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We report the development of a general route to the synthesis of [4.3.1], [3.3.1], an especially [3.2.1] bicyclic compounds structurally related to vitisinol D, a natural product. This allows for diastereoselective synthesis of bicyclic compounds with five adjacent chiral centers. This route was employed in a preliminary SAR investigation into the neuroprotectant effect of small molecules in an in vivo experiment measuring the degree of restorative effect of synaptic transmission in the neuromuscular junction of Drosophila melanogaster larvae under acute oxidative stress. One of the compounds exhibited intriguing potential as a neuroprotectant and outperformed resveratrol in restoring synaptic function under oxidative stress. The hypothesis that bridged bicyclic compounds may hold promise as drug scaffolds due to their conformational rigidity and ability to orient functional appendages in unique orientations is developed. The second focus is a mechanistic investigation into a tetrabutylammoniumcatalyzed cycloaddition as evidence of a novel ammonium-alkyne interaction. A carbamate nitrogen adds to a non-conjugated carbon–carbon triple bond under the action of an ammonium catalyst leading to a cyclic product. Studies in homogeneous systems suggest that the ammonium agent facilitates cyclitive nitrogen–carbon bond formation through a cation–π interaction with the alkyne unit. Using Raman spectroscopy, this cation–π interaction is directly observed for the first time. DFT modeling elucidated the mechanistic factors in this cycloaddition. A teaching experiment was developed based on this mechanistic investigation. Control experiments were employed to demonstrate the testing of two alternative mechanistic hypotheses. Cyclization reactions were performed with a soluble base (sodium phenoxide) with and without tetrabutylammonium bromide under homogeneous conditions. Students observed that ammonium salt accelerates the reaction. They were encouraged to develop a testable hypothesis for the role of the ammonium salt in the cyclization mechanism: typical phase transfer or other. IR spectroscopy was used to directly observe a dose dependent shift of the alkyne stretching mode due to a cation−π interaction. Undergraduates were able to employ the scientific method on a contemporary system and see how data are generated and interpreted to adjudicate between rival hypotheses in a way that emulates authentic and current research in a lab setting. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

by Qi Li. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 192-199). / Acknowledgment --- p.i / Abstract --- p.ii / Table of Contents --- p.iii / Index of Componds --- p.iv / List of Tables --- p.v / List of Figures --- p.vi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1. --- General Survey of Inclusion Chemistry --- p.1 / Chapter 1.2. --- The Importance of Hydrogen Bonds --- p.5 / Chapter 1.3. --- "Classical Inclusion Compounds of Urea, Thiourea and Selenourea" --- p.8 / Chapter 1.4. --- Research Strategy --- p.12 / Chapter 2. --- Description of Crystal Structures --- p.16 / Chapter 2.1. --- Urea-Anion Inclusion Compounds --- p.16 / Chapter 2.1.1. --- Halide complexes --- p.18 / Chapter 2.1.2. --- Bicarbonate complexes --- p.30 / Chapter 2.1.3. --- Allophanate complexes --- p.36 / Chapter 2.1.4. --- Borate and pentaborate complexes --- p.44 / Chapter 2.1.5. --- Complex featuring both host-host and host-guest hydrogen bonding --- p.60 / Chapter 2.1.6. --- Tetraethylammonium and phosphonium chloride complexes --- p.65 / Chapter 2.2. --- Thiourea-Anion Inclusion Compounds --- p.71 / Chapter 2.2.1. --- Halide Complexes --- p.73 / Chapter 2.2.2. --- Bicarbonate Complexes --- p.76 / Chapter 2.2.3. --- Nitrate Complexes --- p.87 / Chapter 2.2.4. --- Formate Complexes --- p.101 / Chapter 2.2.5. --- Acetate Complexes --- p.113 / Chapter 2.2.6. --- Oxalate and Fumarate Complexes --- p.127 / Chapter 2.2.7. --- Unsymmetrical quaternary ammonium ions as guests --- p.138 / Chapter 2.3. --- Selenourea-Anion Inclusion Compounds --- p.152 / Chapter 3. --- Summary and Discussion --- p.161 / Chapter 3.1. --- Structural Features and Relationships --- p.161 / Chapter 3.2. --- Hydrogen Bonding in Urea/Thiourea/Selenourea-Anion Inclusion Compounds --- p.164 / Chapter 3.3. --- Linkage Modes of Urea and Thiourea Molecules --- p.168 / Chapter 3.4. --- Comolecular Aggregates of Urea and Other Host Components --- p.173 / Chapter 3.5. --- Comolecular Aggregates of Thiourea and Other Host Components --- p.175 / Chapter 4. --- Experimental --- p.177 / Chapter 4.1. --- Preparation --- p.177 / Chapter 4.2. --- Crystallography --- p.182 / Chapter 5. --- References --- p.192 / Appendix A: Tables of Atomic coordinates and thermal parameters --- p.200 / Appendix B: Publication Based on Results Reported in This Thesis --- p.243

Energetic materials are a class of material that have large amounts of chemical energy stored within their molecular structure. This energy is released upon decomposition, generally in the form of rapidly expanding, hot gases. They are therefore used for a wide range of applications such as; mining, military, and space exploration, and there is therefore a strong desire to improve the overall performance and safety of such materials. On account of reduced sensitivity to initiation by shock and impact, 2,4-dinitroanisole (DNAN) is a potential replacement for 2,4,6-trinitrotoluene (TNT) in melt-cast formulations for military applications. However, up to 15 % irreversible growth of DNAN has been previously observed upon thermal cycling and is a key reason why DNAN has not yet been universally accepted as a replacement for TNT. DNAN exhibits a complex system of polymorphism. One particular transition from DNAN-II to DNAN-III, which occurs at 266 K, has been observed in these studies to cause 8 - 10 % growth of DNAN-II pellets when temperature cycled for 30 cycles between 256 K and 276 K. What was even more concerning was the appearance of cracking of DNAN pellets after being temperature cycled. Doping the crystal structure of DNAN-II with related molecules, such as 2,4-dinitrotoluene or 2,4-dinitroaniline, was investigated in order to probe how steric and electronic factors affect the transition. The addition of varying amounts of 2,4-dinitroaniline suppressed this transition to varying extents and ultimately as low as 150 K with 10 mol% 2,4-dinitroaniline, and potentially eliminated entirely. This doped material has been designated as phase-stabilised DNAN (PS-DNAN). Temperature cycling of PS-DNAN was conducted over the same 256-276 K range, and this material showed no evidence of irreversible growth compared to undoped DNAN pellets, on account of suppression of the II-III transition. The production of PS-DNAN is therefore a possible route to avoiding problematic irreversible growth in DNAN formulations. Melt-casting of DNAN in a sealed environment consistently results in the metastable form-II, which has proven to be stable for in excess of 32 weeks. However, exposure to seeds of form-I, either via deliberate or accidental seeding, rapidly converted the material to the thermodynamically more stable form-I. This transition was accelerated by increasing temperature which rapidly converted pellets of DNAN-II to DNAN-I. When DNAN-I pellets were temperature cycled, they did not undergo a transition to form-III, and as a result did not illustrate irreversible growth. This presents another approach to avoiding problematic growth in DNAN-based materials. Whilst being one of the most widely used oxidisers in propellant formulations, ammonium perchlorate (AP) has several issues; the formation of porous ammonium perchlorate (PAP) can seriously affect the sensitivity of propellants, the hygroscopicity of AP makes handling and manufacture of formulations difficult, and spherical AP exhibits poor binding properties to the polymer binders used in propellant formulations. Several different approaches were taken to combat these issues. Co-crystallisation of AP was attempted in order to produce new AP co-crystals with reduced reactivity towards the formation of PAP. A theoretical based approach using COSMOtherm was used for rapid screening and selection of potential co-formers to be used in lab-based co-crystallisation trials. Co-crystallisation was attempted using multiple stoichiometries and multiple solvents by solvent evaporation, cooling crystallisation, and Resonant Acoustic Mixing methods. Unfortunately no new co-crystals were obtained, presumably on account of the ionic nature of AP which makes co-crystallisation difficult. The mass of untreated AP increased by 0.027% in a humid environment (90% RH) due to the uptake of water, which resulted in significant caking and hence hindering the processability of AP. In an attempt to counteract the hygroscopicity and improve the processability of AP, particles of AP were coated in graphene nanoplatelets using the technique of Resonant Acoustic Mixing. Low mixing energy (G-force) (30 G) resulted in poor coating of AP, but the flowability of this mixure after exposure to moisture was significantly enhanced, most probably as a result of graphene acting as an effective lubricant. Higher mixing energy (90-100 G) was required to break up agglomerates of graphene nanoplatelets and resulted in AP particles efficiently coated with graphene (APGR). Differential scanning calorimetry showed that the energy released upon decomposition of APGR was greater than pure AP, or AP mixed with graphene, due to the intimacy of the AP particle surface and the graphene coating.

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Daniel K. Cha, Dept. of Civil & Environmental Engineering. Includes bibliographical references.

La tesis describe un método completamente nuevo sobre la aplicación de este micro-tecnología en la producción de los catalizadores, específicamente NH4-dawsonite. Las soluciones acuosas utilizadas para precipitar el material se define como nonahidrato nitrato de aluminio y carbonato de amonio. La preparación del mineral análogo se realizó por primera vez dentro de un micro-mezclador de acero inoxidable (CPMM 1200/8) con un volumen de 78μl y un principio de mezcla “split-recombine”, optimizando los parámetros del proceso para un tiempo de producción continuo que, en este caso, es significativamente afectado por la obstrucción del micro-canal. Además, la síntesis se realizó dentro del micro-sistema presurizado y se han propuesto otro tres diferentes geometrías del micro-canal: en forma de T de acero inoxidable, el poly (metylmetacrylate) (PMMA) spilt-recombine del micromixer Caterpillar y en forma de Y la unión de PMMA dos regímenes diferentes de mezcla (perfecta (spilt-recombine) / imperfecto (T / Y en forma de microsistemas)) con el objetivo de minimizar la obstrucción del canal. El enfoque de unión-Y se ha demostrado ser la mejor alternativa para reducir al mínimo la deposición de partículas en la pared del canal, lo que implica un mejor control del fenómeno de obstrucción, al estar totalmente eliminado. Esto representa un paso adelante en el proceso de intensificación con beneficios en la industria. Al superar este paso, la posibilidad de transferir esta nueva tecnología en la industria es cada vez más tangible a convertirse en realidad. / The thesis presents a new approach regarding the application of microtechnology in production of catalysts, specifically NH4-dawsonite by using microreactor technology. The aqueous solutions used to precipitate the material were defined as aluminium nitrate nonahydrate and ammonium carbonate. The mineral analogue preparation was first held within a 78μl volume split-recombine stainless steel micromixer (CPMM 1200/8 mixer) by optimizing the process parameters for a continuous time of production which in the present case is significantly affected by the channel clogging. Further, the synthesis was carried out within a pressurized micro-system and different geometries of the microchannel: T-shaped stainless steel, poly(metylmetacrylate) (PMMA) spilt-recombine Caterpillar micromixer and Y-shaped PMMA junction with two different mixing regimes (perfect (spli-recombine)/imperfect (T/Y-shaped microsystem)) with the aim of minimizing the clogging. The Y-junction approach was demonstrated to be a great alternative for minimizing the particle deposition on channel’s wall, clogging phenomenon being totally removed. This represents a significant step forward in process intensification with benefits within the industry. Over passing this step the possibility to transfer this new technology into industry is more and more tangible to become reality.

Thesis (Ph. D.)--Lehigh University, 2000. / Includes vita. Includes bibliographical references (leaves 170-174).

Thesis (Ph. D.)--University of Michigan. 1931. / "By Alfred L. Ferguson. Richard Hitchens and Kenneth Van Lentes." From Transactions of the Electrochemical society, v. 71, 1937.

Thesis (M. Phil.)--University of Hong Kong, 1977.

Despite the environmental significance of microbial manganese reduction, the molecular mechanism of microbial manganese respiration remains poorly understood. Soluble Mn(III) has been recently found to be a dominant soluble species in aquatic systems, yet little is known about the identity of microbial populations catalyzing Mn(III) reduction in the environment nor the molecular mechanism of Mn(III) respiration. In this research, a suite of Mn(III) reduction-deficient mutant strains were isolated, including Mn(III) reduction-deficient mutant strain Mn3-1 that also displayed the ability to reduce soluble organic-Fe(III), but not solid Fe(III) oxides, demonstrating for the first time that the reduction of soluble organic-Fe(III) and solid Fe(III) oxides proceed through electron transport pathways with at least one distinct component. This work also shows that the electron transport pathway for Mn(III) reduction in S. oneidensis shares many of the electron transport components of Fe(III) and Mn(IV) reduction pathways and that Mn(IV) reduction to Mn(II) proceeds step-wise through two one-electron transfer reactions with Mn(III) as a transient intermediate. Finally, sediment incubations were carried out to enrich for NH4+ oxidizing- Mn(III) reducing consortia. The Mn(III) reducing consortium was found to be dominated by an electrogenic Ochrobactrum sp. and a Shewanella sp. The isolated Shewanella strain is able to oxidize acetate with Mn(III) as electron acceptor, an activity never observed before in a metal-reducing member of the Shewanella genus.