This work investigates the applicability of fast detectors to the technique of microscope-mode imaging mass spectrometry. By ionising analyte from a large area of the sample, and projecting the desorbed ions by the use of ion optics through a time-of-flight mass spectrometer onto a two- dimensional detector, time- (and hence mass-) dependent distributions of ions may be imaged. To date, this method of imaging mass spectrometry has been limited by the ability to image only one mass window of interest per experimental cycle, limiting throughput and processing speed. Thus, the alternative microprobe-mode imaging mass spectrometry is currently the dominant method of analysis, with its superior mass resolution. The application of fast detectors to microscope-mode imaging lifts the restriction of the detection of a single mass window per experimental cycle, potentially decreasing acquisition time by a factor of the number of mass peaks of interest. Additional advantages include the reduction of sample damage by laser ablation, and the potential identification of coincident eo-fragments of different masses originating from the same parent molecule. Theoretical calculations and simulations have been performed confirming the suitability of conventional time-of-flight velocity-mapped ion imaging apparatus for imaging mass spectrometry. Only small modifications to the repeller plate and laser beam path, together with the adjustment of the accelerating potential field, were required to convert the apparatus to a wide (7 mm diameter) field-of-view ion microscope. Factors affecting the mass and spatial resolution were investigated with these theoretical calculations, with theoretical calculations predicting a spatial resolution of about 26μm and m/m of 93. Typical experimental data collected from velocity-mapped ion imaging experiments were collected, and characterised in order to provide specifications for a novel time-stamping detector, the Pixel Imaging Mass Spectrometry detector. From these data, the suitability of thresholding and centroiding on the new detector was determined. Initial experiments using desorptionjionisation on silicon and conventional charge-coupled device cameras confirmed the correct spatial-mapping of the apparatus. Matrix-assisted laser desorptionjionisation techniques (MALDI) were used in experiments to determine the spatial and mass resolutions attainable with the apparatus. Experimental spatial resolutions of 14.4 μm and m/m of 60 were found. The better experimental spatial resolution indicates a higher di- rectionality of initial velocities from MALDI desorption than used in the theoretical predictions, while the poorer mass resolution could be attributed to limitations imposed by the use of the phosphor screen. Proof-of-concept experiments using fast-framing cameras and the new time-stamping detectors confirmed the feasibility of multiple mass acquisition in time-of-flight microscope mode ion imaging. Mass-dependent distributions were acquired of different pigment distributions in each experimental cycle. Finally, spatial-mapped images of coronal mouse brain sections were acquired using both conventional and fast detectors. The apparatus was demonstrated to provide accurate spatial distributions with a wide field-of-view, and multiple mass distributions were acquired with each experimental cycle using the new time-stamping detector.

A Dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science. / The addition of cyclohexyl substituents to existing ligands was investigated for its potential use as a factor in ligand design for achieving high specificity for particular metal ions, (Abbreviation abstract) / AC 2018

Foram medidas distribuições angulares e funções de excitação do espalhamento de íons de ANTPOT. 16 O e ANTPOT. 18 O por ANTPOT. 92 Zr a energias Incidentes em torno da barreira Coulombiana, visando estudar a interferência nuclear-Coulombiana na excitação inelástica dos estados 2+ (0.934 MeV), 2 IND. 2+ (1.847 MeV) e 3- (2.340 MeV) do ANTPOT. 92 Zr, bem como na excitação do estado 2+ (1.962 MeV) do ANTPOT. 16 O, Além do espalhamento elástico e dos inelásticos, foram também observadas as reações (ANTPOT. 16 O, ANTPOT. 15 N) e ( ANTPOT. 16 O, ANTPOT. 17 O), com Intensidades comparáveis as das transições inelásticas. Foram obtidas distribuições angulares e funções de excitação também para estas reações. Os resultados experimentais foram analisados com cálculos utilizando a aproximação de Born com ondas distorcidas (DWBA) e com o formalismo de canais acoplados. A análise das distribuições angulares mostra que o padrão da interferência nuclear-Coulombiana na excitação do estado 2+ do ANTPOT. 92 zr, tanto por ANTPOT. 16 O como por ANTPOT. 18 O, somente pôde ser reproduzida introduzindo um forte termo de reorientação nuclear, e ao mesmo tempo uma intensidade de transição nuclear multo maior do que o que seria esperado dos valores de B(E2). A Introdução de reorientação no estado 3- também permitiu melhor ajuste a distribuição angular deste estado. A análise da função de excitação do estado 2+ do ANTPOT. 92 Zr mostra que, para ajustar a região da Interferência nuclear-Coulombiana, é necessário Introduzir um termo de acoplamento dependente da energia incidente. Para as reações de transferência, foi obtido um ajuste multo bom, com DWBA, para a reação (ANTPOT. 16 O, ANTPOT. 15 N). Para a reação (ANTPOT. 18 O, ANTPOT. 17 O), entretanto, encontrou-se grande discrepância entre os calculas DWBA e os dados experimentais são discutidas as possíveis origens de tais comportamentos fora dos \"padrões tradicionais\". / Angular distributions and excitation functions for the elastic and inelastic scattering of 16,18 O by 92 Zr were measured at energies in the vicinity of the Coulomb barrier, in order to study the Coulomb-nuclear Interference in the excitation of the 2+ (0.93\"1 MeV), 2 2+ (1.847 MeV) and 3- (2.340 MeV) states of 92 Zr, as well as In the excitation of the 2+ (1.982 MeV) state of 18 O. Besides the elastic and inelastic scattering, the transfer reactions ( 16O, 15N) and (18O, 17O) were also observed, with Intensities comparable to the Inelastic excitations. Angular distributions and excitation functions were thus obtained for these reactions as well. The experimental results were analyzed with DWBA and coupled channels calculations. The results from the analysis of the angular distributions show that the Coulomb-nuclear interference pattern in the 92 Zr (2+) excitation, both by 16 O and 18 O, could only be reproduced by Introducing a strong nuclear reorientation term, and at the same time a nuclear transition coupling much stronger than what would be expected from the B(E2) values. The Introduction of a nuclear reorientation term In the 3- excitation also lended to a better fit in the 3- angular distribution. The results of the analysis of the Zr(2+) excitation function shows that It is necessary to introduce an energy dependent coupling term In order to fit the Coulomb-nuclear Interference pattern. For the transfer reactions It was seen that DWBA can describe very well the ( 16O, 15N) angular distribution. For the (18O,17O) reaction, however, great discrepancies were found between the DWBA calculations and the experimental data. The possible origins of such \"uncommon\" behavior are discussed.

Le travail de recherche présenté dans ce manuscrit est dédié à la synthèse et la caractérisation structurale, électrique et spectroscopique de nouveaux composés à base d'ion uranyle, d'oxoanions de métaux de transition (Niobates, tantalates et antimonates) et des métaux alcalins, susceptibles de se former en fin de cycle du combustible nucléaire. Une large partie de cette étude a été consacrée a la famille de niobates A1-xUNbO6-x/2,(X = 0 et 0,5 et A = alcalin). Cette famille de composés adopte deux types d'architectures structurales: structures tridimensionnelles présentant des tunnels ou structures bidimensionnelles avec empilement de couches, où les contrecations monovalents sont localisés dans les tunnels ou entre les couches. Le rôle du cation alcalin dans la connectivité et la dimensionnalité des structures, ainsi que sur la stabilité de ces phases a été également mis en évidence, en réalisant différentes substitutions entre cations alcalins: Cs1.-xKxUNbO6, CS0.5-xRbxUNbO5.75 et Cs1-xRbxUNb06 ou entre oxoanions : CS0.5UNb1-xTixO5.75-x/2 et CS0.5UNb1-xWxO5.7S+x/2. L'étude s'est également étendue à d'autres oxoanions comme les tantalates et antimoinates. La résolution structurale de nouvelles phases AUMO6 (A = K et Cs ;M = Ta, Sb) et A0,5UTaO5,75 (A = Rb, Cs) a été effectuée à partir des données de diffraction des rayons X sur poudre. / The work presented in this manuscript was dedicated to the synthesis and to the structural, electric and spectroscopic characterization of new compounds containing ion uranyl, transition metal oxoanions (Niobates, tantalates and antimonates) and alkaline metals. The first part of this study was devoted to the niobate family A1-xUNbO6-x/2, with x = 0 and 0,5 and A = alkaline; ln this family, the compounds can adopt two types of structural architectures: three-dimensional structures presenting large tunnels, or two-dimensional structures with a stacking of layers, where the monovalent cations are localized in the tunnels or between the layers. The role of the alkaline cation in the structural connectivity and dimensionality, as also in the stability of these phases, has been evidenced by carrying out various substitutions between alkaline cations: Cs1.- xKxUNbO6, CS0.5-xRbxUNbO5.75 and Cs1-xRbxUNbO6 or between oxoanions: CS0.5UNb1-xTixO5.75-x/2 and CS0.5UNb1-xWxOS.7S+x/2. The last part of that study was devoted to the alkaline uranyl tantalates and antimoinates. The structures of these new compounds AUMO6 (A = K et Cs; M = Ta, Sb) and A0,5UTaO5,75 (A = Rb, Cs) have been determined from powder X-Ray diffraction data.

A estrutura nuclear do primeiro estado excitado do ANTPOT.64 Zn (J POT.= 2 POT.+, E IND.X = 0.992 MeV) foi estudada através de medidas do efeito de reorientação neste núcleo, e de distribuições angulares e funções de excitação do espalhamento de ANTPOT.16 O e ANTPOT.18 O por ANTPOT.64 Zn na região de interferência nuclear-coulombiana. Foram investigados os processos de interação do núcleo ANTPOT.64 Zn com os íons ANTPOT.16 O e ANTPOT.18 O no espalhamento inelástico sem e com excitação do projétil. O efeito de reorientação na excitação coulombiana observado através do retroespalhamento de ANTPOT.4 He, ANTPOT.16 O e ANTPOT.18 O, permitiu a determinação precisa da probabilidade reduzida de transição B(E2; O POT.+ 2 POT.+) e do momento de quadrupolo estático Q IND.2+ do primeiro estado excitado do ANTPOT.64 Zn. As distribuições angulares e funções de excitação experimentais do espalhamento elástico de ANTPOT.16 O e ANTPOT.18 O por ANTPOT.64 Zn foram analisadas com o modelo óptico. Os resultados experimentais do espalhamento inelástico de ANTPOT.16 O e ANTPOT.18 O pelo mesmo núcleo, na região de interferência nuclear-coulombiana, foram analisados com a aproximação de Born com ondas distorcidas (DWBA) e considerando o acoplamento de canais, com fator de forma do modelo coletivo. Foram determinados os parâmetros de deformação nuclear do primeiro estado excitado 2 POT.+ do ANTPOT.64 Zn e do ANTPOT.18 O. / he nuclear structure of the first excited state of 64Zn (J=2+, Ex=0.992MeV) was studied by measuring the reorientation effect in this nucleus, the angular distributions and excitation functions of 16O and 18O scattering by 64Zn, in the Coulomb-nuclear interference region. The interaction processes between the 64Zn nucleus and the 16O and 18O ions in the inelastic scattering, with and without projectile excitation, were also investigated. The reorientation effect in Coulomb excitation, observed through backscattering of 4He, 16O and 18O ions, allowed a precise determination of the reduced transition probability B(E2; O+ 2+) and the static quadrupole moment Q2+ of the first excited state of 64Zn. Analyses of the angular distributions and excitation functions, obtained for the elastic scattering of 16O and18O by 64Zn, were performed in terms of the optical model. The experimental results fot the inelastic scattering of 16O and 18O by the same nucleus, in the Coulomb-nuclear interference region, were analysed by means of both distorted wave Born approximation (DWBA) and channel coupling with a collective form factor. Nuclear deformation parameters were thus determined for the 2+1 state of 64Zn and of 180.

A new preparative route to the only neutral chromium (V) oxide fluoride, chromium oxide trifluoride, has been accomplished by the reaction of xenon difluoride with chromyl fluoride at high temperature. The chromium oxide trifluoride is produced as crystals which are suitable for single crystal studies. In reactions of chromium oxide trifluoride with alkali and alkaline metal fluorides in anhydrous hydrogen fluoride, new chromium(V) oxide fluoride salts were obtained; these salts were not of high purity due to unknown problems. An attempt to prepare chromium oxide tetrafluoride by the reaction of xenon difluoride with chromyl fluoride in anhydrous hydrogen fluoride failed to produce the desired product.

Ph.D. thesis 1970 from the Dept. of Physical & Inorganic Chemistry University of Adelaide / 152 leaves : ill., graphs / Title page, contents and abstract only. The complete thesis in print form is available from the University Library.

Thesis (Ph. D.)--State University of New York at Binghamton, Chemistry Dept., 2006. / Includes bibliographical references.

Bibliography: leaves 143-153. Studies the complexation of metal ions with the macrocyclic ligand, 1, 4, 8, 11-tetrakis (2-hydroxyethyl)-1, 4, 8, 11-tetraazacyclotetradecane (THEC)

The hairpin ribozyme is a small catalytic RNA that cleaves a phosphodiester bond. In order for cleavage to occur, the hairpin ribozyme must properly fold into its docked conformation, in which the two loops interact to form the active site. Metal ions and the four-way junction play critical roles in the stabilization of the docked conformation. The work presented in this thesis attempts to investigate the metal-ion dependence of the docking of the four-way junction construct of the hairpin ribozyme. In addition, the activity of the hairpin ribozyme in the presence of Mn2+ was observed. Initially, a four-stranded four-way junction construct of the hairpin ribozyme and a loopless mutant were characterized by native gel electrophoresis and thermal denaturation to verify ribozyme formation. A novel interaction between the sulfur of a phosphorothioate-substituted mononucleotide, such as adenosine thiomonophosphate (AMPS) or adenosine thiotrisphoshate (ATPgS), and Cd2+ has been characterized by UV-vis spectroscopy. A feature at 208 nm was identified to be a result of sulfur-to-Cd2+ transfer. The apparent binding affinities, the apparent extinction coefficients, and the binding ratios were determined for each complex.