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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

Synchronization in Impulse Based Ultra Wideband Systems

Piratla, Dinakara Phaneendra Kumar 31 July 2008 (has links)
In Impulse Radio based Ultra Wide Band (UWB) systems, where sub-nano second pulses are used, synchronization is very challenging because of their short pulse duration and very low duty cycle. Coherent detection of ultra wide-band signals requires complex channel estimation algorithms. In impulse based UWB systems, suboptimal receivers that require no channel estimation are proposed for low data rate applications using non coherent detection of energy. This approach requires integrators that collect energy and detect the incoming stream of bits for detection and synchronization. These techniques yield reasonable performance when compared to coherent detection techniques that require complex hardware and dissipate more energy. Non-coherent detection is a promising technique for low complexity, low cost and low data rate ultra-wideband communication applications like sensor area networks. In the past, several attempts have been made to characterize the performance of the energy collection receivers for synchronization using various metrics that include time of arrival and BER measurements. A comprehensive study of the synchronization problem using Probability of False Alarm is limited. The current thesis attempts to characterize the synchronization problem using Probability of False Alarm and Probability of Detection under various channel models and also discusses the importance of the length of the integration window for energy collection receivers. The current work also focuses on the performance evaluation of synchronization for Impulse based UWB systems using energy capture method and modeling them using the Probability of False Alarm and Probability of Detection under various channel models. In these systems, the integration region of a receiver integrator significantly affects the bit error rate (BER) performance. The effect of the integration window on the performance of the algorithm is also studied. This work also discusses the trade-offs between complexity and precision in using these algorithms for synchronization of Impulse based Direct Sequence Ultra Wideband Systems (DS-UWB). Signal to Noise Ratio vs. Probability of Detection, Probability of False Alarm are plotted for different channel models. / Master of Science
72

Hydroxytriazole derivatives as potent and selective aldo-keto reductase 1C3 (AKR1C3) inhibitors discovered by bioisosteric scaffold hopping approach

Pippione, A.C., Giraudo, A., Bonanni, D., Carnovale, I.M., Marini, E., Cena, C., Costale, A., Zonari, D., Pors, Klaus, Sadiq, Maria, Boschi, D., Oliaro-Bosso, S., Lolli, M.L. 24 August 2017 (has links)
Yes / The aldo-keto reductase 1C3 isoform (AKR1C3) plays a vital role in the biosynthesis of androgens, making this enzyme an attractive target for castration-resistant prostate cancer therapy. Although AKR1C3 is a promising drug target, no AKR1C3-targeted agent has to date been approved for clinical use. Flufenamic acid, a non-steroidal anti-inflammatory drug, is known to potently inhibit AKR1C3 in a non-selective manner as COX off-target effects are also observed. To diminish off-target effects, we have applied a scaffold hopping strategy replacing the benzoic acid moiety of flufenamic acid with an acidic hydroxyazolecarbonylic scaffold. In particular, differently N-substituted hydroxylated triazoles were designed to simultaneously interact with both subpockets 1 and 2 in the active site of AKR1C3, larger for AKR1C3 than other AKR1Cs isoforms. Through computational design and iterative rounds of synthesis and biological evaluation, novel compounds are reported, sharing high selectivity (up to 230-fold) for AKR1C3 over 1C2 isoform and minimal COX1 and COX2 off-target inhibition. A docking study of compound 8, the most interesting compound of the series, suggested that its methoxybenzyl substitution has the ability to fit inside subpocket 2, being involved in π-π staking interaction with Trp227 (partial overlapping) and in a T-shape π-π staking with Trp86. This compound was also shown to diminish testosterone production in the AKR1C3-expressing 22RV1 prostate cancer cell line while synergistic effect was observed when 8 was administered in combination with abiraterone or enzalutamide. / University of Turin (Ricerca Locale grant 2014 and 2015) and Prostate Cancer UK grant S12-027
73

Structural, magnetic and electrical transport properties of GaN-based magnetic semiconductors and hybrid structures / Strukturelle, magnetische und elektrische Eigenschaften von GaN-basierten verdünnten magnetischen Halbleiter und Hybridstrukturen

Bedoya Pinto, Amilcar 09 November 2010 (has links)
No description available.
74

Modelagem molecular na caracteriza??o eletr?nica de oligopept?deos e na descri??o qu?ntica da intera??o f?rmaco-receptor

Oliveira, Jonas Ivan Nobre 02 March 2012 (has links)
Made available in DSpace on 2014-12-17T14:10:24Z (GMT). No. of bitstreams: 1 JonasINO_DISSERT.pdf: 890224 bytes, checksum: a68b1b3f5f169bb87b98314d116a12b3 (MD5) Previous issue date: 2012-03-02 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this dissertation, the theoretical principles governing the molecular modeling were applied for electronic characterization of oligopeptide α3 and its variants (5Q, 7Q)-α3, as well as in the quantum description of the interaction of the aminoglycoside hygromycin B and the 30S subunit of bacterial ribosome. In the first study, the linear and neutral dipeptides which make up the mentioned oligopeptides were modeled and then optimized for a structure of lower potential energy and appropriate dihedral angles. In this case, three subsequent geometric optimization processes, based on classical Newtonian theory, the semi-empirical and density functional theory (DFT), explore the energy landscape of each dipeptide during the search of ideal minimum energy structures. Finally, great conformers were described about its electrostatic potential, ionization energy (amino acids), and frontier molecular orbitals and hopping term. From the hopping terms described in this study, it was possible in subsequent studies to characterize the charge transport propertie of these peptides models. It envisioned a new biosensor technology capable of diagnosing amyloid diseases, related to an accumulation of misshapen proteins, based on the conductivity displayed by proteins of the patient. In a second step of this dissertation, a study carried out by quantum molecular modeling of the interaction energy of an antibiotic ribosomal aminoglicos?dico on your receiver. It is known that the hygromycin B (hygB) is an aminoglycoside antibiotic that affects ribosomal translocation by direct interaction with the small subunit of the bacterial ribosome (30S), specifically with nucleotides in helix 44 of the 16S ribosomal RNA (16S rRNA). Due to strong electrostatic character of this connection, it was proposed an energetic investigation of the binding mechanism of this complex using different values of dielectric constants (ε = 0, 4, 10, 20 and 40), which have been widely used to study the electrostatic properties of biomolecules. For this, increasing radii centered on the hygB centroid were measured from the 30S-hygB crystal structure (1HNZ.pdb), and only the individual interaction energy of each enclosed nucleotide was determined for quantum calculations using molecular fractionation with conjugate caps (MFCC) strategy. It was noticed that the dielectric constants underestimated the energies of individual interactions, allowing the convergence state is achieved quickly. But only for ε = 40, the total binding energy of drug-receptor interaction is stabilized at r = 18A, which provided an appropriate binding pocket because it encompassed the main residues that interact more strongly with the hygB - C1403, C1404, G1405, A1493, G1494, U1495, U1498 and C1496. Thus, the dielectric constant ≈ 40 is ideal for the treatment of systems with many electrical charges. By comparing the individual binding energies of 16S rRNA nucleotides with the experimental tests that determine the minimum inhibitory concentration (MIC) of hygB, it is believed that those residues with high binding values generated bacterial resistance to the drug when mutated. With the same reasoning, since those with low interaction energy do not influence effectively the affinity of the hygB in its binding site, there is no loss of effectiveness if they were replaced. / Nessa disserta??o, os princ?pios te?ricos que regem a Modelagem Molecular foram aplicados na caracteriza??o eletr?nica do oligopept?deo α3 e seus variantes (5Q,7Q)-α3, como tamb?m na descri??o qu?ntica da intera??o do aminoglicos?deo higromicina B e a subunidade 30S do ribossomo bacteriano. No primeiro estudo, os dipept?deos lineares e neutros constituintes das biomol?culas mencionados foram modelados e posteriormente otimizados at? uma estrutura de menor energia potencial e ?ngulos diedros adequados. No caso, tr?s processos de otimiza??o geom?trica, baseados subsequentemente na teoria cl?ssica newtoniana, na semi-emp?rica e na teoria do funcional da densidade (DFT), varreram a paisagem de energia de cada dipept?deos na busca de uma estrutura de energia m?nima ideal. Por fim, os conf?rmeros ?timos foram descritos quanto ao potencial eletrost?tico, energia de ioniza??o (amino?cidos), orbitais de fronteira HOMO/HOMO-1 e termo de hopping. A partir dos termos de hopping descritos nesse trabalho, foi poss?vel, em estudos subsequentes, caracterizar as propriedades de transporte de cargas destes modelos pept?dicos. Vislumbra-se uma nova tecnologia de biosensores capaz de diagnosticar doen?as amiloides, relacionadas ao ac?mulo de pept?deos disformes, a partir do perfil de condutividade el?trica apresentado pelas prote?nas do paciente. Em um segundo momento dessa disserta??o, realiza-se um estudo qu?ntico por modelagem molecular da energia de intera??o de um antibi?tico aminoglicos?dico em seu receptor riboss?mico. Sabe-se que a higromicina B (higB) ? um antibi?tico aminoglicos?deo que afeta a transloca??o ribossomal pela intera??o direta com a subunidade menor do ribossomo bacteriano (30S), especificamente com nucleot?deos da h?lice 44 do RNA riboss?mico 16S (rRNA 16S). Devido ao forte car?ter eletrost?tico desta conex?o, foi proposta a investiga??o energ?tica do mecanismo de liga??o da higB no 30S usando diferentes valores de constantes diel?tricas (ε=0, 4, 10, 20 e 40), as quais s?o amplamente utilizadas no estudo das propriedades eletrost?ticas de biomol?culas. Para isso, foram medidos raios crescentes centralizados no centr?ide da higB tendo por base a estrutura cristalina higB-30S (1HNZ.pdb), e apenas a energia de intera??o individual de cada nucleot?deo englobado foi calculada quanticamente utilizando a estrat?gia de fracionamento molecular com capuzes conjugados (MFCC). Percebeu-se que as constantes diel?tricas subestimam as energias de intera??o individuais, permitindo que o estado de converg?ncia energ?tica seja alcan?ado rapidamente. Por?m apenas para ε=40, a energia de intera??o total droga-receptor se estabilizou em r=18?, o que se constituiu como um adequado s?tio de liga??o, pois englobou os res?duos do 16S que interagem mais fortemente com a higB - C1403, C1404, G1405, A1493, G1494, U1495, C1496 e U1498. Assim, a constante diel?trica ≈40 ? ideal para o tratamento de sistemas com muitas cargas. Confrontando as energias de liga??o individuais dos nucleot?deos 16SrRNA com ensaios experimentais para determina??o da concentra??o inibit?ria m?nima (MIC) da higB, acredita-se que esses res?duos com elevados valores de intera??o gerariam resist?ncia bacteriana ? droga quando mutados. Com o mesmo racioc?nio, visto que aqueles com baixa energia n?o influenciariam de forma eficaz a afinidade da higB em seu s?tio de liga??o, n?o ocorreria perda de efic?cia caso fossem substitu?dos.
75

Transporte eletr?nico e propriedades termodin?micas de nanobiomol?culas

Bezerril, Leonardo Mafra 18 December 2009 (has links)
Made available in DSpace on 2015-03-03T15:16:23Z (GMT). No. of bitstreams: 1 LeonardoM.pdf: 1880413 bytes, checksum: c785ee7cbc933eb3ac782dc9ac382e6c (MD5) Previous issue date: 2009-12-18 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / We use a tight-binding formulation to investigate the transmissivity and the currentvoltage (I_V) characteristics of sequences of double-strand DNA molecules. In order to reveal the relevance of the underlying correlations in the nucleotides distribution, we compare theresults for the genomic DNA sequence with those of arti_cial sequences (the long-range correlated Fibonacci and RudinShapiro one) and a random sequence, which is a kind of prototype of a short-range correlated system. The random sequence is presented here with the same _rst neighbors pair correlations of the human DNA sequence. We found that the long-range character of the correlations is important to the transmissivity spectra, although the I_V curves seem to be mostly inuenced by the short-range correlations. We also analyze in this work the electronic and thermal properties along an _-helix sequence obtained from an _3 peptide which has the uni-dimensional sequence (Leu-Glu-Thr- Leu-Ala-Lys-Ala)3. An ab initio quantum chemical calculation procedure is used to obtain the highest occupied molecular orbital (HOMO) as well as their charge transfer integrals, when the _-helix sequence forms two di_erent variants with (the so-called 5Q variant) and without (the 7Q variant) _brous assemblies that can be observed by transmission electron microscopy. The di_erence between the two structures is that the 5Q (7Q) structure have Ala ! Gln substitution at the 5th (7th) position, respectively. We estimate theoretically the density of states as well as the electronic transmission spectra for the peptides using a tight-binding Hamiltonian model together with the Dyson's equation. Besides, we solve the time dependent Schrodinger equation to compute the spread of an initially localized wave-packet. We also compute the localization length in the _nite _-helix segment and the quantum especi_c heat. Keeping in mind that _brous protein can be associated with diseases, the important di_erences observed in the present vi electronic transport studies encourage us to suggest this method as a molecular diagnostic tool / Nesta tese, investigamos a transmissividade e as caracter?sticas de corrente como fun??o da diferen?a de potencial, no contexto da liga??o forte, em seq??ncias de dupla fita do DNA. Com o intuito de investigar a relev?ncia das correla??es subjacentes nas distribui??es dos nucleot?deos, comparamos os resultados de uma seq??ncia gen?mica do DNA com duas seq??ncias artificiais (Fibonacci e Rudin-Shapiro, que apresentam correla??o de longo alcance) e uma seq??ncia aleat?ria, prot?tipo de sistemas de correla??o de curto alcance. A seq??ncia aleat?ria utilizada apresenta a mesma correla??o de pares de primeiros vizinhos que a seq??ncia do DNA humano. Observamos que a caracter?stica de correla??o de longo alcance ? importante para o espectro de transmissividade, apesar das curvas IXV serem mais influenciadas por correla??es de curto alcance. Neste trabalho, analisamos tamb?m as propriedades t?rmicas e eletr?nicas de uma seq?encia α-h?lice, obtida de um pept?deo α3, o qual apresenta a seguinte seq??ncia unidimensional (Leu-Glu-Thr-Leu-Ala-Lys-Ala)3 (estrutura prim?ria). C?lculos ab initio qu?nticos s?o utilizados para obter as energias dos orbitais moleculares mais altos (HOMO, highest occupied molecular orbital), bem como suas integrais de transfer?ncias de cargas quando a seq??ncia α-h?lice forma uma estrutura fibrosa (variante 5Q) e n?o fibrosa (variante 7Q), as quais podem ser observadas atrav?s de microscopia eletr?nica de transmiss?o. A diferen?a entre as duas estruturas ? que a estrutura 5Q (7Q) apresenta a substitui??o Ala → Gln na 5a (7a) posi??o, respectivamente. N?s estimamos, teoricamente, a densidade de estado bem como o espectro de transmiss?o eletr?nico dos pept?deos, utilizando um Hamiltoniano no formalismo da liga??o-forte juntamente com a equa??o de Dyson. Al?m disso, n?s resolvemos a equa??o de Schr?dinger dependente do tempo para obter o espalhamento de um pacote de onda inicialmente localizado. N?s calculamos tamb?m o comprimento de localiza??o e, por fim, o calor espec?fico qu?ntico. Vale lembrar que a forma??o de prote?nas fibrosas podem estar associadas ? doen?as, de forma que as importantes diferen?as observadas no estudo das propriedades eletr?nicas de transporte nos encorajam a sugerir este m?todo como uma ferramenta de diagn?stico molecular
76

Contribution à la conception d'un système de radio impulsionnelle ultra large bande intelligent / No title

Akbar, Rizwan 15 January 2013 (has links)
Face à une demande sans cesse croissante de haut débit et d’adaptabilité des systèmes existants, qui à son tour se traduit par l’encombrement du spectre, le développement de nouvelles solutions dans le domaine des communications sans fil devient nécessaire afin de répondre aux exigences des applications émergentes. Parmi les innovations récentes dans ce domaine, l’ultra large bande (UWB) a suscité un vif intérêt. La radio impulsionnelle UWB (IR-UWB), qui est une solution intéressante pour réaliser des systèmes UWB, est caractérisée par la transmission des impulsions de très courte durée, occupant une largeur de bande allant jusqu’à 7,5 GHz, avec une densité spectrale de puissance extrêmement faible. Cette largeur de bande importante permet de réaliser plusieurs fonctionnalités intéressantes, telles que l’implémentation à faible complexité et à coût réduit, la possibilité de se superposer aux systèmes à bande étroite, la diversité spatiale et la localisation très précise de l’ordre centimétrique, en raison de la résolution temporelle très fine.Dans cette thèse, nous examinons certains éléments clés dans la réalisation d'un système IR-UWB intelligent. Nous avons tout d’abord proposé le concept de radio UWB cognitive à partir des similarités existantes entre l'IR-UWB et la radio cognitive. Dans sa définition la plus simple, un tel système est conscient de son environnement et s'y adapte intelligemment. Ainsi, nous avons tout d’abord focalisé notre recherché sur l’analyse de la disponibilité des ressources spectrales (spectrum sensing) et la conception d’une forme d’onde UWB adaptative, considérées comme deux étapes importantes dans la réalisation d'une radio cognitive UWB. Les algorithmes de spectrum sensing devraient fonctionner avec un minimum de connaissances a priori et détecter rapidement les utilisateurs primaires. Nous avons donc développé de tels algorithmes utilisant des résultats récents sur la théorie des matrices aléatoires, qui sont capables de fournir de bonnes performances, avec un petit nombre d'échantillons. Ensuite, nous avons proposé une méthode de conception de la forme d'onde UWB, vue comme une superposition de fonctions B-splines, dont les coefficients de pondération sont optimisés par des algorithmes génétiques. Il en résulte une forme d'onde UWB qui est spectralement efficace et peut s’adapter pour intégrer les contraintes liées à la radio cognitive. Dans la 2ème partie de cette thèse, nous nous sommes attaqués à deux autres problématiques importantes pour le fonctionnement des systèmes UWB, à savoir la synchronisation et l’estimation du canal UWB, qui est très dense en trajets multiples. Ainsi, nous avons proposé plusieurs algorithmes de synchronisation, de faible complexité et sans séquence d’apprentissage, pour les modulations BPSK et PSM, en exploitant l'orthogonalité des formes d'onde UWB ou la cyclostationnarité inhérente à la signalisation IR-UWB. Enfin, nous avons travaillé sur l'estimation du canal UWB, qui est un élément critique pour les récepteurs Rake cohérents. Ainsi, nous avons proposé une méthode d’estimation du canal basée sur une combinaison de deux approches complémentaires, le maximum de vraisemblance et la décomposition en sous-espaces orthogonaux,d’améliorer globalement les performances. / Faced with an ever increasing demand of high data-rates and improved adaptability among existing systems, which inturn is resulting in spectrum scarcity, the development of new radio solutions becomes mandatory in order to answer the requirements of these emergent applications. Among the recent innovations in the field of wireless communications,ultra wideband (UWB) has generated significant interest. Impulse based UWB (IR-UWB) is one attractive way of realizing UWB systems, which is characterized by the transmission of sub nanoseconds UWB pulses, occupying a band width up to 7.5 GHz with extremely low power density. This large band width results in several captivating features such as low-complexity low-cost transceiver, ability to overlay existing narrowband systems, ample multipath diversity, and precise ranging at centimeter level due to extremely fine temporal resolution.In this PhD dissertation, we investigate some of the key elements in the realization of an intelligent time-hopping based IR-UWB system. Due to striking resemblance of IR-UWB inherent features with cognitive radio (CR) requirements, acognitive UWB based system is first studied. A CR in its simplest form can be described as a radio, which is aware ofits surroundings and adapts intelligently. As sensing the environment for the availability of resources and then consequently adapting radio’s internal parameters to exploit them opportunistically constitute the major blocks of any CR, we first focus on robust spectrum sensing algorithms and the design of adaptive UWB waveforms for realizing a cognitive UWB radio. The spectrum sensing module needs to function with minimum a-priori knowledge available about the operating characteristics and detect the primary users as quickly as possible. Keeping this in mind, we develop several spectrum sensing algorithms invoking recent results on the random matrix theory, which can provide efficient performance with a few number of samples. Next, we design the UWB waveform using a linear combination of Bsp lines with weight coefficients being optimized by genetic algorithms. This results in a UWB waveform that is spectrally efficient and at the same time adaptable to incorporate the cognitive radio requirements. In the 2nd part of this thesis, some research challenges related to signal processing in UWB systems, namely synchronization and dense multipath channel estimation are addressed. Several low-complexity non-data-aided (NDA) synchronization algorithms are proposed for BPSK and PSM modulations, exploiting either the orthogonality of UWB waveforms or theinherent cyclostationarity of IR-UWB signaling. Finally, we look into the channel estimation problem in UWB, whichis very demanding due to particular nature of UWB channels and at the same time very critical for the coherent Rake receivers. A method based on a joint maximum-likelihood (ML) and orthogonal subspace (OS) approaches is proposed which exhibits improved performance than both of these methods individually.
77

Simulátor provozu stanic s kmitočtovým skákáním a vyhýbáním se kolizí / Simulator of stations with frequency hopping and collision avoidance

Akkizová, Dinara January 2011 (has links)
The master's thesis aims to introduce and study the issue of frequency hopping with collsion avoidance (FH/CA). On this basis, design a computer program for simulating the operation of a radio systém FHCA, who works in the band used by other systems FH/CA . This simulation programm using MATLAB software to implement verify the correctness of programs. Use simulator to obtain date about the intensity of interference systems FH/CA for the chosen scenario. This work consists of five parts: the first part consists of describing the queuing system, the second part of the description of the radio frequency system with collision avoidence FH / CA, the third part of the description of the simulation model. The fourth part includes verification of the model in the fifth and last section inspects results are shown.
78

Theoretical Studies of Structural and Electronic Properties of Donor-Acceptor Polymers

Günther, Florian 17 September 2018 (has links)
The development of new electronic devices requires the design of novel materials since the existing technologies are not suitable for all applications. In recent years, semiconducting polymers (SCPs) have evolved as fundamental components for the next generation of costumer electronics. They provide interesting features, especially flexibility, light weight, optical transparency and low-cost processability from solution. The research presented in this thesis was devoted to theoretical studies of donor-acceptor (DA) copolymers formed by electron-deficient 3,6-(dithiophene-2-yl)-diketopyrrolo[3,4-c]pyrrole (TDPP) and different electron-rich thiophene compounds. This novel type of SCPs has received a lot of attention due to experimental reports on very good electronic properties which yielded record values for organic field-effect transistor applications. In order to get a deeper understanding of the structural and electronic properties, the main objective of this work was to study this material type on the atomic scale by means of electronic structure methods. For this, density functional theory (DFT) methods were used as they are efficient tools to consider the complex molecular structure. This work comprises three main parts: a comparative study of the structural and the electronic properties of TDPP based DA polymers obtained by means of different theory levels, the calculation of the intermolecular charge transfer between pi-pi stacked DA polymer chains based on the Marcus transfer theory and investigations of molecular p-doping of TDPP based DA polymers. For the first, DFT using different functionals was compared to the density functional based tight binding (DFTB) method, which is computationally very efficient. Although differences in structural properties were observed, the DFTB method was found to be the best choice to study DA polymers in the crystalline phase. For the second, correlations between the molecular structure and the reorganization energy are found. Moreover, the dependency of the electronic coupling element on the spatial shape of the frontier orbitals is shown. Furthermore, a Boltzmann-type statistical approach is introduced in order to enable a qualitative comparison of different isomers and chemical structures. For the last part, the p-doping properties of small, multi-polar dopant molecules with local dipole provided by cyano groups were investigated theoretically and compared with experimental observations. The one with the strongest p-doping properties was studied in this work for the first time on a theoretical basis. Comparing these different p-dopants, rich evidence was found supporting the experimentally observed doping strength.
79

Analysis of the rolling motion of loaded hoops

Theron, Willem F.D. 03 1900 (has links)
Thesis (PhD (Mathematical Sciences. Applied Mathematics))--University of Stellenbosch, 2008. / This dissertation contains a detailed report on the results of a research project on the behaviour of a dynamical system consisting of a hoop to which a heavy particle is fixed at the rim. This loaded hoop rolls on a rough surface while remaining in the vertical plane. The motion of the hoop consists of various, possibly alternating, phases consisting of rolling without slipping, spinning or skidding motion and in some cases ends by hopping off the surface. A general mathematical model is developed, consisting of a system of second order ordinary differential equations, one for each of the three degrees of freedom. Analytic solutions are obtained in some cases; otherwise numerical solutions are used. Three specific applications of the general model are dealt with. In the first application the problem of massless hoops is investigated. The main emphasis is on the somewhat controversial question of what happens after the normal reaction becomes zero in a position where the particle is still moving downwards. A new result shows that the hoop can continue to move horizontally in a motion defined as skimming. The second application deals with rigid hoops and a large number of detailed results are presented. Classification schemes for the different types of behaviour are introduced and summarised in the form of phase diagrams. Some emphasis is placed on the rather amazing number of different patterns of motion that can be obtained by varying the parameters. In the third application two elastic models are analysed, with the primary purpose of explaining one aspect of the reported behaviour of experimental hoops, namely hopping while the particle is moving downwards. A chapter on experimental models rounds off the project.
80

Conducting Polymers Containing In-Chain Metal Centres : Electropolymerisation and Charge Transport

Hjelm, Johan January 2003 (has links)
<p>Conjugated polymers that exhibit high electronic conductivities play key roles in the emerging field of molecular electronics. In particular, linking metal centres with useful electrochemical, photophysical, or catalytic properties to the backbone, or within the polymer chain itself, is a topic which has attracted a significant amount of interest lately. Structurally rigid monomers that can be electropolymerised to form highly conducting molecular wires may provide new insights into conduction mechanisms, e.g., exploiting resonant superexchange (electron-hopping) by tuning the energies of redox centre and bridge states. The focus of this thesis lies on the electrochemical investigation of preparation, growth dynamics, and charge transport dynamics of oligothiophene/transition metal hybrid materials. The incorporation of ruthenium(II) and osmium(II) terpyridine complexes into such polymeric assemblies was accomplished by an electropolymerisation procedure, to produce rod-like oligothienyl-bridged metallopolymers. The properties of the monomers used were characterised by optical spectroscopy and electrochemical techniques. Charge transport was studied in detail for some of the materials created, and it was found that the electron transport rate and dc conductivity was enhanced by up to two orders of magnitude compared to relevant non-conjugated polymers, demonstrating the usefulness of this approach for optimization of charge transport in metallopolymers. The charge transport diffusion coefficent was determined to (2.6 ± 0.5) x 10<sup>-6</sup> cm<sup>2</sup> s<sup>-1</sup> for a quaterthienyl-bridged {Os(tpy)<sub>2</sub>} polymer by use of an electrochemical steady-state method carried out using a transistor-like experimental geometry. It was found that charge transport in these materials is concentration-gradient driven. The rate limiting step of the charge transport process was investigated using electrochemical impedance spectroscopy. The electropolymerisation dynamics of one of the monomers was studied using microelectrodes, and the results obtained shows that electropolymerisation is highly efficient, and indicate that mass transport controls this process. Through a combination of controlled potential deposition and SEM imaging it was demonstrated that it is possible to exploit the edge effect of microelectrodes to promote film growth in a direction co-planar with the electrode surface.</p>

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