Thesis (doctoral) -- Universität Hamburg, 2006/7. / Includes bibliographical references (p. 135-139).

Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (leaves [161]-163).

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 73-77).

Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xx, 198 p.; also includes graphics (some col.). Includes bibliographical references (p. 191-198). Available online via OhioLINK's ETD Center.

The advances achieved using X-ray Free Electron Lasers such as the Linac Coherent Light Source (LCLS), have revolutionised the routine production of uniform solid-density plasmas. Pulses of X-rays above 1 keV and with durations shorter than 100 fs attaining intensities on target of around 10¹⁷ Wcm^-2 are now routinely created. Through simple single-photon photoionization events with atoms in ambient solid conditions, it is possible to create uniform samples that are simultaneously hot, dense, and highly ionized which may be easily modelled. This thesis describes measurements of the spectrally-resolved X-rays emitted from solid-density magnesium targets of varying sub-μm thicknesses isochorically heated by an X-ray laser. The data exhibit a thickness-independent source function, allowing the extraction of a measure of the opacity to K-shell X-rays within well-defined regimes of electron density and temperature, extremely close to Local Thermodynamic Equilibrium conditions by fitting to the simple 1D slab solution of the equation of radiative transfer. The deduced opacities at the peak of the K-α transitions of the ions are consistent with those predicted by detailed atomic-kinetics calculations. The extracted opacities transpire to be robust to a plethora of variations in X-ray drive conditions, including the shape, pulse-length, and energy content. Furthermore the approximations in using the 1D slab solution are examined in detail and found to be good. A full three-dimensional model of the plasma is advanced which includes attenuation, line-of-sight effects, full longitudinal and transverse gradients, and photon time-of-flight effects. The results from this model are found to also agree with the simpler 1D slab solution. This novel method of elucidating opacities may complement other methods based on absorption and could be important for further benchmarking of opacities in solar-interior relevant conditions.

No description available.

Orientador: Marco Aurélio Cebim / Coorientador: Marian Rosaly Davolos / Banca: José Clayston Melo Pereira / Banca: José Maurício Almeida Caiut / Resumo: Alguns compostos orgânicos de origem natural apresentam grande interesse para aplicação médica devido suas atividades biológicas como antioxidante, antiviral, antimicrobiano, antitumoral, entre outras. Destes estes compostos, alguns se destacam por apresentarem a possibilidade de agir como ligante em compostos de coordenação. Para o desenvolvimento desse projeto de pesquisa, em especial, foram selecionados os ligantes 3,5,7,3',4'- pentahidroxiflavona (quercetina), ácido 3,4,5-triidroxibenóico (ácido gálico), ácido (E)-3fenil- 2-propenóico (ácido cinâmico) e (E)-3-(4-hidroxifenil)-2-propanoico (ácido p-cumárico). Pretende-se, portanto, maximizar as atividades antioxidantes e antitumorais destes ligantes de origem natural, por meio da complexação em compostos de coordenação. Além disso, estudar as propriedades estruturais e ópticas dos complexos obtidos. O desenvolvimento dessa pesquisa permitiu encontrar uma relação entre a estrutura do ligante e suas propriedades ópticas quando excitados com radiação ultravioleta e raios X. Conseguiu-se também levantar algumas hipóteses sobre a potencialidade de utilização destes compostos de coordenação como filtros solares. / Some organic compounds of natural origin are of great interest for medical application due to their biological activities as antioxidant, antiviral, antimicrobial, antitumor, among others. Of these compounds, some are notable for their ability to act as a binder in coordination compounds. For the development of this research project, in particular, the binders were selected quercetin (2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxy-4H-chromen-4-one), Cinnamic acid (3-phenyl-2-propenoic acid) and p-coumaric acid ((E)-3-(4-hydroxyphenyl)-2-propenoic acid). It is therefore intended to maximize the antioxidant and antitumor activities of these naturally occurring binders by complexing into coordination compounds. In addition, to study the structural and optical properties of the complexes obtained. The development of this research allowed to find a relation between the structure of the binder and its optical properties when excited with ultraviolet radiation and X-rays. It was also possible to raise some hypotheses about the potential of using these coordination compounds as sunscreens. / Mestre

Made available in DSpace on 2015-08-20T17:09:27Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-04-17. Added 1 bitstream(s) on 2015-08-20T17:27:09Z : No. of bitstreams: 1 000774381_20160417.pdf: 1714369 bytes, checksum: 5c214799660b39542efb0866fe559790 (MD5) Bitstreams deleted on 2016-04-25T15:55:54Z: 000774381_20160417.pdf,. Added 1 bitstream(s) on 2016-04-25T15:56:51Z : No. of bitstreams: 1 000774381.pdf: 5960727 bytes, checksum: 0ebf015f50f4bdcf797b4b89b7c40b61 (MD5) / Neste trabalho, foram obtidos e caracterizados complexos luminescentes com íons Ln3+ (Ln = Eu, Gd, Tb, Dy) homo e/ou heterobilantanídicos com o ligante ácido tiofeno-2- carboxílico, que atua eficientemente como antena, absorvendo energia e transferindo-a para o íon emissor. A presença do anel tiofênico nos ligantes confere características interessantes, como por exemplo, maior polarizabilidade por conter em sua estrutura um átomo de enxofre. Os complexos foram caracterizados por análise elementar, análise de Ln3+ por análise titulométrica com uso de edta, análise térmica, espectroscopia vibracional na região do infravermelho e DRX, que permitiram propor as estequiometrias [Ln(α-tpc)3(α-Htpc)2]n e [Ln(α-tpc)3(α-Htpc)] e que a coordenação se dá pelo modo bidentado. Pelas espectroscopias eletrônica UV-vis, fotoluminescência e de excitação por raios X, foram observadas as transições características dos íons Ln3+ envolvidos neste trabalho. São propostos mecanismos de transferência de energia em compostos puros e nos complexos heterobilantanídicos, à partir da elaboração de diagramas de energia, baseados nos resultados de fotoluminescência. Os complexos também tiveram suas propriedades magnéticas investigadas, em alguns casos, pela utilização da técnica de EPR, PPMS e VSM, sendo observado um comportamento predominantemente paramagnético para os complexos. Os complexos foram expostos à radiação ionizante por um tempo prolongado, a fim de verificar o comportamento e estabilidade química desses complexos homo e heterolantanídicos sob radiação ionizante e os resultados mostraram que os complexos são estáveis frente à excitação com raios-X. / Monometallic and/or heterobimetallic Ln3+ (Ln = Eu, Gd, Tb, Dy) luminescent complex with thiophen-2-carboxylic acid was investigated. The ligand employed in this work, acts efficiently as antenna, absorbing and transfer energy to the emitter ion. The thiophen ring provides interesting features to the system, like higher polarizability due the sulphur atom. The complex were characterized by elemental analysis, complexometric titrimetry with edta, in order to quantify Ln3+, thermal analysis, FTIR and XRD which allowed propose two different stoichiometries [Ln(α-tpc)3(α-Htpc)2]n and [Ln(α-tpc)3(α-Htpc)] and the coordination of the ligand to the Ln3+ occurs through the bidentate coordination mode. By the UV-vis, photoluminescence and X rays spectroscopies, were observed the Ln3+ transitions. Energy transfer mechanism were proposed in monometallic and heterobimetallic complexes, from the drafting of the energy diagram, based on results of fotoluminescence. The complex also have the magnetic properties investigated, by the EPR, PPMS and VSM techniques and the results shows a predominantly paramagnetic behavior to the complexes. The complexes were exposure to ionizing radiation during a extended time, in order to verify the chemical stability of the homo and hetero-lanthanide complex forward to ionizing radiation and is observed high stability over X-ray excitation.

abstract: The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes a question of understanding biomolecular dynamics that span a variety of timescales (from electronic rearrangements in the femtoseconds to side-chain alteration in the microseconds and more). This dissertation deals with the study of biomolecular dynamics in the ultrafast timescales (fs-ns) using electron and X-ray probes in both time and frequency domains. It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided. Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016