Thesis (M.S.)--University of Missouri--Rolla, 2007. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed June 17, 2008) Includes bibliographical references.

Thesis (Master)--İzmir Institute of Technology, İzmir, 2004. / Includes bibliographical references (leaves. 50-54).

Thesis (M. Phil.)--University of Hong Kong, 1993.

Thesis (M. Phil.)--University of Hong Kong, 1994. / Includes bibliographical references (leaves 93-101).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Typescript. Includes: Thermodynamic properties of ions at high temperatures / John W. Green, Duncan E. Poland, John L. Margrave. (Wright-Patterson Air Force Base, Ohio : Aeronautical Research Laboratory, Office of Aerospace Research, United States Air Force, 1961) -- Ideal gas thermodynamic functions of some selected elements / D.E. Poland, J.W. Green and J.L. Margrave. Reprinted from Journal of chemical & engineering data, v. 7, no. 3 (July 1962), p. 389-390 -- Corrected optical pyrometer readings / D.E. Poland, J.W. Green and J.L. Margrave. National Bureau of Standards monograph ; 30 (Washington, 1961), 74 p. -- Absorption spectrum of chlorine in the vacuum ultraviolet / Raymond P. Iczkowski, Raymond P., John L. Margrave and John W. Green. Reprinted from Journal of chemical physics, v. 33, no. 4 (Oct. 1960), p. 1261-1262. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2004. / Includes bibliographical references (leaves R1-R14). Also available online.

Thesis (Ph. D. in Chemistry)--Vanderbilt University, Dec. 2006. / Title from title screen. Includes bibliographical references.

Orientador: Denise Bevilaqua / Orientador: Oswaldo Garcia Júnior (in memoriam) / Banca: Elizabeth Berwerth Stucchi / Banca: Peter Hammer / Banca: Antonio Carlos Augusto da Costa / Banca: Ana Teresa Lombardi / Resumo: O processo de biossorção tem sido reconhecido como alternativa potencial na concentração de metais pesados e radioisótopos a partir de corpos d'água que recebem ação antropogênica (indústria, mineração, etc.). A biossorção é um processo que se baseia na remoção de íons metálicos em solução aquosa através de interações entre o metal e determinados sítios ativos presentes em revestimentos celulares, provenientes de biomassas como algas, bactérias e fungos. Na última década, há na literatura um crescente interesse na aplicação deste processo para concentração, recuperação e separação de metais de alto valor agregado e/ou de grande demanda tecnológica, tais como as terras-raras (TR) - essenciais para fabricação de um sem-número de produtos, a citar: laseres, supercondutores, equipamentos miniaturizados, etc. Apesar de apresentarem uma considerável disponibilidade na natureza, as TR possuem alto valor agregado devido aos dispendiosos e complexos processos de separação e purificação de misturas de TR, resultado da alta similaridade química entre os elementos do grupo. Poucos países detêm processos industriais completos de separação destes metais, dessa forma, o domínio dessa tecnologia determina uma importância considerável nos aspectos geopolíticos, estratégicos e econômicos, visto a extensão de investimentos em P&D envolvidos e as descobertas geológicas nas últimas décadas das jazidas chinesas, que abrangem 80% das reservas mundiais. Este trabalho consiste em uma avaliação preliminar da utilização do processo de biossorção na biomassa Sargassum sp. para a concentração, recuperação e separação de misturas de metais TR a partir de soluções sintéticas. As interações metal-biomassa seguem uma cinética de pseudo-segunda ordem e são descritas pelo modelo de adsorção de Langmuir... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The biosorption process has been recognized as potential alternative to concentrate heavy metal and radioisotopes from wastewaters of the anthropogenic activities (industry, mining, etc.). The biosorption is a process based on removal of metallic ions in aqueous solution from interactions among the metal and determined active sites on cellular envelope of biomasses as such algae, bacteria, and fungus. In last decade, there are in the literature a crescent interest to apply this process for the concentration, recovery, and separation of metals of high aggregated value and/or high technologic demand as the rare earth metal (RE), which are essential for the manufacturing of a great number of products; e.g. lasers, superconductors, miniaturized equipments, etc. Despite of the RE present a relevant availability, they have high aggregated value due to expansive and complicate processes of separation and purification of RE mixtures, which is resulted of the high chemical similarities of the group. Few countries have complete industrial processes of separation of these metals, so the domain of this technology determines a considerable importance in geopolitical, economic, and strategic aspects because the extension of R&D investments involved and the geological discoveries of the Chinese ore deposits in the last decades, which comprise 80 % of world reserves. This work consists on evaluation of the biosorption process by Sargassum sp. biomass for the concentration, recovery, and separation of RE metals from synthetic solutions. The metalbiomass interactions follow the pseudo-second-order kinetics and they are described by the Langmuir adsorption model. Potentiometric and spectroscopic (SEM/EDX, FTIR e XPS) analyses indicate that the biomass is bounded to the RE by oxygenated groups via ionexchange and complexation mechanisms... (Complete abstract click electronic access below) / Doutor

Submitted by RAFAEL MIGUEL SÁBIO null (rafaelmsabio@gmail.com) on 2016-11-01T21:14:55Z No. of bitstreams: 1 THESE RAFAEL MIGUEL SABIO 26_10_2016.pdf: 9769437 bytes, checksum: 37a38ed4b54498b696d4fe43ebcdfa2e (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-11-10T13:19:03Z (GMT) No. of bitstreams: 1 sabio_rm_dr_araiq_par.pdf: 1635130 bytes, checksum: e5de0aa69e20b9d8d68afedc85cab297 (MD5) / Made available in DSpace on 2016-11-10T13:19:03Z (GMT). No. of bitstreams: 1 sabio_rm_dr_araiq_par.pdf: 1635130 bytes, checksum: e5de0aa69e20b9d8d68afedc85cab297 (MD5) Previous issue date: 2016-10-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Le design de complexes luminescents hétérobimétalliques a suscité ces dernières années un intérêt croissant en raison de leurs propriétés photophysiques uniques. Dans ces complexes de lanthanide (Nd (III) et Yb (III)) associé à des chromophores du bloc d, la forte émission des métaux de transition dans le visible est utilisée pour sensibiliser de façon efficace les niveaux f-f des lanthanides(III) qui émettent à leur tour dans le visible ou l’IR selon les terres rares. Plus spécifiquement l’attention s’est focalisée sur le développement de complexes hétérobimétalliques d-f pour l’émission dans le proche infrarouge (NIR). En effet le proche infrarouge, comparé à l’UV, pénètre plus facilement les tissus biologiques humains notamment la peau. Bien que de telles propriétés confèrent à ces complexes bimétalliques un fort potentiel pour le diagnostic médical, aucun complexe hétérobimétallique d-f greffé de façon covalente à une matrice de silice n’a été décrit. Dans ce travail de nouveaux complexes hétérobimétalliques d-f contenant des ligands silylés ont été préparés et greffés sur la silice. Les complexes monomères [Ru(bpy)2(bpmd)]Cl2 (noté Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (noté RuL) et [Ln(TTA-Si)3] (noté LnL3) et les complexes hétérobimétalliques d-f Ru-LnL3 et Ln-RuL (Ln = Nd3+, Yb3+) ont été préparés. La caractérisation des complexes a été effectuée par spectroscopie Raman, RMN 1H et 13C RMN. Les spectres RMN 1D 1H et 13C NMR ainsi que 2D de corrélation HSQC confirment les structures proposées. L’étude des propriétés photophysiques met en évidence l’émission de l’élément lanthanide dans le proche infrarouge ainsi que l'efficacité du processus de transfert d'énergie Ru-Ln qui est facilité par le ligand (2,2'-bipyrimidine). Les mesures de durée de vie et de rendement quantique (ET) pour le transfert d'énergie indiquent des valeurs remarquables comprises entre 30 et 84 %. La valeur du rendement quantique (ET) du complexe d'Yb-RuL, 73,4 %, est à ce jour la plus grande valeur rapportée pour un complexe hétérobimétallique Ru (II)-Yb (III). Le greffage sur différentes matrices de silice, mésoporeuse SiO2 ou dense SiO2 d, a été réalisé. Les nanohybrides SiO2-RuL, SiO2-NdL3 et SiO2-YbL3 ont été obtenus avec des taux de greffage allant de 0,08 à 0,18 mmol de complexe par gramme de silice. SiO2-RuNd et SiO2- RuYb ont été obtenus par greffage simultané des complexes silylés monomères de ruthénium et de lanthanide, des taux de greffage de 0,10 à 0,16 mmol.g-1 ont été obtenus, respectivement. Les rendements quantiques ET de transfert d’énergie des nanohybrides SiO2-RuNd et SiO2-RuYb sont respectivement de 40 and 27,5 %. La valeur remarquable obtenue pour le nanohybride impliquant le néodyme, SiO2-RuNd, s’explique par bonne adéquation entre les niveaux d’énergie du donneur et de l’accepteur. Les nanohybrides SiO2- RuYbL3, SiO2-YbRuL, SiO2d-YbRuL et SiO2-NdRuL ont été obtenus par greffage des complexes silylés hétérobimétallic d-f élaborés dans ce travail, les taux de greffage, de 0,03 à 0,17 mmol.g-1 permettent d’envisager une fonctionnalisation chimique ultérieure de ces nanoobjets. Les propriétés de luminescence de ces nanohybrides sont similaires à celles des complexes non greffés hormis pour SiO2-YbRuL and SiO2d-YbRuL qui présentent des profils de luminescence différents comparés au complexe libre Yb—RuL. Le greffage à l'intérieur des pores de la silice pourrait éviter le processus de désactivation de la luminescent contrairement au greffage sur la matrice de silice dense. Les propriétés photophysiques associées à la morphologie et à la stabilité de la matrice de silice mésoporeuse permettent d’envisager l’utilisation de ces nouveaux nanohybrides luminescents dans le proche infrarouge comme nanosondes ou nanomarqueurs de systèmes biologiques. / The design of heterobimetallic luminescent complexes has gained growing interest in recent years due to their unique photophysical properties. More specifically, the development of heterobimetallic complexes using d-block chromophores to sensitize the near-infrared (NIR) emission of lanthanide complexes (such as Nd(III) and Yb(III)) has received significant attention taking into account their longer emission wavelengths and the interest of the NIR emission which penetrates human tissue more effectively than UV light. These properties give them potential applications in medical diagnostics or biomedical assays. Transitions to excited state levels of transition metal complexes occurring in the visible and characterized by large absorption coefficients, could efficiently sensitize f-f levels of Ln(III) ions. In this work new d-f heterobimetallic complexes containing silylated ligands were prepared supported on silica materials. [Ru(bpy)2(bpmd)]Cl2 (labeled Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (labeled RuL) and [Ln(TTA-Si)3] (labeled LnL3) and d-f heterobimetallic complexes, Ru—LnL3 and Ln—RuL (Ln = Nd3+, Yb3+) were prepared. Structural characterization was carried out by Raman Scattering, 1H and 13C NMR spectroscopies. Results obtained from 1H-13C HMBC and HSQC correlation NMR spectra confirm the formation of proposed complexes. Photophysical properties studies highlight the efficiency of Ru—Ln energy transfer processes in NIR-emitting lanthanide complexes mediated by conjugated bridging ligand (2,2'-bipyrimidine). Lifetime measurements were carried out and values of quantum yield for energy transfer (ET) between 30 and 84 % could be evaluated. ET of 73.4 % obtained for the Yb—RuL complex is the largest value reported for Ru(II)—Yb(III) heterobimetallic complexes so far. Grafting on different silica matrix was also demonstrated. SiO2-Ru, SiO2-NdL3 and SiO2-YbL3 nanohybrids were obtained with grafting efficiencies from 0.08 to 0.18 mmol g-1 of silica. SiO2-RuNd and SiO2-RuYb were performed from simultaneous grafting of ruthenium and lanthanides silylated complexes. Grafting efficiencies from 0.10 to 0.16 were obtained. ET of 40 and 27.5 % were obtained from SiO2-RuNd and SiO2-RuYb, respectively. The higher values observed for the Nd(III) nanohybrid is well explained by the matching of donor and acceptor energy levels. SiO2-RuYbL3, SiO2-YbRuL, SiO2 d-YbRuL and SiO2-NdRuL were carried out from grafting of d-f heterobimetallic silylated complexes. Grafting efficiencies from 0.03 to 0.17 were obtained. Luminescent properties from these nanohybrids were similar to the free complexes. However the SiO2-YbRuL and SiO2 d-YbRuL showed distinct luminescent profiles compared with the free Yb—RuL. The grafting inside the mesoporous channels may prevent luminescent desactivation processes comparing to the dense silica matrix. The photophysical properties associated with the morphology and stability of the mesoporous silica matrix allow suggesting these new NIR luminescent nanohybrids as nanoprobes or nanomarkers in biomedicine.

To serve well as luminescent labels in biological applications, complexes of the lanthanide ions need to fulfil many criteria, including the requirement of high quantum yields, stability towards dissociation in biological media and preferably, excitation at wavelengths over 350 nm. Herein, a number of aspects regarding the sensitization of europium(III) and terbium(III) ions are discussed with respect to the design and development of novel complexes. The effect of the addition of anions such as fluoride and phosphate to the Eu(III) and Tb(III) complexes of a known tris(bipyridyl) cryptate, are studied with a view to gaining a better understanding of non-radiative deactivation pathways of the lanthanide excited state. Enhancements of Eu3+ emission within the cryptate are noted whilst with the Tb3+ analogue, emission is significantly reduced upon displacement of OH by these ions. A new ligand based on a polyaminocarboxylate structure with a single bipyridyl chromophore is then reported, which displays nine-coordination around the enclosed lanthanide ion. The luminescence properties of the europium complex are very good but the terbium complex shows more complex behaviour, suggestive of a back energy transfer mechanism from the terbium excited state to the ligand triplet level. The development of ligands with mixed N,O pyrido-phenol chromophoric groups, which are expected to be better sensitizers of terbium(III) luminescence, is also outlined. Finally, in the quest to sensitize europium using longer wavelengths, acridone is incorporated into an azamacrocyclic structure and luminescence is observed from the complexed Eu3+. The quantum yield of luminescence is found to increase with decreasing distance between the sensitizer and the ion, and in the presence of coordinating donor atoms.