.

Spectroscopic second-harmonic generation (SHG) and reflectance-anisotropy spectroscopy (RAS) are used to probe molecular adsorption on clean reconstructed single-domain stepped Si(001) in ultra-high vacuum (UHV). We implement a simplified bond hyperpolarizability model (SBHM) as a common microscopic analysis for SHG and RAS. Three different scenarios are studied: (i) The dissociative adsorption of molecular hydrogen on dangling bonds of D[subscript B] step-edges. (ii) Structural changes to rebonded r-D[subscript B] steps induced by exposure to atomic hydrogen. (iii) The adsorption of cyclopentene on Si(001)(2x1) terrace dimers in a [2+2] cycloaddition pathway. Using the SBHM we develop a new optical fingerprinting method to isolate, identify and monitor individual types of bonds (e.g. dimers, rebonds, dangling bonds, backbonds) and their chemical activity on a single-domain stepped Si(001) surface using nonresonant, but rotationally-anisotropic, second-harmonic generation (RA-SHG). The methods presented here will be applicable to many material systems and allow to track, in-situ and in real-time, the chemical action of adsorbates on surfaces. / text

Palladium-catalyzed olefin dioxygenation is a powerful tool in the generation of complex and valuable substrates, one which may become complimentary to the well known Sharpless dihydroxylation. In this work the mechanism of this transformation is examined via reaction kinetics and Hammett studies, which corroborate a PdII/IV catalytic cycle and suggest that the rate determining step is the oxidation of PdII to PdIV. Olefin dioxygenation was also found to proceed in the presence of catalytic quantities of BF3•OEt2 or triflic acid, with stoichiometric hypervalent iodine oxidant and an acetic acid solvent. Furthermore, asymmetric variants of intramolecular palladium-catalyzed olefin dioxygenation were also investigated, which resulted in the formation of tetrahydrofuran products in up to 36% ee. Next, chelate-assisted C–H bond functionalization of indoles at the C7 position and of carbazoles at the C1 position was investigated with a variety of arylation, halogenation and oxygenation techniques. Lastly, our efforts towards the synthesis of a mono-phosphine based [5]helicene ligand via olefin metathesis and photocyclization strategies will be discussed.

Palladium-catalyzed olefin dioxygenation is a powerful tool in the generation of complex and valuable substrates, one which may become complimentary to the well known Sharpless dihydroxylation. In this work the mechanism of this transformation is examined via reaction kinetics and Hammett studies, which corroborate a PdII/IV catalytic cycle and suggest that the rate determining step is the oxidation of PdII to PdIV. Olefin dioxygenation was also found to proceed in the presence of catalytic quantities of BF3•OEt2 or triflic acid, with stoichiometric hypervalent iodine oxidant and an acetic acid solvent. Furthermore, asymmetric variants of intramolecular palladium-catalyzed olefin dioxygenation were also investigated, which resulted in the formation of tetrahydrofuran products in up to 36% ee. Next, chelate-assisted C–H bond functionalization of indoles at the C7 position and of carbazoles at the C1 position was investigated with a variety of arylation, halogenation and oxygenation techniques. Lastly, our efforts towards the synthesis of a mono-phosphine based [5]helicene ligand via olefin metathesis and photocyclization strategies will be discussed.

No description available.

The chiral vicinal diamine moiety is “privileged” and is widely found in catalysts and bio-active compounds. A series of seven chiral vicinal diamines with heterocyclic substituents have been synthesized with great enantiospecificity via the resonance assisted hydrogen bond driven diaza-Cope rearrangement reaction using 1,2-bis(2-hydroxyphenyl)-1,2-diaminoethane and heterocyclic aldehydes as starting materials. This thesis will also discuss the development of a new guanidine-based chiral shift rea-gent for determining the enantiopurity and the absolute configuration of α-amino acids by proton nuclear magnetic resonance (1H NMR) spectroscopy. The chiral shift reagent is easily synthesized from the commercially-available 1,2-diphenyl-1,2-diaminoethane. This method is advantageous over many previously described procedures for determining amino acid enantiopurity as it does not require prior derivatization of the analyte.

The chiral vicinal diamine moiety is “privileged” and is widely found in catalysts and bio-active compounds. A series of seven chiral vicinal diamines with heterocyclic substituents have been synthesized with great enantiospecificity via the resonance assisted hydrogen bond driven diaza-Cope rearrangement reaction using 1,2-bis(2-hydroxyphenyl)-1,2-diaminoethane and heterocyclic aldehydes as starting materials. This thesis will also discuss the development of a new guanidine-based chiral shift rea-gent for determining the enantiopurity and the absolute configuration of α-amino acids by proton nuclear magnetic resonance (1H NMR) spectroscopy. The chiral shift reagent is easily synthesized from the commercially-available 1,2-diphenyl-1,2-diaminoethane. This method is advantageous over many previously described procedures for determining amino acid enantiopurity as it does not require prior derivatization of the analyte.

Orientador: Fernando Antônio Santos Coelho / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T04:45:55Z (GMT). No. of bitstreams: 1 Santos_MariliaSimaodos_M.pdf: 8319783 bytes, checksum: b09561f94bf536402f8e5e21e0e6dc3c (MD5) Previous issue date: 2012 / Resumo: A potenciabilidade sintética dos adutos de Morita-Baylis-Hillman foi explorada no desenvolvimento de uma nova estratégia para a preparação de compostos tricarbonilados vicinais e derivados ciclopenta[b]indólicos. Os compostos tricarbonilados vicinais representam um padrão estrutural de grande interesse sintético, pois são empregados na síntese de heterociclos e diversas moléculas com atividade biológica. A metodologia desenvolvida envolve três etapas que constituem na síntese do aduto de MBH e de duas oxidações subsequentes. A rota se mostrou rápida, simples e eficiente, com rendimentos globais variando entre 15-75%. Além da facilidade operacional essa estratégia é quimicamente sustentável já que apresenta um baixo nível de geração de resíduos químicos. Os núcleos ciclopenta[b]indólicos estão presentes na estrutura de diversos produtos naturais e moléculas bioativas, fato que se torna um estímulo para o desenvolvimento de novas rotas sintéticas. A estratégia baseia-se na oxidação do aduto de MBH seguida de adição de Michael utilizando indol. O produto gerado sofre redução e em seguida é ciclizado em meio ácido levando à obtenção do núcleo de interesse. A síntese se mostrou altamente diastereosseletiva e o mecanismo da etapa de ciclização foi investigado através de espectrometria de massas. Os compostos foram avaliados contra algumas linhagens de células tumorais exibindo atividade citótóxica promissora / Abstract: The synthetic potential of Morita-Baylis-Hillman adducts was exploited towards the development of a new strategy for the preparation of vicinal tricarbonyl compounds and cyclopenta [b] indole derivatives. The vicinal tricarbonyl compounds represent a structural pattern of great synthetic interest because they are employed in the synthesis of heterocycles and several biologically active compounds. The three steps methodology involves the the preparation of MBH adducts, followed by two subsequent oxidations. The route proved to be fast, simple and efficient, with overall yields ranging from 15 to 75%. This strategy is operationally ease and sustainable, since a low level of waste is generated. The nuclei cyclopenta [b]indoles are present in the structure of some natural products and bioactive compounds. This has stimulated efforts towards the development of new synthetic routes to prepare this heterocyclic pattern. Our strategy is based on the oxidation of MBH adduct followed by Michael addition using indole as nucleophile to provide a substituted b-ketoester. The keto carbonyl was reduced and the substituted b-hydroxyester was therefore cyclized in acid conditions leading the desired heterocycles. The synthesis was highly diastereoselectivity and mechanism of the cyclization step was monitored by mass spectrometry. The compounds were evaluated against some tumor cell lines exhibiting promising cytotoxic activity / Mestrado / Quimica Organica / Mestra em Química

Made available in DSpace on 2014-07-29T16:24:14Z (GMT). No. of bitstreams: 1 JOaO FONSECA DE OLIVEIRA.pdf: 1294832 bytes, checksum: 022b50e9a3fc392dd2bef5f7fcc5d895 (MD5) Previous issue date: 2008-02-21 / This work was developed mainly aiming the determination of the erodibility and the critical shear stress in non-paved roads, focusing on the reduction of the eminent risks of occurring erosion in these roads, based upon a drainage system dimensioning using local resistance values. In order to achieve these values a yield simulator was built, which model consists of an improved version of the equipment proposed by Griebeler (2005), utilized in superficial yield testing directly at the drainage channel of the road and in collecting the eroded material. The simulator was installed in soils of roads of Goiânia (E1), Baliza (E2), Doverlândia (E3) and Morrinhos (E4, E5 e E6) , all of which are in the state of Goiás. The tests were performed with three repetitions for each passage of the vicinal roads. For each test were utilized five channels with different crescent volumetric flow rates, in a way to simulate the ascending curve of a yielding hydrogram, where each channel was collected in a proper recipient, for later determination of the amount of eroded material (debris). Samples were also collected from non-deformed soil, utilizing an Uhland sampler, aiming to determine the density of the soil. Furthermore, the declivity of the road and samples for characterizing the granulometric curves and determining the Atterberg limits were also measured and collected. The results found showed erodibility (g.cm-2.min- 1.Pa-1) and critical shear stress values respectively of 0.0036 and 2.00 for E1; 0.0099 and 2.06 for E2; 0.0582 and 3.93 for E3; 0.0073 and 3.78 for E4; 0.0075 and 4.87 for E5; and, 0.0054 and 3.74 for E6. These values appear highly elevated for the condition of roads, indicating high erosion risk, a fact that can be observed from the conservation state in which they can be found. The soils of the roads were classified as Sandy loam (E1), Sandy (E2), Clay loam (E3), Sandy clay (E4), Sandy loam (E5) and Sandy clay loam (E6). The classification of the soils of the roads, with little clay material, which works as a cementer, helps explain the elevated values obtained for the erodibility and critical shear stress. The soil density values (g.cm-3) observed were, respectively for roads E1 to E6, 1.58; 1.64; 1.53; 1.41; 1.63 and 1.60. Through the simulation performed using the Roads Griebeler (2005) software and utilizing the values observed in the field, the fact that road E1 obtained the greatest space management, mainly due to its lower erodibility. However, for the remaining roads, the software pointed out the need to build drains nearby, further indicating the need to make alterations in their drainage channels as well as their consisting material, so that their erodibility would be reduced. The composition of the material can be made through the mixture of a greater quantity of cementing material, such as clayey soil, to the material of the road, enhancing the soil s resistance to the erosive process. The model has proven to be highly sensitive to the alterations in the erodibility of the soil and in the declivity of the road. / Este trabalho foi desenvolvido tendo como objetivo principal a determinação da erodibilidade e da tensão crítica de cisalhamento em estradas não pavimentadas, visando a redução dos riscos de ocorrência de erosão nestas estradas com base em dimensionamentos de sistemas de drenagem através de valores locais de resistência. Para a obtenção destes valores foi construído um simulador de escoamento, cujo modelo consiste em um aperfeiçoamento do equipamento proposto por Griebeler et al. (2005), utilizado para testes de escoamento superficial diretamente no canal de drenagem da estrada e para a coleta de material erodido. O simulador foi instalado em solos de estradas de Goiânia (E1), Baliza (E2), Doverlândia (E3) e Morrinhos (E4, E5 e E6), todas no estado de Goiás. Os testes foram realizados com três repetições para cada canal de estrada. Em cada teste foram utilizadas cinco vazões diferentes e crescentes, de modo a simular a curva ascendente de um hidrograma de escoamento, sendo cada vazão coletada em um recipiente próprio, para posterior determinação da quantidade de material erodido. Foram coletadas amostras de solo indeformadas, utilizando um amostrador Uhland, visando à determinação da densidade do solo. Coletou-se também, amostras para a caracterização das curvas granulométricas e determinação dos limites de Atterberg e determinou-se, ainda, a declividade da estrada. Os resultados encontrados mostraram valores de erodibilidade (g.cm-2.min-1.Pa-1) e de tensão crítica de cisalhamento (Pa) respectivamente de 0,0036 e 2,00 para a E1; 0,0099 e 2,06 para E2; 0,0582 e 3,93 para E3; 0,0073 e 3,78 para E4; 0,0075 e 4,87 para E5; e, 0,0054 e 3,74 para E6. Estes valores mostram-se bastante elevados para a condição de estradas, indicando alto risco de erosão, fato este observado pelo estado de conservação destas em campo. Os solos das estradas foram classificados como Franco arenoso (E1), Arenoso (E2), Franco argiloso (E3), Argilo arenoso (E4), Franco arenoso (E5) e Franco argilo arenoso (E6). A classificação dos solos das estradas, com pouco material argiloso, que funciona como cimentante, ajuda a explicar os elevados valores obtidos para a erodibilidade e tensão crítica de cisalhamento. Os valores de densidade (g.cm-3) do solo observados foram de 1,58; 1,64; 1,53; 1,41; 1,63 e 1,60, respectivamente para as estradas de E1 a E6. Pela simulação realizada com o software Estradas (Griebeler et al., 2005), utilizando os valores observados em campo, pode-se observar que o maior espaçamento foi obtido para a estrada E1, em vista, principalmente, da sua menor erodibilidade. Nas demais estradas o software indicou a necessidade de desaguadouros bastante próximos indicando a necessidade de alterações nos canais de drenagem das estradas bem como no seu material constituinte, de modo que sua erodibilidade seja reduzida. A composição do material pode ser feita pela mistura de uma maior quantidade de material cimentante, como solo argiloso, ao material da estrada, aumentando a resistência do solo ao processo erosivo. O modelo mostrou-se bastante sensível às alterações na erodibilidade do solo e na declividade da estrada.

Cette thèse de doctorat est dédiée à l’étude, avec des méthodes de calcul ab initio, desplasmons de surface et des états de surface de surfaces d’or, plate ou comportant desmarches (surface vicinale), par la simulation numérique de spectres de perte d’énergieélectronique (EEL) au moyen de la théorie de la fonctionnelle de la densité (DFT) et de lathéorie de perturbation de la fonctionnelle de la densité dépendant du temps (TDDFPT).L’influence du couplage spin-orbite (CSO) et celle de la géométrie de la surface ont étéétudiées. Dans l’or cristallin, j’ai étudié l’effet des électrons de semicoeur sur les spectresEEL à q = 0. J’ai montré en particulier que pour produire un spectre EEL sur une largegamme de fréquences, de 0 à 60 eV, il est nécessaire de tenir compte des électrons desemicoeur dans le pseudopotentiel, et qu’ils peuvent néanmoins être gelés dans le coeurpour l’étude de la partie basse en énergie du spectre EEL, pour des énergies inférieures à20 eV. J’ai réalisé des développements méthodologiques pour la TDDFPT avec CSO cou-plée à l’emploi de pseudopotentiels ultradoux, qui ont permis l’implémentation pratiquede cette approche dans les algorithmes de Liouville-Lanczos et de Sternheimer. J’ai utiliséavec succès ces approches qui m’ont permis de traiter des systèmes à plusieurs centainesd’atomes. J’ai examiné à nouveau le spectre EEL de l’or cristallin à q = 0, montrant enparticulier les traces d’un plasmon écranté dans le spectre EEL calculé sans inclure leseffets de CSO. J’ai ensuite montré que l’inclusion du CSO a un effet petit mais détectablesur le spectre EEL et le pic de plasmon, donnant un meilleur accord avec l’expérienceà q = 0. J’ai trouvé que la dispersion du plasmon acoustique (PAS) de la surface Au(111) est légèrement modifiée par le CSO, provenant du fait que la structure de bandesest elle-même modifiée par le dédoublement de Rashba de certains niveaux électroniques,dédoublement induit par le CSO. Puis, pour étudier les effets de géométrie, j’ai étudié lessurfaces vicinales (322), (455) et (788) de l’or. J’ai en particulier mené l’étude théoriquedes états électroniques de surface, et analysé l’évolution de l’état de surface de Shockleyentre la surface plate Au(111) et les surfaces ayant des marches dont les terrasses avaientdifférentes largeurs. J’ai montré la transition d’un état de surface résonant pour Au(322)à un état localisé pour Au(455) et pour Au(788), ainsi que le passage d’un état 2D étenduà travers la marche pour Au(322) à un état quasi-1D confiné dans la terrasse de la marchepour Au(455) et pour Au(788). Ces résultats sont en accord avec l’expérience, et avecceux d’un modèle de Kronig-Penney de potentiel périodique. J’ai calculé le spectre EELSpour la surface d’or (455) que j’ai modélisé par une tranche de 5 nm d’or séparée de sesvoisines (répétées périodiquement) par 5 nm de vide. J’ai identifié la signature du plas-mon acoustique de surface. J’ai montré que, pour un moment transféré perpendiculaireà la marche de la surface, la dispersion du PAS n’est pas modifiée par rapport à celle duPAS de la surface plate Au(111) pour q < 0.125 Å −1 . Cependant, pour des valeurs plusgrandes du moment transféré, le pic du PAS a une énergie plus basse que celle du PASde Au(111), montrant les signes du confinement du PAS et suggérant que deux types dePAS peuvent se produire: un plasmon intra(sous)bande, similaire à celui de la surfaceAu(111), et un plasmon inter(sub)band, caractéristique de cette surface vicinale. / The PhD thesis is devoted to the ab initio study of surface plasmons and surface states offlat and vicinal surfaces of Au through the simulation of electron energy loss (EEL) spectraby means of the density functional theory (DFT) and the time-dependent density func-tional perturbation theory (TDDFPT). The influence of the spin-orbit coupling (SOC)and of the surface geometry has been investigated. In bulk Au I have studied the effect ofthe inclusion of semi-core electrons on the EEL spectrum at q = 0 and the plasmon peakposition and intensity. In particular, I have shown that in order to reproduce the EELspectrum on a wide frequency range (0-60 eV) it is important to account for semi-coreelectrons in the pseudopotential although they can be frozen in the core in studies of thelow energy part of the spectrum (below 20 eV). I have made methodological developmentsfor TDDFPT with SOC in the ultrasoft pseudopotential scheme that led to the practicalimplementation of SOC in the Liouville-Lanczos and Sternheimer approaches. I have thensuccessfully applied these approaches that allowed me to model systems with hundreds ofatoms. I have revisited the plasmonic excitations in bulk Au, pointing out that, in partic-ular, one can observe traces of an unscreened s-like bulk plasmon in the EEL spectrum atq = 0 calculated without SOC. I have also demonstrated that SOC has a small but notice-able effect on the Au EEL spectrum and plasmon peak, mainly modifying the unscreeneds-like plasmon peak and thus bringing the calculated spectrum into a better agreementwith experimental results at q = 0. Moreover I have observed that the dispersion ofthe acoustic surface plasmon (ASP) on the Au(111) surface is slightly modified by SOC,because the ASP comes from the surface state that itself is modified by SOC through theRashba splitting. To investigate the effect of geometry I have studied the vicinal (322),(455) and (788) surfaces of Au. In particular I have performed the theoretical study of thesurface states, analyzing the evolution of the Shockley surface state from the flat Au(111)surface towards the surfaces with terraces of different width. I have shown the surfaceresonance-to-surface state transition from (322) to (455) and (788) surfaces. I have shownalso the transition from the average-surface-modulated to the terrace-modulated statefrom (322) to (455) and (788) surfaces, as well as the transition from the extended 2Dstate to the quasi-1D state confined within the terrace. These results are in agreementwith experiments and results obtained with the Kronig-Penney periodic potential model.I have performed the EEL spectrum calculations for the Au(455) surface which I havemodeled with a 5 nm sized slab separated from its periodic neighbors by 5 nm of vacuum.I have identified signatures of the ASP in these spectra, showing that indeed, for the caseof the transferred electron wavevector momentum perpendicular to the step, the ASPdispersion is not changed with respect to the ASP dispersion of the Au(111) surface forq < 0.125 Å −1 . For bigger values of q, however, the ASP peak has a lower energy com-pared to the ASP peak of the Au(111) surface, showing signs of the ASP confinement, andsuggesting that two types of the ASP could occur: an intra(sub)band plasmon, similarto the Au(111) surface plasmon, and an inter(sub)band plasmon, characteristic of thisvicinal surface.