 0.2898. DPUFP8: C55H84N8O11. (0.5) H2O; P21; a = 18.0950 (4), b = 23.0316 (5) Å, c = 18.6368 (5) Å, β = 117.471 (2); Z = 4; R = 0.0915, wR2 = 0.2096. YDPPP8: C56H83N8O12. (1.5) H2O; P21; a = 14.3184 (8), b = 18.9924 (9) Å, c = 25.1569 (14) Å, β = 105.590 (4); Z = 4; R = 0.1249, wR2 = 0.2929. Chapter 6 provides a comprehensive overview of the β-hairpin peptide crystal structures published in the literature as well as those included in the thesis. The hairpins are classified based on the residues composing the β-strands and the mode of their packing in the crystals. In the crystal structures the hairpins are observed to adopt either a Type II′ or Type I′β-turns. The indexing of the crystal faces of a few representative hairpin peptides crystallographically characterized in this thesis, provides a rational explanation for the preferential growth of the crystals in certain directions, when correlated with the strong directional forces (hydrogen bonding) and weak interactions (van der Waals, aromatic-aromatic) observed in the crystal packing. The insights gained by these studies would be highly valuable in understanding the nucleation and growth of β-hairpin peptides and the formation of β-sheet structures. Appendix I describes the Cambridge Structural Database (CSD) analysis of the conformational preferences of the proline residues found in the peptide crystal structures. The frequency distributions of the backbone φ, ψ and ω and side chain χ1, χ2, χ3, χ4 and θ torsion angles of the proline residues are calculated, tabulated and represented as graphical plots. The correlation between the backbone and endocyclic torsion angles provides for a clear evidence of the role of a particular torsion variable χ2 in deciding the state of puckering. In addition, the endocyclic bond angles also appear to be correlated, relatively strongly, with the χ2 torsion. This provides a geometrical explanation of the factors governing the puckering of the proline ring.

La théorie de Landau des liquides de Fermi prévoit que la charge et la chaleur sont transportées par les mêmes objets: les quasi-particules fermionics de Landau. De façon très général, ceci est vrai, si l'écrantage parmi les particules dans le système est assez fort pour pouvoir continuer à considérer le système comme composé de particules indépendantes. C'est le cas, par exemple, pour la mer d'électrons dans un métal ordinaire. L'existence d'un même responsable pour le transport de la charge et de la chaleur est exprimé par la lois de Wiedemann-Franz (WF) qui affirme que le rapport entre la conductivité thermique et électrique dépend de la température par une constante qui est plus au moins la même pour plusieurs métaux. La constante de proportionnalité est appelé nombre de Lorenz. <br /> Que se passe-t-il si les conditions concernant l'écrantage que nous avons mentionnées ne sont plus satisfaites, comme par exemple dans les systèmes à dimensionalité réduite, ou des système à basse densité électronique? <br /> Le travail de thèse est divisé en deux parties. Dans la première partie, nous avons étudié le transport thermique et électrique dans un fil quantique désordonné; dans la deuxième, l'influence des fluctuations supraconductives sur la conductivité thermique dans un métal granulaire.<br /><br /> -)Fils Quantiques: <br /><br /> Généralement, on appelle fil quantique un conducteur uni-dimensionel. Aujourd'hui, il est possible de réaliser des conducteurs qui présentent de très forts potentielles de confinement le long de un ou deux des dimensions linéaire. En particulier, les fils quantiques se comportent comme des véritables guides d'onde pour les électrons car ils peuvent avoirs des diamètres qui sont comparable à la longueur d'onde de Fermi. <br /> A cause de la basse dimensionalité, des tels systèmes sont étudiés dans le contexte de la théorie des liquides de Luttinger qui permet de bien prendre en compte les effets d'interaction parmi les particules. <br /> Pour un fil quantique propre connecté à deux réservoirs, la conductance électrique n'est pas renormalisée, alors que celle thermique l'est fortement à cause de la présence des connexions aux réservoirs. La présence d'un faible désordre renormalise aussi la conductance électrique. Ceci était déjà connu. <br /> Nous avons évalué la renormalisation due aux impuretés pour la conductance thermique. Cela nous a permis de pouvoir évaluer la correction au nombre de Lorenz. <br /> A très basses températures, la correction est nulle, alors que à hautes température elle ne l'est jamais. Nous pouvons affirmer qu'un fil quantique avec impuretés n'est pas dans un état type liquide de Fermi.<br /><br /> -) Métaux Granulaires: <br /> <br /> Dans un métal normal en présence d' interactions de type BCS, les électrons peuvent former des pairs de Cooper même à une température plus élevé que la température critique. Dans ce cas, les propriétés de transport du métal normal se mélangent avec celle de l'état supraconducteur. Cela donne lieu à des contributions qui déterminent le transport de la charge et de l'énergie. <br /> Notamment, sont trois les termes qui contribuent: la contribution Aslamazov -Larkin (AL), la contribution Maki-Thomson (MT), et la contribution Densité d'état (DOS). <br /> La première prend en compte la facilité des électrons formants un pair de Cooper à se propager à travers le système. Cette contribution est aussi appelé paraconductivité; les électrons formants des pairs de Cooper ne sont plus disponibles pour le transport à une seul particule. Cela est pris en compte par la contribution DOS. Le terme MT prend en compte la diffusion cohérent des électrons formants un pair de Cooper sur la même impureté.<br /> Pour un système massif, il a été démontré que les contributions DOS et MT se compense exactement. Il ne reste que le terme AL qui n'est pas singulier dans la température. <br /> Un métal granulaire peut être considéré comme un ensemble D-dimensionel the grains metallics plongé dans un milieux isolant. Les grains communiquent entre eux par effet tunnel.<br /> C'est raisonnable imaginer que la présence de l'effet tunnel renormalise les propriétés de transport. En effet, un comportement dépendant de la température émerge. Les contributions AL et MT sont d'ordre supérieur par rapport au terme DOS.<br /> On peut distinguer deux régions différentes: loin et près de la température critique. Loin de la température critique, le tunneling parmi les grains n'est pas efficace, et la structure granulaire l'emporte; une suppression de la correction à la conductivité thermique est retrouvée. Près de la température critique, le tunneling est efficace est la structure massive est retrouvée. Le signe de la correction n'est pas défini de manière univoque. Il dépend de la transparence de la barrière et de la compétition parmi les différentes contributions.<br /> Dans les deus différents régimes, la lois de WF est violée.

Some special features of polaritons, quasi-particles being normal modes of system of excitons interacting with photons in so called strong coupling regime, are theoretically and numerically analyze in low dimensional systems. In Chapter 1 is given a brief overview of 0D, 1D and 2D semiconductor structures with a general introduction to the polariton field. Chapter 2 is devoted to micro / nano wires. The so called whispering gallery modes are studied in the general case of an anisotropic systems as well as polariton formation in ZnO wires. Theoretical model is compared with an experiment. In the Chapter 3 Josephson type dynamics with Bose-Einstein condensates of polaritons is analyzed taking into account pseudospin degree of freedom. Chapter 4 start with an introduction to Aharonov-Bohm effect, as the best known represent of geometrical phases. An another geometrical phase - Berry phase, occurring for a wide class of systems performing adiabatic motion on a closed ring, is main subject of this section. We considered one proposition for an exciton polariton ring interferometer based on Berry phase effect. Chapter 5 concerns one 0D system : strongly coupled quantum dot exciton to cavity photon. We have discussed possibility of obtaining entangled states from a quantum dot embedded in a photonic crystal in polariton regime.

As the convergence of multiple functions in a single electronic device drives current electronic trends, the need for increasing integration density is becoming more emphasized than in the past. To keep up with the industrial need and realize the new system integration law, three-dimensional (3-D) integration called System-on-Package (SoP) is becoming necessary. However, the commercialization of 3-D integration should overcome several technical barriers, one of which is the difficulty for the electrical design of interconnections. The 3-D interconnection design is difficult because of the modeling challenge of electrical coupling from the complicated structures of a large number of interconnections. In addition, mixed-signal design requires broadband modeling, which covers a large frequency spectrum for integrated microsystems. By using currently available methods, the electrical modeling of 3-D interconnections can be a very challenging task. This dissertation proposes a new method for constructing a broadband model of a large number of 3-D interconnections. The basic idea to address the many interconnections is using modal basis functions that capture electrical effects in interconnections. Since the use of global modal basis functions alleviates the need for discretization process of the interconnection structure, the computational cost is reduced considerably. The resultant interconnection model is a RLGC model that describes the broadband electrical behavior including losses and couplings. The smaller number of basis functions makes the interconnection model simpler, and therefore allows the generation of network parameters at reduced computational cost. Focusing on the modeling of bonding wires in stacked ICs and through-silicon via (TSV) interconnections, this research validates the interconnection modeling approach using several examples from 3-D full-wave EM simulation results.