The Miocene rhyolites of the Spor Mountain Formation hosts the world's largest beryllium deposit which produced 85% of the world's beryllium in 2010. The fresh lava is extremely enriched in Be (up to 75 ppm in matrix glass). We have examined the rhyolite to understand the Be enrichment. The Spor Mountain rhyolite contains ~40% quartz, ~40% sanidine, ~10% biotite, and ~10% plagioclase, along with accessory fluorite, columbite, euxenite, fergusonite, monazite, thorite, and zircon. Two types of rhyolite erupted within the Spor Mountain Formation, a less evolved magma (1150 ppm Rb, 42 ppm Be, 0.68 wt% F in matrix glass) and an evolved magma (1710 ppm Rb, 75 ppm Be, 1.56 wt% F in matrix glass). Eruption temperatures estimated using zircon saturation, feldspar-liquid, two feldspar, and Ti-in-quartz geothermometers converge on 718 °C for the less evolved magma and 682 °C for the evolved magma. Using the Ti-in-Qz equation of Huang and Audetat (2012), the pressure of the Spor Mountain rhyolite system is estimated to be around 2 kbar at 700°C. Water content of the rhyolite melt was less than <5 wt%, based on the presence of all four major mineral phases at 700°C and the magma was water undersaturated (Webster et al., 1987). Viscosity of the rhyolite was about 6.2 log Pa·s for the less evolved rhyolite and 5.8 log Pa·s for the evolved rhyolite. Magma viscosities calculated using the Einstein-Roscoe question suggest the evolved magma has a slightly higher viscosity than the less evolved magma (7.0 log Pa·s in the evolved magma vs 6.7 log Pa·s in the less evolved magma) because of higher phenocryst content. Fluorine lowered the melt viscosity, though not by a significant amount (less than 0.5 log units at 1.7 wt% F). Partition coefficients for 32 elements have been calculated for biotite, for 21 elements for sanidine and plagioclase, and for 6 elements for quartz, using data acquired by laser ablation inductively coupled plasma mass spectrometry. Partition coefficients for feldspars in the Spor Mountain rhyolite are generally higher than other silicic magmas, and lower for biotite. Beryllium is one of the most incompatible trace elements in the Spor Mountain rhyolite, with a bulk partition coefficient <0.1. Volatile content of the melt (specifically F), melt composition, and the low temperature of crystallization act as the major controls of trace element partitioning. Trace element models using these partition coefficients suggests that crystal fractionation is the dominant magmatic enrichment process within the rhyolite, requiring ~45% crystallization (f = 55%) of the observed phenocrysts to get compositions from the less evolved to evolved rhyolite. Accumulation of batches of melt formed by different degrees of partial melting cannot explain the great depletion of compatible elements.

The use of principles of supramolecular chemistry to direct reactions in the crystalline state has emerged as a reliable means to facilitate highly selective reactions in a solvent-free environment. In this context, we have utilized the fixed spatial arrangements of molecules in a crystal lattice to promote intermolecular [2+2] photodimerizations. We have shown how principles of supramolecular chemistry can be used to preorganize olefins to undergo intermolecular [2+2] photodimerizations in the solid state. Explorations into fluorinated and partially fluorinated olefinic substrates has allowed for development of underutilized supramolecular interactions to direct such chemical reactions. We reported interactions between fluorinated molecules in inorganic complexes and organic solids that supported intermolecular [2+2] photodimerizations as well as cross-reactions between olefinic species. Analogous to the hydrogen bond templates commonly utilized by our group to engineer reactive solids, we expanded the methodology by developing templates that direct reactions via halogen bonding. We report on the use of a halogen-bond-acceptor template to direct the formation of a small molecule lined with I- and F-atoms. We demonstrate the olefins in the solid undergo a [2+2] photodimerization with UV radiation in a stereoselective and quantitative manner. Our work provides the first use of halogen bonds to direct the formation of a small-molecule lined with halogen atoms in a solid. We reveal the halogenated product provides access to a unique family of host-guest materials that exhibit an extremely rare form of self-inclusion. We describe the ability of halogen bonds to undergo bending deformations. There are currently great interests in halogen bonds as related to applications to organic synthesis, supramolecular chemistry, and materials science. While halogen bonds are often compared to hydrogen bonds, the wealth of knowledge concerning the fundamentals and behavior of halogen bonds has admittedly experienced less time to develop. In our work on single-crystal reactions and transformations, we have discovered the ability of halogen bonds based on rigid interacting partners to bend and deform. We provide a quantitative comparison of the bending to the literature to demonstrate how the geometric landscape of the bending compares to known data. We report a single-crystal-to-single-crystal transformation of a cocrystalline material involving a fluorinated, olefinic compound. The olefins adopt a well-defined, reactive geometry mediated by halogen-bonding templates. We exploit metal-organic complexes to fix spatial arrangements of molecules in crystal lattices to promote intermolecular [2+2] photodimerizations. Perfluorophenyl-perfluorophenyl (C6F5···C6F5) interactions have recently emerged as a means to control supramolecular architectures and frameworks. However, it was not clear whether perfluorophenyl-perfluorophenyl interactions can be integrated in [2+2] photodimerizations in solids. We describe the significant effect fluorine exercised on the structure and photoreactivity of an octafluoro stilbene derivative in the solid state. Specifically, we report the olefin, trans-1,2-bis(2,3,5,6-tetrafluorophenyl)ethylene, self-assembles via C-H···F and perfluorophenyl-perfluorophenyl interactions for a stereoselective and quantitative topochemical photodimerization. Lastly, principles of crystal engineering and supramolecular chemistry are exploited to design and achieve a supramolecular protecting group strategy for the solid-state synthesis of a cyclobutane—a cyclobutane that supports a rare hydrogen-bonded self-catenating framework. The application of a hydrogen bonding coformer to separate a trans-isomer of a pyrimidyl olefin directly from a Wittig reaction is demonstrated. The coformer supports a head-to-head [2+2] photodimerization in the solid state. The work demonstrated here describes our explorations into the supramolecular interactions of organic fluorine, and how such interactions can be used to facilitate the synthesis of small molecules via [2+2] photodimerizations in solids—alone and in accompaniment of other crystal engineering strategies.

La chimie du fluor suscite un intérêt croissant de la part des chimistes organiciens de par son exploitation industrielle dans les domaines pharmaceutique et agrochimique. Ainsi, depuis plusieurs années, de nouvelles méthodes permettant d'introduire de manière efficace et sélective des groupements fluorés - et plus particulièrement des fluoroalkyles - sur des molécules cibles sont activement recherchées. Les hydrazones sont des molécules largement utilisées en synthèse organique, notamment comme précurseurs de nombreux composés très recherchés par les industries pharmaceutiques ou agrochimiques, incluant les amines primaires et les hétérocycles azotés tels que les pyrazoles et les indoles. Dans le cadre de cette thèse, nous nous sommes intéressés à la fluoroalkylation des hydrazones. Les premières études ont visé la trifluorométhylation cupro-catalysée d'hydrazones d'aldéhydes et de cétones, lesquelles ont conduit respectivement à la formation d'hydrazones trifluorométhylées et de diimides alpha-trifluorométhylés. Par la suite, cette transformation a été entendue à la béta-trifluorométhylation régiosélective d'hydrazones alpha,béta-insaturées. Enfin, nous nous sommes intéressés au développement de réactions de difluoroalkylation d'hydrazones d'aldéhydes catalysées par le palladium ou le cuivre. Les divers composés obtenus lors de ces études se sont avérés être d'excellents précurseurs de cétones et d'indoles trifluorométhylés, d'alpha,alpha-difluoro-béta-cétoesters, ou encore d'alpha,alpha-difluorocétones / Fluorine chemistry is attracting the growing interest of organic chemists due to its industrial exploitation in the pharmaceutical and agrochemical fields. Thus, new methods for the effective and selective introduction of fluorinated groups – and particularly fluoroalkyls - on target molecules have been sought in recent years. Hydrazones are widely used reagents in organic synthesis, notably as precursors of many compounds pursued by the pharmaceutical or agrochemical industries, including primary amines and nitrogen heterocycles such as pyrazoles and indoles. This thesis work focused on the fluoroalkylation of hydrazones. The first studies have been directed toward the copper-catalyzed trifluoromethylation of aldehyde- and ketone-derived hydrazones, which led to the formation of trifluoromethylated hydrazones and alpha-trifluoromethylated azenes, respectively. Subsequently, this transformation was extended to the regioselective beta-trifluoromethylation of alpha,beta-unsaturated hydrazones. Finally, our interest focused on the development of difluoroalkylation reactions of aldehyde-derived hydrazones under palladium or copper catalysis. The various compounds obtained in these investigations have proven to be valuable precursors of trifluoromethylated ketones and indoles, alpha, alpha-difluoro-beta-ketoesters, as well as alpha,alpha-difluoroketones

ABSTRACT Anaplastic lymphoma kinase (ALK) is a tyrosine kinase receptor, which plays a pivotal part in the development of the central nervous system. Aberrant expression of full-length ALK occurs in neuroblastoma and chromosomal translocation or inversion of the ALK gene can generate novel fusion-ALK proteins that possess constitutive kinase activity and contribute to oncogenic processes. One of the well-studied fusion proteins is nucleophosmin (NPM-ALK), which draws a lot of attention for medicinal chemists to design small molecules as kinase inhibitors for this target. In this dissertation, [1, 2, 4]-Dihydrotriazine dimers as competitors of the lead compound NVP-TAE684 targeting NPM-ALK have been designed and synthesized. Molecular modelling studies show that those dihydrotriazine dimers have a great potential to be better kinase inhibitors. Chapter two describes imaging in the drug discovery and development arena. One of important imaging techniques is positron emission tomography (PET). PET is a radionuclide based molecular imaging technique, which can be used for early detection, characterization, "real time" monitoring of diseases, and investigation of the efficacy of drugs. Fluorine-18 (18F) based molecular probes for PET imaging still remain big challenging to prepare but have gained increased interest by radiochemists in the past two decades. In this study, a novel approach to introduce fluorine into a molecular probe has been discovered based on boron chemistry. A few novel fluorine capture reagents have been synthesized and described in this Chapter.

It is the responsibility of humans, as environmental stewards, to monitor our impact on the environment so that efforts can be made to remediate the effects of our actions and change behaviors. To better understand our environmental footprint, sensitive and simple analytical methods are needed to quantify the contaminants that we discharge into our natural surroundings. Emerging environmental contaminants are of particular concern because there is limited or no information available on their occurrence, fate, and toxicity. As a result, the implications of using these chemicals are not well understood. Therefore, accurate environmental data are needed to help scientists and government policy-makers make informed decisions on research directions and chemical regulation. However, challenges exist for the analysis of emerging contaminants, including a lack of suitable analytical standards and internal standards, their broad range of chemical properties, and that they are frequently present at trace levels and in complex environmental matrices. The work presented within this dissertation focuses on the development, validation, and comparison of analytical methodologies based on large-volume injection high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS) for the analysis of emerging environmental contaminants in aqueous environmental matrices. Large-volume injection (e.g. 900 μL to 4,500 μL) is an analytical technique that eliminates sample preparation associated with pre-concentration by injecting larger-than-traditional volumes of sample directly onto a HPLC column. In Chapter 2, a direct aqueous large-volume injection method was developed and validated for the quantification of natural and synthetic androgenic steroids in wastewater influent, wastewater effluent, and river water. This method was then applied to hourly composite samples of wastewater influent that were taken over the course of a single day. This work expands on the research of the endocrine-disrupting chemicals that occur in wastewater and provides an estimate of the community use/abuse of synthetic androgenic steroids. Environmental analytical methods should be as environmentally friendly as possible and efforts should be made to reduce the waste generated during analysis while maintaining analytical performance. In Chapter 3, a method based on large-volume injection was compared to two methods based on solid-phase extraction. The purpose of this comparison was to demonstrate that the same method performance could be achieved by large-volume injection as that by solid-phase extraction while reducing waste, labor, and costs. Estrogens and perfluorinated chemicals were used as model analytes and wastewater influent was used as a model matrix. The results of this study provide convincing reasons for analysts to adopt large-volume injection as an alternative to solid-phase extraction. In Chapter 4, a novel analytical method was developed and validated to quantify newly-identified and legacy fluorinated chemicals in groundwater. The final method combined micro liquid-liquid extraction, non-aqueous large-volume injection, and orthogonal chromatographic separations. Ground water samples collected from six different U.S. military bases was used to demonstrate the method. This is the first report on the occurrence of these newly-identified fluorinated chemicals in any environmental media and serves as a rational for conducting future research on their environmental fate and toxicity. The breadth of the research presented in this dissertation advances the field of environmental analytical chemistry in several areas. First, classes of environmental contaminants for which there is limited (synthetic androgenic steroids) or no (newly-identified fluorochemicals) environmental data were studied. Second, novel methods based on direct-aqueous and non-aqueous large-volume injection were developed and validated to identify and quantify those contaminants. Third, it was demonstrated that solid-phase extraction is not a "necessary evil" needed to develop methods for emerging environmental contaminants in aqueous matrices. Finally, this work is a platform on which other environmental chemists can use to develop large-volume injection methods in the future. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 2, 2012 - Feb. 2, 2013

This work improved the radiosynthesis of a known M2 muscarinic receptor imaging agent, [18F]FP-TZTP, and subsequent syntheses and in vitro evaluation of several novel TZTP derivatives highlighted a lead compound which exhibited M4 potency and selectivity, the thioether fluoro-polyethyleneglycol, which was then adapted for radiolabelling (23% radiochemical yield (uncorrected), >99% radiochemical purity, reaction time of 37 minutes). The present study also seeked to utilize aziridines as intermediates in [18F]-radiolabelling chemistry for the facile radiosynthesis of [18F]-labelled beta-blockers. Novel [18F]-labelled amines were synthesized via ring-opening and deprotection to yield the [18F]-1-fluoro-2-propanamine moiety (85%) favourably over the regioisomer [18F]-2-fluoro-1-propanamine (15%). Subsequent attempts to use these amine synthons in the synthesis of the beta-blocker [18F]Exaprolol resulted in poor radiochemical yields (1-3%). The chemistry of aziridine ring-opening with 19F-fluoride sources was thoroughly explored in order to understand the fundamentals of this chemistry, and the 1-fluoro-2-propanamine moiety was characterized by X-ray crystallography and NMR spectroscopy.

This work improved the radiosynthesis of a known M2 muscarinic receptor imaging agent, [18F]FP-TZTP, and subsequent syntheses and in vitro evaluation of several novel TZTP derivatives highlighted a lead compound which exhibited M4 potency and selectivity, the thioether fluoro-polyethyleneglycol, which was then adapted for radiolabelling (23% radiochemical yield (uncorrected), >99% radiochemical purity, reaction time of 37 minutes). The present study also seeked to utilize aziridines as intermediates in [18F]-radiolabelling chemistry for the facile radiosynthesis of [18F]-labelled beta-blockers. Novel [18F]-labelled amines were synthesized via ring-opening and deprotection to yield the [18F]-1-fluoro-2-propanamine moiety (85%) favourably over the regioisomer [18F]-2-fluoro-1-propanamine (15%). Subsequent attempts to use these amine synthons in the synthesis of the beta-blocker [18F]Exaprolol resulted in poor radiochemical yields (1-3%). The chemistry of aziridine ring-opening with 19F-fluoride sources was thoroughly explored in order to understand the fundamentals of this chemistry, and the 1-fluoro-2-propanamine moiety was characterized by X-ray crystallography and NMR spectroscopy.

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (leaves 169-182).

Στα πλαίσια της παρούσας μεταπτυχιακής εργασίας μελετώνται οι υδρογεωλογικές και υδροχημικές συνθήκες που επικρατούν στην ευρύτερη περιοχή του Αιγίου, με έμφαση στη μελέτη του προσχωματικού υδροφόρου της περιοχής. Η περιοχή έρευνας έχει ως γεωλογικό υπόβαθρο τους σχηματισμούς της ζώνης της Πίνδου, ενώ το πεδινό και ημιορεινό της τμήμα είναι πληρωμένο από Πλειο-Πλειστοκαινικά και Ολοκαινικά ιζήματα. Τα Πλειο-Πλειστοκαινικά ιζήματα της περιοχής που αποτελούνται από πακέτα στρωμάτων που έχουν ταπεινωθεί από τα ρήγματα αποτελούν έναν ενιαίο υδροφόρο από επάλληλα στρώματα με μεταβαλλόμενη διαπερατότητα. Υπέρκεινται ενός καρστικού υδροφόρου ορίζοντα που φιλοξενείται σε σχηματισμούς που έχουν κατακερματιστεί και στραφεί από τα κανονικά ρήγματα. Οι δυο αυτοί υδροφόροι αποτελούν και τα κύρια υδροφόρα στρώματα της περιοχής. Τα υπόγεια νερά της περιοχής ομαδοποιούνται σε τρείς κύριους υδροχημικούς τύπους (Ca-HCO3, Ca-HCO3-SO4 και Na-HCO3). Ως προς την ποιότητά τους, κατά τόπους φαίνονται εμπλουτισμένα σε ενώσεις του αζώτου, σε ιόντα φθορίου και σε συγκεκριμένα ιχνοστοιχεία όπως ο ψευδάργυρος, ο μόλυβδος και το μαγγάνιο. Από την αξιολόγηση των αποτελεσμάτων πειραμάτων έκπλυσης και ορυκτολογικών προσδιορισμών, που αφορούν στην επίδραση που έχει η χημική σύσταση των ιζημάτων στην σύσταση του υπόγειου νερού, διαπιστώνεται ότι ο εμπλουτισμός των νερών της περιοχής των Νεραντζιών σε φθόριο πιθανά οφείλεται στην εμφάνιση λιγνιτικών οριζόντων της περιοχής. Με τη χρήση των ισοτόπων οξυγόνου και υδρογόνου διαπιστώνεται ότι το νερό του ελεύθερου υδροφόρου με μικρές αποκλίσεις προέρχεται από το μετεωρικό νερό της περιοχής. Επιπλέον από την μέτρηση του διαλελυμένου 220Rn στο νερό προέκυψε ότι τα αέρια αυτά στην περιοχή έρευνας, είναι δυνατόν να αποτελέσουν ιχνηλάτες των ενεργών ρηγμάτων της περιοχής. / In the frame of the present thesis the hydrogeological and hydrochemical conditions that prevail in the broader Aigion region are analyzed and interpreted. The study emphasizes in the unconfined aquifer of Plio-Pleistocene sediments. The geological background of the research area consists of the carbonate rocks and the flysch of the Olonos Pindos zone, whereas at the lower parts these formations are overlain with Plio-Pleistocene sediments as well as Holocene fluvial deposits. The study area hosts two major aquifers, one of Plio-Pleistocene sediments consisting of subsided blocks formed by tectonic activity, forming a uniform, unconfined aquifer with diverse permeability. These formations are underlain by a karstic aquifer which is faulted and rotated by normal faults. Groundwaters of the region can be grouped in three main hydrochemical types (Ca-HCO3, Ca-HCO3-SO4 and Na-HCO3). Concerning their quality it is shown that they are enriched in nitrogen compounds and fluorine, as well in certain trace elements, such as Pb, Zn, Mn. The results from the leaching experiments and mineralogical determination, concerning the effect of the chemical composition of sediments in the groundwater chemistry indicate that there is a possible enrichment of fluorine in Neratzies aquifer due to lignite outcrops in this region. The relationship between meteoric and underground water was investigated by the use of δD and δ18O isotopes. It is concluded that the water is mainly of meteoric origin. Moreover by the measurement of diluted 220Rn in water it is suggested that, these in the research area can be used as pathfinders of active cracks and faults.

No description available.