Thesis (Ph. D.)--Princeton University, 1924.

Integrins are transmembrane heterodimer protein receptors that mediate adherence to both the intracellular cytoskeleton and extracellular matrix. They play a major role in cellular adhesion and the breadth of their importance in biology is only recently being understood. The ability to detect concentrations of integrins on the cell surface, spatially resolve them, and study the dynamics of their behavior would be a significant advance in this field. Ultimately, the ability to detect dynamic changes of integrins on the surface of a cell maybe possible by developing a combined device such as an atomic force microscope (AFM) and surface enhanced Raman spectroscopy (SERS) system. However, the focus of this research is to first determine if integrins can be detected using SERS. Surface enhanced Raman spectroscopy (SERS) is technique used to detect the presence of analytes at the nanomolar level or below, through detection of inelastically scattered light. This thesis discusses the detection of integrins employing SERS as the detection modality. Integrins have been detected, in solution, using two silver colloids as the enhancing surface. Two silver colloid preparation methods are compared by ease of formulation and degree of enhancement in this thesis. Citrate and hydroxylamine hydrochloride (HA-HCl) reduced silver colloids were prepared through wet chemistry,compared using UV-Vis light spectroscopy, and tested for surface enhancement using adenine (a strong SERS active molecule), and two different integrins, (alpha)V(beta)3 and (alpha)5(beta)1. Results indicated that both colloids demonstrate SERS activity for varying concentrations of adenine as compared to standard non-enhanced Raman, however, only the citrate reduced colloid showed significant enhancement effect for the integrins.

AbstractEugen Bomberger's original work was concerned with the rearrangement of the substituted N-phenylhydroxylamines, but the mechanism responsible for the wide variety of products has remained unsettled.First, this investigation was concerned with a suitable synthesis for the substituted N-alkyl-N-phenylhydroxylamines. Secondly, a better understanding of the mechanism could be accomplished by the identification of the decomposition products and through a kinetic study of the rearrangement utilizing ultraviolet spectroscopy. The study was successful with the product identification of five decomposed substituted N-.phenylhydroxylamines, but numerous products, which interfered with the kinetic study, were isolated from the rearrangement and only uninterpretable kinetic data could be collected.Ball State UniversityMuncie, IN 47306

In the U.S. Chemical Safety and Hazard Investigation Board (CSB) report, Improving Reactive Hazard Management, there are 37 out of 167 accidents, which occurred in a storage tank or a storage area. This fact demonstrates that thermal runaway problems in chemical storage processes have not been give enough attention. Hydroxylamine Nitrate (HAN) is an important member of the hydroxylamine compound family and its diluted aqueous solution is widely used in the nuclear industry for equipment decontamination. It is also used as a solid or aqueous propellant. Due to its instability and autocatalytic behavior, it has been involved in several incidents at the Hanford and Savannah River Sites (SRS). Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work focuses on extracting its autocatalytic kinetics mechanism and studying its critical behavior from adiabatic calorimetry measurements. The lumped autocatalytic kinetics model, the associated model parameters and HAN critical condition are determined for the first time. The contamination effect of iron ions and nitric acid on diluted hydroxylamine nitrate solution is also studied. This work also identified the safe storage conditions for a small quantity HAN diluted solution with thermal explosion theory. Computational Fluid Dynamics (CFD) was used to further study the influence of natural convection and system scale on the critical behavior for a large quantity of chemical and thus proposed the practical storage guidelines for industrial practice.

Integrins are transmembrane heterodimer protein receptors that mediate adherence to both the intracellular cytoskeleton and extracellular matrix. They play a major role in cellular adhesion and the breadth of their importance in biology is only recently being understood. The ability to detect concentrations of integrins on the cell surface, spatially resolve them, and study the dynamics of their behavior would be a significant advance in this field. Ultimately, the ability to detect dynamic changes of integrins on the surface of a cell maybe possible by developing a combined device such as an atomic force microscope (AFM) and surface enhanced Raman spectroscopy (SERS) system. However, the focus of this research is to first determine if integrins can be detected using SERS. Surface enhanced Raman spectroscopy (SERS) is technique used to detect the presence of analytes at the nanomolar level or below, through detection of inelastically scattered light. This thesis discusses the detection of integrins employing SERS as the detection modality. Integrins have been detected, in solution, using two silver colloids as the enhancing surface. Two silver colloid preparation methods are compared by ease of formulation and degree of enhancement in this thesis. Citrate and hydroxylamine hydrochloride (HA-HCl) reduced silver colloids were prepared through wet chemistry,compared using UV-Vis light spectroscopy, and tested for surface enhancement using adenine (a strong SERS active molecule), and two different integrins, (alpha)V(beta)3 and (alpha)5(beta)1. Results indicated that both colloids demonstrate SERS activity for varying concentrations of adenine as compared to standard non-enhanced Raman, however, only the citrate reduced colloid showed significant enhancement effect for the integrins.

Thesis (Ph. D.)--University of Washington, 1998. / Vita. Includes bibliographical references (leaves [134]-149).

<p> Conditions for the precipitation of nickel salicylaldoximate from homogeneous solution were examined and procedures were recommended for the determination of nickel when present alone or mixed with some diverse ions. </p> <p> The reaction between salicylaldehyde and hydroxylamine was studied in aqueous solution and some of the reaction parameters were evaluated. </p> / Thesis / Master of Science (MSc)

<p>The complex nature and composition of regolith cover in Southern Africa is a major challenge to geochemical mapping for concealed mineralization. Some of the setbacks to successful geochemical exploration may be ascribed to the use of various partial extraction techniques,without a profound understanding of the regolith components and their composition. This investigation therefore focuses on the use of hydroxylamine partial extraction geochemistry for geochemical mapping in regolith over two contrasting environments viz / aeolian sand-calcrete regolith over Au mineralization at Amalia Blue Dot Mine in South Africa and lateritic regolith covering the Ni-Cu deposit at Kabanga Main and Luhuma in Tanzania. Regolith samples from the above areas were sieved and extracted with hydroxylamine hydrochloride solution and analyzed for multi-element by AAS and ICP-MS techniques. A stepwise optimization of the hydroxylamine extraction technique of samples from both areas was carried out and incorporated into the analytical programme (in a pilot study). Results of hydroxylamine partial extraction generally gave better anomaly contrast and reflection of bedrock mineralization than the conventional aqua regia techniques that were previously used in the region. The results however show that lateritic regolith may be best extracted using 0.25M hydroxylamine while 0.1M concentration appears most suitable for extraction of aeolian-calcrete regolith. The above results are corroborated by principal component analysis of the analytical data that show various element associations, e.g. with Fe-Mn oxides while others possibly belong to the loosely adsorbed or exchangeable group. The&nbsp / gochemical maps in the pilot study areas at Amalia, Kabanga and Luhuma show elevated element contents or clusters of anomalies of diverse elements associated with Fe-Mn oxides. Geochemical mapping at Kabanga with deeply concealed mineralization however shows variability of subdued element patterns over mineralized areas. Geochemical signatures associated with hydroxylamine hydrochloride partial leach are therefore characterized by a lower geochemical background than that using conventional aqua regia leach. This study leads recommending for further investigations into partial extraction of the exchangeable group of elements, possibly using ammonium acetate.</p>

Hydroamination stands as a desirable approach to nitrogen-containing molecules, which have important applications ranging from pharmaceuticals (fine chemicals) to paints, coatings, insecticides and agrochemicals (bulk chemicals). It features the use of alkene and alkyne starting materials, which are abundant and rarely used in the formation of C-N bonds. This work aims at building on the improved Cope-type reactivity developed in the Beauchemin group by expanding the reach of the reaction and understanding its mechanistic complexities. The first part of this thesis describes the development of cascade reactions to provide a thermodynamic driving force for the intermolecular Cope-type hydroamination of alkenes. The methodology serves as a proof of concept that the dipolar reaction intermediates can be engineered to further react irreversibly to more stable products, and has shown potential in improving the syntheses of natural alkaloids. The second part of the thesis describes the expansion of Cope-type hydrazide hydroaminations through a systematic investigation of hydrazine analogs as reactants. Optimized reagents are featured in the first reported intermolecular Cope-type hydrohydrazidation of alkenes. Mechanistic investigations and isolation of ammonium ylide intermediates support a 5-membered concerted and planar mechanistic pathway for hydrazide hydroaminations, similar to that observed with hydroxylamines. The final section presents mechanistic data disproving a previously assumed difficult proton transfer step in the hydroamination using hydroxylamines. From such findings, early results are presented towards a hydrogen-bond catalyzed hydroamination, which has potential applicability across the field of Cope-type hydroaminations and beyond.

<p>The complex nature and composition of regolith cover in Southern Africa is a major challenge to geochemical mapping for concealed mineralization. Some of the setbacks to successful geochemical exploration may be ascribed to the use of various partial extraction techniques,without a profound understanding of the regolith components and their composition. This investigation therefore focuses on the use of hydroxylamine partial extraction geochemistry for geochemical mapping in regolith over two contrasting environments viz / aeolian sand-calcrete regolith over Au mineralization at Amalia Blue Dot Mine in South Africa and lateritic regolith covering the Ni-Cu deposit at Kabanga Main and Luhuma in Tanzania. Regolith samples from the above areas were sieved and extracted with hydroxylamine hydrochloride solution and analyzed for multi-element by AAS and ICP-MS techniques. A stepwise optimization of the hydroxylamine extraction technique of samples from both areas was carried out and incorporated into the analytical programme (in a pilot study). Results of hydroxylamine partial extraction generally gave better anomaly contrast and reflection of bedrock mineralization than the conventional aqua regia techniques that were previously used in the region. The results however show that lateritic regolith may be best extracted using 0.25M hydroxylamine while 0.1M concentration appears most suitable for extraction of aeolian-calcrete regolith. The above results are corroborated by principal component analysis of the analytical data that show various element associations, e.g. with Fe-Mn oxides while others possibly belong to the loosely adsorbed or exchangeable group. The&nbsp / gochemical maps in the pilot study areas at Amalia, Kabanga and Luhuma show elevated element contents or clusters of anomalies of diverse elements associated with Fe-Mn oxides. Geochemical mapping at Kabanga with deeply concealed mineralization however shows variability of subdued element patterns over mineralized areas. Geochemical signatures associated with hydroxylamine hydrochloride partial leach are therefore characterized by a lower geochemical background than that using conventional aqua regia leach. This study leads recommending for further investigations into partial extraction of the exchangeable group of elements, possibly using ammonium acetate.</p>