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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.
51

Photophysical Properties of Organic and Organometallic molecules

Rubio Pons, Oscar January 2004 (has links)
<p>Highly correlated quantum chemical methods have been appliedto study the photophysical properties of substituted benzenes.With the inclusion of spin-orbit coupling, the phosphorescencesof these molecules have been calculated usingMulti-CongurationalSelf- Consistent Field (MCSCF) quadraticresponse theory. The Herzberg-Teller approximation has beenadopted to evaluate the vibronic contributions tophosphorescence.</p><p>The performance of hybrid density functional theory (DFT) atthe B3LYP level is examined in comparison to the MP2, CCSD andCCSD(T) methods for the geometry and permanent dipole moment ofp-aminobenzoic acid. The time-dependent DFT/B3LYP method isapplied to calculate the two-photon absorption of a series ofZinc-porphyrin derivatives in combination with a two-statemodel. The transitions between excited singlet and tripletstates of Zinc and Platinum based organometallic compounds havebeen computed using DFT quadratic response theory. The resultsare used to simulate the non-linear propagation of laser pulsesthrough these materials utilizing a dynamical wave propagationmethod.</p>
52

Étude par absorption transitoire de naphtopyranes liés à des oligothiophènes par différents types de jonctions

Moine, Baptiste 07 December 2006 (has links) (PDF)
Une série de naphtopyranes, substitués en position 3 et 8 par des oligothiophènes via différents types de jonctions, a récemment été synthétisée en vue d'élaborer des polymères conducteurs de type polythiophène comportant un interrupteur photo-commandable. Dans cette famille, le photochromisme met en jeu la rupture de la liaison simple carbonespiro-oxygène. Nous présentons ici une étude des propriétés photophysiques et photochimiques de ces composés en solution réalisée par absorption transitoire dans le domaine de la femtoseconde à la microseconde. Nous avons observé que l'accroissement de la longueur de la chaîne oligothiophénique s'accompagne d'une augmentation de la durée de vie de l'état S<sub>1</sub> et d'une diminution de son énergie. L'accroissement de la conjugaison entre la chaîne et le naphtopyrane produit un effet similaire. Nous pensons que lorsque la chaîne oligothiophénique est courte et peu conjuguée, la réaction d'ouverture de cycle désactive l'état S<sub>1</sub> de manière ultrarapide. Au contraire, lorsque cette chaîne devient longue et fortement conjuguée, l'énergie globale de S<sub>1</sub> passe sous un seuil et on observe la perte du caractère photochrome. La réaction d'ouverture de cycle ne désactive plus l'état S<sub>1</sub> ce qui explique l'augmentation de son temps de vie. On observe alors la formation d'un état triplet non réactif et l'apparition de fluorescence. Pour certains composés intermédiaires, on remarque à la fois la formation de photomérocyanine et d'état triplet. Enfin la substitution en position 3 par des oligothiophènes tend à favoriser la production de forme ouverte en abaissant la barrière énergétique de la réaction d'ouverture de cycle.
53

DNA Replication and Trinucleotide Repeat Instability in Myotonic Dystrophy Type 1

Cleary, John 06 August 2010 (has links)
The expansion of gene-specific trinucleotide repeats is responsible for a growing list of human disorders, including myotonic dystrophy type 1 (DM1). Repeat instability for most of these disorders, including DM1, is characterized by complex patterns of inherited and ongoing tissue-specific instability and pathogenesis. While the mechanistic basis behind the unique locus-specific instability of trinucleotide repeats is currently unknown, DNA metabolic processes are likely to play a role. My thesis involves investigating the contribution of DNA replication to the trinucleotide instability of myotonic dystrophy type 1. Herein I have designed an in vivo primate model system, based on the SV40 replication system, to assess the contribution of DNA replication to DM1 repeat instability. This system allows the assessment, under controlled conditions, and manipulation of variables that may affect replication-associated repeat instability, under a primate cellular system. Using the SV40 model system, I not only confirmed previous observations that repeat length and replication direction affect repeat instability, but also for the first time determined that the location of the replication origin relative to the repeat tract plays an important role in repeat instability. This novel observation allowed for the development of a fork-shift model of repeat instability, in which cis-elements adjacent to the repeat tract affect replication, in turn altering the propensity for repeat instability. To further my study of DNA replication in DM1 repeat instability, I have mapped the origin of replication adjacent to the DM1 locus in human patient cells and the tissues of DM1 transgenic mice actively undergoing repeat instability. The position of the replication origins adjacent to the repeat tract at the DM1 locus places several known cis-elements, including CTCF binding sites, in a position to alter replication as predicted by the fork-shift model. My analysis of the CTCF sites showed them capable of altering replication and repeat instability at the DM1 locus. Taken together these results suggest that the placement of replication origins, repeat tracts and cis-elements, may mark trinucleotide repeat tracts, such as the DM1, for locus-, tissue- and development-specific replication-associated repeat instability.
54

Estudo da supercondutividade nos sistemas intermetálicos não-centrossimétricos de composição YCo1-xC2 e Lu1-xThxNiC2 / Analysis of the superconductivity in the intermetallic noncentrosymmetric systems YCo1-xC2 and Lu1-xThxNiC2

Velazquez, Orlando Cigarroa 20 November 2015 (has links)
Recentemente, os compostos não-centrossimétricos têm sido intensamente estudados devido à grande variedade de comportamentos magnéticos, os quais são induzidos pela ausência de centro de simetria na sua estrutura cristalográfica. Esta assimetria induz uma modificação na estrutura de bandas, causando um acoplamento spin-orbita antissimétrico quem é responsável por mecanismos de interação magnética inusuais. A supercondutividade em este tipo de compostos apresenta propriedades que divergem do comportamento esperado pela teoria BCS. Neste trabalho será apresentado um estudo sobre a investigação de supercondutividade em dois sistemas ternários, Y-Co-C e Lu-Ni-C particularmente nos compostos YCo1-xC2 e Lu1-xThNiC2. Estes compostos cristalizam na estrutura CeNiC2 de simetria ortorrômbica é do grupo espacial 38 Amm2 que não possui centro de inversão. As técnicas de caracterização usadas neste trabalho incluem medidas de magnetização, resistividade e calor especifico como funções da temperatura, assim como magnetização como função do campo magnético aplicado. O composto YCo0.7C2 é supercondutor com Tc = 4 K e exibe um comportamento que diverge da teoria BCS. As medidas realizadas neste trabalho sugerem que este material é um forte candidato como supercondutor não convencional, onde poderia existir uma mistura de contribuições nos canais singleto e tripleto. No caso do sistema Lu1-xThxNiC2 os resultados preliminares indicam claramente supercondutividade nos compostos dopados com Th, onde a composição Lu0.6Th0.4NiC2 apresenta uma Tc= 8 K. / In recent years, non-centrosymmetric compounds have attracted a great interest because of their wealth variety of topical behaviors, induced by the lack of the inversion center on the crystallographic structure. This asymmetry leads to a strong modification in the band structures, causing an antisymmetric spin-orbit coupling which is responsible for unusual magnetic interaction mechanisms. Superconductivity in compounds whose crystal structure lacks inversion symmetry are known to display intriguing properties that deviate from conventional BCS superconducting behavior. Here we report the analysis of the ternary systems Y-Co-C and Lu-Ni-C, We focused our analysis in the intermetallic compounds YCo1-xC2 and Lu1-xThxNiC2. Magnetization, resistivity, and heat capacity measurements on polycrystalline samples of noncentrosymmetric YCo0.7C2, showing clear evidence of bulk superconductivity with a critical temperature of Tc =4 K. Interestingly the specific heat of the superconducting state deviates from conventional exponential temperature dependence, which is suggestive of possible unconventional superconducting behavior in YCo0.7C2, similar to that seen in the isostructural and isoelectronic superconductor LaNiC2. Besides, these results strongly suggest that this material is a strong candidate of multiband superconductivity. In the case of the system Lu1- xThxNiC2 our results showed a clear superconducting signal in the Th doped samples, where the composition Lu0.6Th0.4NiC2 has a Tc= 8 K.
55

Synthesis of Rigidly Linked Polychromophores for Intramolecular Energy Transfer Study

Zhang, Rong 09 January 2002 (has links)
Intramolecular energy transfer is reviewed from several perspectives, such as the generally accepted mechanism and molecular structure dependence. Some unique molecules with bichromophores or trichromophores linked by rigid bridges were designed to serve as models for studying the intramolecular triplet-triplet energy transfer. Bichromophoric molecules containing an anthracene donor and phenanthrene or diphenylpolyene acceptors linked by linearly fused norbornane units were synthesized. Approaches to the analogous compounds with anthracene as the donor and benzophenone or p-terphenyl as acceptors are presented. Synthetic approaches to cis, exo-1, 4-dihydro-1, 4-methanotriphenylene, a precursor to the polynorbornyl-linked polychromophore, and trichromophoric compounds linked by adamantane spacers were explored.
56

Estudo da supercondutividade nos sistemas intermetálicos não-centrossimétricos de composição YCo1-xC2 e Lu1-xThxNiC2 / Analysis of the superconductivity in the intermetallic noncentrosymmetric systems YCo1-xC2 and Lu1-xThxNiC2

Orlando Cigarroa Velazquez 20 November 2015 (has links)
Recentemente, os compostos não-centrossimétricos têm sido intensamente estudados devido à grande variedade de comportamentos magnéticos, os quais são induzidos pela ausência de centro de simetria na sua estrutura cristalográfica. Esta assimetria induz uma modificação na estrutura de bandas, causando um acoplamento spin-orbita antissimétrico quem é responsável por mecanismos de interação magnética inusuais. A supercondutividade em este tipo de compostos apresenta propriedades que divergem do comportamento esperado pela teoria BCS. Neste trabalho será apresentado um estudo sobre a investigação de supercondutividade em dois sistemas ternários, Y-Co-C e Lu-Ni-C particularmente nos compostos YCo1-xC2 e Lu1-xThNiC2. Estes compostos cristalizam na estrutura CeNiC2 de simetria ortorrômbica é do grupo espacial 38 Amm2 que não possui centro de inversão. As técnicas de caracterização usadas neste trabalho incluem medidas de magnetização, resistividade e calor especifico como funções da temperatura, assim como magnetização como função do campo magnético aplicado. O composto YCo0.7C2 é supercondutor com Tc = 4 K e exibe um comportamento que diverge da teoria BCS. As medidas realizadas neste trabalho sugerem que este material é um forte candidato como supercondutor não convencional, onde poderia existir uma mistura de contribuições nos canais singleto e tripleto. No caso do sistema Lu1-xThxNiC2 os resultados preliminares indicam claramente supercondutividade nos compostos dopados com Th, onde a composição Lu0.6Th0.4NiC2 apresenta uma Tc= 8 K. / In recent years, non-centrosymmetric compounds have attracted a great interest because of their wealth variety of topical behaviors, induced by the lack of the inversion center on the crystallographic structure. This asymmetry leads to a strong modification in the band structures, causing an antisymmetric spin-orbit coupling which is responsible for unusual magnetic interaction mechanisms. Superconductivity in compounds whose crystal structure lacks inversion symmetry are known to display intriguing properties that deviate from conventional BCS superconducting behavior. Here we report the analysis of the ternary systems Y-Co-C and Lu-Ni-C, We focused our analysis in the intermetallic compounds YCo1-xC2 and Lu1-xThxNiC2. Magnetization, resistivity, and heat capacity measurements on polycrystalline samples of noncentrosymmetric YCo0.7C2, showing clear evidence of bulk superconductivity with a critical temperature of Tc =4 K. Interestingly the specific heat of the superconducting state deviates from conventional exponential temperature dependence, which is suggestive of possible unconventional superconducting behavior in YCo0.7C2, similar to that seen in the isostructural and isoelectronic superconductor LaNiC2. Besides, these results strongly suggest that this material is a strong candidate of multiband superconductivity. In the case of the system Lu1- xThxNiC2 our results showed a clear superconducting signal in the Th doped samples, where the composition Lu0.6Th0.4NiC2 has a Tc= 8 K.
57

Reatividade de lipídeos e metabólitos da cafeína frente a estados excitados de flavinas / Reactivity of lipids and caffeine metabolites front of excited states of flavins

Scurachio, Regina Spricigo 18 September 2015 (has links)
A presente tese descreve o estudo cinético e mecanístico da desativação do estado singlete- e triplete-excitado de flavinas por esteróis (colesterol e ergosterol), vitamina D, coenzima Q10, vitamina K, ácidos graxos e metabólitos da cafeína. Através da análise de Stern-Volmer da supressão de fluorescência da riboflavina pelo colesterol, ergosterol, vitamina D, vitamina K, e pela coenzima Q10 observa-se que o estado singlete excitado da riboflavina é desativado com constante de velocidade superior ao limite da difusão. No entanto, a presença de colesterol, ergosterol, vitamina D, vitamina K e coenzima Q10 não afeta o tempo de vida do estado singlete excitado da riboflavina como demonstrado por experimentos de contagem de fótons resolvido no tempo sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo 1:1 formado entre a riboflavina e a vitamina D apresenta Ka = 4 x 104 &plusmn; 3 mol&sdot;L-1 a 25 0C com &Delta;H0 = -36 &plusmn; 7 kJ&sdot;mol-1 e &Delta;S0 = -5 &plusmn; 3 J&sdot;mol-1 &sdot;K-1. O complexo 1:1 entre a riboflavina e a vitamina K (vit K) e a riboflavina com a coenzima Q10 (CoQ10) apresentam Ka = 1 x 103 &plusmn; 1 mol&sdot;L-1 com &Delta;H0 = -110 &plusmn; 22 kJ&sdot;mol-1 e &Delta;S0 = 51 &plusmn; 9 J &sdot;mol-1&sdot;K-1 para a vit K e Ka = 4 x 102 &plusmn; 1 mol&sdot;L-1, &Delta;H0 = -120 &plusmn; 27 kJ &sdot;mol-1 e &Delta;S0 = 41 &plusmn; 7 J &sdot;mol-1&sdot;K-1 para a CoQ10 a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes bimoleculares de velocidade variando de 1,4 x 108 L &sdot;mol-1&sdot;s-1 (vit D) a 1,4 x 109 L &sdot;mol-1&sdot;s-1 (CoQ10). Observa-se supressão da emissão de fluorescência da riboflavina na presença de metabolitos da cafeína, no entanto, sem alterar o tempo de vida do estado singlete excitado da riboflavina sugerindo a formação de um complexo precursor [riboflavina...substrato]. O complexo formado entre a riboflavina e os metabólitos da cafeína apresentam Ka = 295 &plusmn; 1 mol&sdot;L-1 com &Delta;H0 = -45 &plusmn; 8 kJ&sdot;mol-1 e &Delta;S0 = 12 &plusmn; 1 J&sdot;mol-1&sdot;K-1 para o ácido 1,7-dimetil úrico, Ka = 289 &plusmn; 1 mol&sdot;L-1 com &Delta;H0 = -38 &plusmn; 5 kJ &sdot;mol-1 e &Delta;S0 = 9 &plusmn; 2 J &sdot;mol-1&sdot;K-1 para o ácido 1-metil úrico e Ka = 275 &plusmn; 1 mol&sdot;L-1 com &Delta;H0 = 16 &plusmn; 3 kJ &sdot;mol-1 e &Delta;S0 = 6 &plusmn; 1J &sdot;mol-1&sdot;K-1 para a 1,7-dimetilxantina a 25 0C. Para a desativação do estado triplete da riboflavina, foram obtidas constantes de velocidade de 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimetilxantina, 3kq = 1,0 x 108 L.mol-1.s-1 para o ácido 1,7-dimetil úrico e 3kq = 1,4 x 108 L.mol-1.s-1 para o ácido 1-metil úrico. Os ésteres metílicos (oleato de metila, ácido linoléico conjugado (CLA), linoleato de metila, linolenato de metila, araquidonato de metila, eicosapentanoato de metila, e docosahexanoato de metila) não desativam o estado singlete-excitado da riboflavina. Entretanto, os ésteres metílicos se mostraram reativos frente ao estado triplete da riboflavina com constantes de velocidades 3kq variando de 8,4 x 105 a 3,3 x 107 L&sdot;smol-1 &sdot;s-1 com uma dependência linear do número de hidrogênios bis-alílicos com excessão do CLA. / The present thesis describes the kinetic and mechanistic studies of flavin singlet- and triplet-excited states deactivation by sterols (ergosterol and cholesterol), vitamin D, coenzyme Q10, vitamin K, fatty acids, and caffeine metabolites. From the Stern-Volmer analysis of the riboflavin fluorescence quenching by cholesterol, ergosterol, vitamin D, vitamin K and coenzyme Q10, it is noted that the singlet-excited state of riboflavin is deactivated with a rate constant exceeding the diffusion limit. However, the presence of cholesterol, ergosterol, vitamin D, vitamin K, coenzyme Q10 did not affect the lifetime of singlet-excited riboflavin as probed by single photon counting experiments suggesting the formation of a ground-state precursor complex [riboflavin ...substrate]. The 1:1 complex formed between riboflavin and vitamin D showed Ka = 4 x 104 &plusmn; 3 mol&sdot;L-1 a 25 0C with &Delta;H0 = -36 &plusmn; 7 kJ&sdot;mol-1 and &Delta;S0 = -5 &plusmn; 3 J&sdot;mol-1 &sdot;K-1. The 1:1 complex formed between riboflavin and vitamin K (vit K) and riboflavin with coenzyme Q10 (CoQ10) showed Ka = 1 x 103 &plusmn; 1 mol&sdot;L-1 with &Delta;H0 = -110 &plusmn; 22 kJ&sdot;mol-1 and &Delta;S0 = 51 &plusmn; 9 J &sdot;mol-1&sdot;K-1 for vit K e Ka =4 x 102 &plusmn; 1 mol&sdot;L-1, &Delta;H0 = -120 &plusmn; 27 kJ &sdot;mol-1 and &Delta;S0 = 41 &plusmn; 7 J &sdot;mol-1&sdot;K-1 for CoQ10 a 25 0C. For the deactivation of triplet riboflavin, bimolecular rate constants were found to vary from 1,4 x 108 L &sdot;mol-1&sdot;s-1 (vit D) a 1,4 x 109 L &sdot;mol-1&sdot;s-1 (CoQ10). The caffeine metabolites quench fluorescence emission of riboflavin however, without affecting the lifetime of the singlet-excited state, suggesting the formation of a ground state precursor complex [riboflavin ... substrate]. The complex formed between riboflavin and caffeine metabolites showed Ka = 295 &plusmn; 1 mol&sdot;L-1 with &Delta;H0 = -45 &plusmn; 8 kJ&sdot;mol-1 and &Delta;S0 = 12 &plusmn; 1 J&sdot;mol-1&sdot;K-1for 1,7-dimetyl uric acid, Ka = 289 &plusmn; 1 mol&sdot;L-1 with &Delta;H0 = -38 &plusmn; 5 kJ &sdot;mol-1 and &Delta;S0 = 9 &plusmn; 2 J &sdot;mol-1&sdot;K-1 for 1-methyl uric acid and Ka = 275 &plusmn; 1 mol&sdot;L-1 with &Delta;H0 = 16 &plusmn; 3 kJ &sdot;mol-1 and &Delta;S0 = 6 &plusmn; 1J &sdot;mol-1&sdot;K-1 for 1,7-dimethylxanthine at 25 0C. For the deactivation of triplet riboflavin, rate constant were obtained with 3kq = 4,2 x 108 L.mol-1.s-1 para a 1,7-dimethylxanthine, 3kq = 1,0 x 108 L.mol-1.s-1 for 1,7-dimethyl uric acid, and 3kq = 1,4 x 108 L.mol-1.s-1 for 1-methyl uric acid. The methyl esters (methyl oleate, conjugated linoleic acid (CLA), methyl linoleate, methyl linoleate, methyl arachidonate, methyl eicosapentanoate, and methyl docosahexanoate) did not quench the singlet-excited riboflavin. However, the methyl esters were shown to be reactive towards triplet riboflavin with rate constants ranging from 8,4 x 105 a 3,3 x 107 L&sdot;mol-1 &sdot;s-1and depending linearly with the number of bis-allylic hydrogens with exception to CLA.
58

Action spectrale en géométrie non commutative et calcul pseudodifférentiel global

Levy, Cyril 12 June 2009 (has links) (PDF)
Dans cette thèse nous avons étudié certaines questions mathématiques associées au calcul de l'action spectrale de Chamseddine--Connes sur des exemples fondamentaux de triplets spectraux non commutatifs, tels que le tore non commutatif et la 3-sphère quantique SUq(2). Nous avons montré en particulier qu'une condition diophantienne sur la matrice de déformation du tore est cruciale pour obtenir l'action spectrale en tenant compte de la structure réelle. <br />Nous avons aussi étudié la question de l'existence de tadpoles (termes linéaires par rapport au potentiel de jauge de la fluctuation de la métrique dans l'action spectrale) dans le cas de géométries riemanniennes commutatives, et la construction d'un calcul pseudodifférentiel global permettant une généralisation du produit de Weyl--Moyal sur un espace de Schwartz de sections rapidement décroissantes sur un fibré cotangent d'une variété avec linéarisation.
59

Excitation transfer between conjugated polyelectrolytes and triplet emitter confined in protein nanowires

Thinprakong, Chorpure January 2010 (has links)
<p>Phosphorescent metal complexes can be incorporated into amyloid-like fibrils, and these fibrils can be decorated with conjugated polyelectrolytes (CPEs). In this study, <em>fac</em>-tris[2-phenylpyridinato-<em>C</em><sup>2</sup>,N]irdium(III) complexes [Ir(piq)<sub>3</sub>] were used as the phosphorescence emitter and Sodium-poly(3-thiophene acetic acid) (PTAA-Na) compounds were used as CPEs. Herein we study the energy transfer processes between the iridium complexes and the CPEs. To investigate these mechanisms, the analysis of the emission quenching and time-resolved measurements were done. Our measurements show that energy can be transfered from singlet state of PTAA to the singlet state of Ir(piq)<sub>3</sub>. Moreover, incorporation of iridium into amyloid fibrils decreases the importance of energy transfer by the Dexter mechanism. Finally we propose a geometry of interaction to explain the obtained results.</p>
60

Synthesis and development of compounds for nonlinear absorption of light

Kindahl, Tomas January 2012 (has links)
High-intensity light — for instance that from a laser — can be destructive, not only to the human eye, but also to equipment such as imaging sensors and optical communication devices. Therefore, effective protection against such light is desirable. A protection device should ideally have high transmission to non-damaging light, and should also be fast-acting in order to effectively stop high-intensity light. In working towards a protection device, there is a need to conduct fundamental research in order to understand the processes involved. One of the photophysical processes of special interest in the field of optical power limiting (OPL) is reverse saturable absorption, where a compound in an excited state absorbs light more strongly than it does in its ground state. In this work, several novel organoplatinum compounds for OPL, rationally designed to have a strong reverse saturable absorption, have been synthesized. The compounds have been analyzed using linear and nonlinear absorption spectroscopy, luminescence spectroscopy, and quantum chemistry calculations to gain further knowledge regarding their photophysical properties. In addition to this fundamental research, the absorption capabilities of some of these compounds indicate that they can be used for OPL applications. Consequently, compounds from these studies have been incorporated into a sol–gel glass that could be used in optical systems. / <p>Finansiellt stöd från Kempestiftelsen.</p>

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