Through the cosmic matter cycle, the chemical evolution of the Milky Way is imprinted in the elemental abundance patterns of late-type stars (spectral types F to K). Due to their long lifetimes ( 1 Hubble time), these stars are of particular importance when it comes to studying the build-up of elements during the early times of our Galaxy. The chemical composition of the atmospheric layers of such stars is believed to resemble the gas from which they were formed. However, recent observations in globular clusters seem to contradict this assumption. The observations indicate that processes are at work that alter the surface compositions in these stars. The combined effect of processes responsible for an exchange of material between the stellar interior and atmosphere during the main sequence lifetime of the star, is referred to as atomic diffusion. Yet, the extent to which these processes alter surface abundances is still debated. By comparing abundances in unevolved and evolved stars all drawn from the same stellar population, any surface abundance anomalies can be traced. The anomalies, if found, can be compared to theoretical predictions from stellar structure models including atomic diffusion. Globular clusters provide stellar populations suitable to conduct such a comparison. In this thesis, the results of three independent analyses of two globular clusters, NGC 6752 and M4, at different metallicities are presented. The comparison between observations and models yields constraints on the models and finally a better understanding of the physical processes at work inside stars.

Collagen is one of the major protein constituents in mammals and is present in all tissues and organs with the exceptions of keratin tissues such as hair and nails. Collagen monomers self-aggregate into a number of structures. In order to understand the physical bases for the structural polymorphism observed in collagen, a good starting point is one of the simplest collagen aggregates, segmental long spacing (SLS) collagen. Although SLS collagen formation induced by the presence of adenosine 5’-triphosphate is widely known, effects of other triphosphates, on the other hand, are much less studied. By varying the pH, it is discovered that all the nucleoside 5’-triphophsates, as well as inorganic triphosphate, are able to induce SLS formation over certain pH ranges. Adenosine 5’-diphosphate and para-nitrophenylphosphate cannot induce SLS formation at any pH. Based on the pH ranges at which SLS collagen can be formed, it is concluded the triphosphate functionality, with one negative charge per phosphate group, is primarily responsible for the formation of SLS collagen. Since inorganic triphosphate is able to induce SLS collagen formation, the presence of the nucleoside is optional for the assembly process; however if present, the assembly process prefers the nucleosides carrying acidic protons. Using electron spectroscopic imaging (ESI) technique, it is found phosphorus, present only in nucleotides but not in polypeptides, is localized in certain regions of SLS collagen, forming a unique banding pattern transverse the long axis of the SLS collagen. Nitrogen mapping indicates the localization of phosphorus is not due to accumulation of materials. The phosphorus banding pattern demonstrates an excellent consistency across SLS collagen assembled from both bovine and recombinant human collagen monomers. Results from molecular simulation are consistent with the experimental results. All threephosphate groups seem to be involved in the assembly process to some degree. In the last chapter of the thesis, a reliable protocol to synthesis native type collagen fibers is introduced.

Collagen is one of the major protein constituents in mammals and is present in all tissues and organs with the exceptions of keratin tissues such as hair and nails. Collagen monomers self-aggregate into a number of structures. In order to understand the physical bases for the structural polymorphism observed in collagen, a good starting point is one of the simplest collagen aggregates, segmental long spacing (SLS) collagen. Although SLS collagen formation induced by the presence of adenosine 5’-triphosphate is widely known, effects of other triphosphates, on the other hand, are much less studied. By varying the pH, it is discovered that all the nucleoside 5’-triphophsates, as well as inorganic triphosphate, are able to induce SLS formation over certain pH ranges. Adenosine 5’-diphosphate and para-nitrophenylphosphate cannot induce SLS formation at any pH. Based on the pH ranges at which SLS collagen can be formed, it is concluded the triphosphate functionality, with one negative charge per phosphate group, is primarily responsible for the formation of SLS collagen. Since inorganic triphosphate is able to induce SLS collagen formation, the presence of the nucleoside is optional for the assembly process; however if present, the assembly process prefers the nucleosides carrying acidic protons. Using electron spectroscopic imaging (ESI) technique, it is found phosphorus, present only in nucleotides but not in polypeptides, is localized in certain regions of SLS collagen, forming a unique banding pattern transverse the long axis of the SLS collagen. Nitrogen mapping indicates the localization of phosphorus is not due to accumulation of materials. The phosphorus banding pattern demonstrates an excellent consistency across SLS collagen assembled from both bovine and recombinant human collagen monomers. Results from molecular simulation are consistent with the experimental results. All threephosphate groups seem to be involved in the assembly process to some degree. In the last chapter of the thesis, a reliable protocol to synthesis native type collagen fibers is introduced.

Detailed knowledge of solar-type stars is essential in the understanding of the evolutionary past, presence and future of the Sun as well as the formation of its planetary system. Moreover, solar-type stars are of key significance for the study of the evolution of the Galaxy. The ages of solar-type stars map the full galactic evolution. Their surface layers are well mixed and just little affected by the interior nuclear processes. They may therefore be used as samples of the gas from which the stars were once formed. Models of stellar atmospheres are used to derive fundamental stellar quantities such as chemical composition, effective temperature, surface gravity, age and rotation. It is therefore also important to investigate the progress and shortcomings of the atmospheric models and the reliability of calibrations based upon these. In this thesis we explore the potential of synthetic uvbyHβ colours for deriving atmospheric parameters. The theoretical colours are derived using high-resolution synthetic spectra based on 1D atmosphere models of late-type stars. Furthermore, possible applications of the established synthetic colours on globular stellar clusters are tested. Observations of solar-type stars have demonstrated the existence of stars very similar to the Sun, so-called solar twins. A detailed chemical analysis of these stars, however, shows that most solar-twins are systematically richer, as compared with the Sun, in refractory elements such as Fe, Ni and Al, relative to volatile elements like C, N and O. This chemical abundance pattern has been suggested to be related to the formation of planets or the birth environment of the respective star. In this thesis we present a high-accuracy study on a solar-twin star in the old open cluster M67. We find that the star is very similar to the Sun when comparing their atmospheric parameters, effective temperature, surface gravity and metallicity. Remarkably enough, unlike most solar twins observed in the solar vicinity, the cluster twin shows the same refractory to volatile pattern as the Sun.The reason for this similarity is still unknown but further observations of the cluster will help to clarify the matter. M dwarfs constitute a large fraction of the detectable baryonic matter. In spite of this, detailed knowledge on the numerous neighbouring low-mass stars is still not available. The presence of strong molecular features in the spectra, and incomplete line lists for the corresponding molecules have made metallicity determinations of M dwarfs difficult. Furthermore, the faint M dwarfs require long exposure times for a signal-to-noise ratio sufficient for detailed spectroscopic abundance analysis. In this thesis we present a high resolution spectroscopic study of early-type M dwarfs in the infrared. The lack of prominent molecular bands in parts of the infrared J-band (1100--1400 nm) allows a precise continuum placement. Furthermore, we verify the adequacy of using the model atmospheres for abundance determination by observing a set of binary systems with a solar-type primary and an M dwarf companion. We present a reliable zero-point for the metallicity scale of early-type M dwarfs and verify the reliability of spectroscopic abundance analyses in the infrared.

Doctor of Philosophy (PhD) / This thesis presents the development of new techniques for measuring the mean redshifted 21 cm line of neutral hydrogen during reionization. This is called the 21 cm cosmological reionization monopole. Successful observations could identify the nature of the first stars and test theories of galaxy and large-scale structure formation. The goal was to specify, construct and calibrate a portable radio telescope to measure the 21 cm monopole in the frequency range 114 MHz to 228 MHz, which corresponds to the redshift range 11.5 > z > 5.2. The chosen approach combined a frequency independent antenna with a digital correlation spectrometer to form a correlation radiometer. The system was calibrated against injected noise and against a modelled galactic foreground. Components were specified for calibration of the sky spectrum to 1 mK/MHz relative accuracy. Comparing simulated and measured spectra showed that bandpass calibration is limited to 11 K, that is 1% of the foreground emission, due to larger than expected frequency dependence of the antenna pattern. Overall calibration, including additive contributions from the system and the radio foreground, is limited to 60 K. This is 160 times larger than the maximum possible monopole amplitude at redshift eight. Future work will refine and extend the system known as the Cosmological Reionization Experiment Mark I (CoRE Mk I).

Thesis (Ph. D.)--Miami University, Dept. of Chemistry and Biochemistry, 2008. / Title from second page of PDF document. Includes bibliographical references.

Thesis (M.S.)--Indiana University, 2008. / Title from screen (viewed on June 3, 2009). Department of Earth Science, Indiana University-Purdue University Indianapolis (IUPUI). Advisor(s): Lin Li, Pierre Jacinthe, Gabriel M. Filippelli. Includes vita. Includes bibliographical references (leaves 78-81).

Made available in DSpace on 2014-06-11T19:27:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-08-20Bitstream added on 2014-06-13T19:35:04Z : No. of bitstreams: 1 silva_ml_me_bauru.pdf: 1014691 bytes, checksum: d6234b7cfd38238526074b3a223731a8 (MD5) / Neste trabalho investigaram-se a fabricação dos filmes de Langmuir e de filmes Langmuir-Blodgett (LB) mistos obtidos do azopolímero poli(metacrilato de lauroila-cometacrilato de DR1) com estearato de cádmio (StCd). A fabricação dos filmes LB desse azopolímero somente foi possível utilizando-se o StCd como suporte molecular. A caracterização espectroscópica dos filmes LB foi feita através de espectroscopia de absorção no UV-Visível e no infravermelho. As medidas de birrefringência fotoinduzida dos filmes LB mistos do azopolímero com StCd foram feitas em função do tempo durante a formação da birrefringência e no decaimento após a luz de excitação ter sido desligada. Os resultados experimentais obtidos nas medidas mostraram que a amplitude máxima da birrefringência obtida durante a excitação aumenta com a intensidade da luz de excitação e o número de camadas dos filmes LB. Foi também estudada a dinâmica da formação e do decaimento determinando-se as constantes de tempo dos processos de orientação usando funções biexponenciais do modelo de Sekkat / Fabrication of Langmuir and Langmuir-Blodgett (LB) mixed films of poly(lauroyl-methacrylate co-DR1 methacrylate) and cadmium stearate (CdSt) were investigated. The fabrication of LB films from this azopolymer was achieved only if CdSt molecular support is used. Spectroscopic characterization of films were performed by means of UV-Vis and infrared measurements. Photoinduced birefringence measurements of LB mixed films of azopolymer with CdSt were performed as function of time during the buildup of the birefringence and the decay after turning off the excitation light. Experimental results showed that the maximum birefringence achieved during the light excitation increased with the number of layers of the LB film and light intensity. Photoinduced birefringence dynamics was also investigated during the buildup and decay aiming to determine the time constants of bi-exponential functions given by the Sekkat model

Orientador: José Alberto Giacometti / Banca: José Leonil Duarte / Banca: Neri Alves / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Neste trabalho investigaram-se a fabricação dos filmes de Langmuir e de filmes Langmuir-Blodgett (LB) mistos obtidos do azopolímero poli(metacrilato de lauroila-cometacrilato de DR1) com estearato de cádmio (StCd). A fabricação dos filmes LB desse azopolímero somente foi possível utilizando-se o StCd como suporte molecular. A caracterização espectroscópica dos filmes LB foi feita através de espectroscopia de absorção no UV-Visível e no infravermelho. As medidas de birrefringência fotoinduzida dos filmes LB mistos do azopolímero com StCd foram feitas em função do tempo durante a formação da birrefringência e no decaimento após a luz de excitação ter sido desligada. Os resultados experimentais obtidos nas medidas mostraram que a amplitude máxima da birrefringência obtida durante a excitação aumenta com a intensidade da luz de excitação e o número de camadas dos filmes LB. Foi também estudada a dinâmica da formação e do decaimento determinando-se as constantes de tempo dos processos de orientação usando funções biexponenciais do modelo de Sekkat / Abstract: Fabrication of Langmuir and Langmuir-Blodgett (LB) mixed films of poly(lauroyl-methacrylate co-DR1 methacrylate) and cadmium stearate (CdSt) were investigated. The fabrication of LB films from this azopolymer was achieved only if CdSt molecular support is used. Spectroscopic characterization of films were performed by means of UV-Vis and infrared measurements. Photoinduced birefringence measurements of LB mixed films of azopolymer with CdSt were performed as function of time during the buildup of the birefringence and the decay after turning off the excitation light. Experimental results showed that the maximum birefringence achieved during the light excitation increased with the number of layers of the LB film and light intensity. Photoinduced birefringence dynamics was also investigated during the buildup and decay aiming to determine the time constants of bi-exponential functions given by the Sekkat model / Mestre

Made available in DSpace on 2015-05-14T13:00:17Z (GMT). No. of bitstreams: 1 parte1.pdf: 2218079 bytes, checksum: 8c3306b1c24bd11212cd191d547b9f95 (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Turnera subulata Sm., popularly known as Chanana or flor-do-Guaruja , is a Brazilian medicinal plant belonging to the family Turneraceae. In Brazil this family is represented by two genera, Piriqueta and Turnera, being Turnera the most representative. The Genus Turnera is characterized by the presence of terpenoids, flavonoids, steroids, benzenoids, alkaloids and lipids. Aiming at contributing to the chemical profile of the family Turneraceae and considering the absence of data in literature about the chemical constitution of the species Turnera subulata, the latter was submitted to a phytochemical study to isolate its chemical constituents, through usual chromatographic methods, and after identifying them by means of spectroscopic methods such as IR and 1H and 13C NMR, with the add of two-dimensional techniques. Six constituents were isolated through this phytochemical study with Turnera subulata: Phaeophytin purpurin 18 phytyl ester (Ts-5); Phaeophytin (a) (Ts-1); 132- hydroxy - (132-S)- Phaeophytin (a) (Ts-2); Phaeophytin (b) (Ts-4) and mixture of steroids sitosterol-3- O-D-glucopyranoside and Stigmasterol-3-O-β-D-glucopyranoside (Ts-3). / Turnera subulata Sm, conhecida popularmente como chanana ou flor-do-Guarujá , é uma espécie da família Turneraceae. No Brasil esta família é representada pelos gêneros, Piriqueta e Turnera, sendo Turnera o mais representativo, com cerca de 80 espécies. Este Gênero é caracterizado pela presença de terpenóides, flavonóides, esteróides, benzenóides, alcalóides e lipídios. Visando contribuir com o perfil químico da família Turneraceae e tendo em vista a ausência de dados na literatura acerca da constituição química da espécie Turnera subulata Sm, esta foi submetida a um estudo fitoquímico para o isolamento de seus constituintes químicos, através dos métodos cromatográficos usuais, e posterior caracterização estrutural dos mesmos, utilizando-se os métodos espectroscópicos de IV e RMN 1H e 13C uni e bidimensionais. Deste estudo pioneiro com Turnera subulata foram isolados e identificados seis constituintes: Feofitina Purpurina 18 fitil éster (Ts-5); Feofitina (a) (Ts-1); 132-hidroxi- (132-S)-feofitina (a) (Ts-2); Feofitina (b) (Ts-4) e uma mistura dos esteróides glicosilados sitosterol-3-O-D-glicopiranosídeo e estigmasterol-3-O-β-D-glicopiranosídeo (Ts-3).