DEVELOPMENT OF FUNCTIONAL NANOPARTICULATE MATERIALS: Examination of the Functional and Structural Properties of Nanoparticulate Metal Complexes Prepared by Precipitation with Compressed Antisolvent Technology

A diverse set of systems that interact with nitric oxide (NO) is important because of its adverse role in environmental chemistry and importance in mammalian biology. Towards this effort, nanomaterials that interact with NO have been developed because they can display beneficial and unique chemical and physical properties from their larger counterparts. While several nanomaterials have been developed that store and release NO, few systems composed entirely of metal complexes have been reported. The research described in this dissertation involves the development of nanomaterials that interact with NO. Molecule-based nanoparticulate metal complexes were prepared using precipitation with compressed antisolvent technology. Microscopy and powder x-ray diffraction were used to determine that the nanoparticles form lamellar structures during processing. These nanoparticulates also displayed enhanced reactivity towards NO and O2 compared to their unprocessed analogs. The preparative routes towards the synthesis of immobilized metal complexes within silica particles are also discussed

Long-term Informative Path Planning with Autonomous Soaring

The ability of UAVs to cover large areas efficiently is valuable for information gathering missions. For long-term information gathering, a UAV may extend its endurance by accessing energy sources present in the atmosphere. Thermals are a favourable source of wind energy and thermal soaring is adopted in this thesis to enable long-term information gathering. This thesis proposes energy-constrained path planning algorithms for a gliding UAV to maximise information gain given a mission time that greatly exceeds the UAV's endurance. This thesis is motivated by the problem of probabilistic target-search performed by an energy-constrained UAV, which is tasked to simultaneously search for a lost ground target and explore for thermals to regain energy. This problem is termed informative soaring (IFS) and combines informative path planning (IPP) with energy constraints. IFS is shown to be NP-hard by showing that it has a similar problem structure to the weight-constrained shortest path problem with replenishments. While an optimal solution may not exist in polynomial time, this thesis proposes path planning algorithms based on informed tree search to find high quality plans with low computational cost. This thesis addresses complex probabilistic belief maps and three primary contributions are presented: • First, IFS is formulated as a graph search problem by observing that any feasible long-term plan must alternate between 1) information gathering between thermals and 2) replenishing energy within thermals. This is a first step to reducing the large search state space. • The second contribution is observing that a complex belief map can be viewed as a collection of information clusters and using a divide and conquer approach, cluster tree search (CTS), to efficiently find high-quality plans in the large search state space. In CTS, near-greedy tree search is used to find locally optimal plans and two global planning versions are proposed to combine local plans into a full plan. Monte Carlo simulation studies show that CTS produces similar plans to variations of exhaustive search, but runs five to 20 times faster. The more computationally efficient version, CTSDP, uses dynamic programming (DP) to optimally combine local plans. CTSDP is executed in real time on board a UAV to demonstrate computational feasibility. • The third contribution is an extension of CTS to unknown drifting thermals. A thermal exploration map is created to detect new thermals that will eventually intercept clusters, and therefore be valuable to the mission. Time windows are computed for known thermals and an optimal cluster visit schedule is formed. A tree search algorithm called CTSDrift combines CTS and thermal exploration. Using 2400 Monte Carlo simulations, CTSDrift is evaluated against a Full Knowledge method that has full knowledge of the thermal field and a Greedy method. On average, CTSDrift outperforms Greedy in one-third of trials, and achieves similar performance to Full Knowledge when environmental conditions are favourable

Tin-selenium compounds at ambient and high pressures

SnxSey crystalline compounds consisting of Sn and Se atoms of varying composition are systematically investigated at pressures from 0 to 100 GPa using the first-principles evolutionary crystal structure search method based on density functional theory (DFT). All known experimental phases of SnSe and SnSe2 are found without any prior input. A second order polymorphic phase transition from SnSe-Pnma phase to SnSe-Cmcm phase is predicted at 2.5 GPa. Initially being semiconducting, this phase becomes metallic at 7.3 GPa. Upon further increase of pressure up to 36.6 GPa, SnSe-Cmcm phase is transformed to CsCl-type SnSe-Pm3m phase, which remains stable at even higher pressures. A metallic compound with different stoichiometry, Sn3Se4-I43d, is found to be thermodynamically stable from 18 GPa to 70 GPa. Known semiconductor tin diselenide SnSe2-P3m1 phase is found to be thermodynamically stable from ambient pressure up to 18 GPa. Initially being semiconducting, it experiences metalization at pressures above 8 GPa

Existence and uniqueness for the non-compact Yamabe problem of negative curvature type

We study existence and uniqueness results for the Yamabe problem on non-compact manifolds of negative curvature type. Our first existence and uniqueness result concerns those such manifolds which are asymptotically locally hyperbolic. In this context, our result requires only a partial $C^2$ decay of the metric, namely the full decay of the metric in $C^1$ and the decay of the scalar curvature. In particular, no decay of the Ricci curvature is assumed. In our second result we establish that a local volume ratio condition, when combined with negativity of the scalar curvature at infinity, is sufficient for existence of a solution. Our volume ratio condition appears tight. This paper is based on the DPhil thesis of the first author.Comment: To appear in Analysis in Theory and Application