Biotic interactions are known to shape natural community assemblages and biodiversity. Positive interactions such as facilitation have recently received attention in ecological food webs. Mechanistic models have improved our understanding of these complex food web interactions. Here, focus is given to a three-species food web system with a beach dune natural community in mind. In the last decade, there has been a series of studies investigating intraguild predation between two major loggerhead sea turtle nest predators, North American raccoons and Atlantic ghost crabs. Studies have also highlighted that ghost crab predation assists raccoons in finding nests (i.e., facilitated predation). However, the combined effects of these two intraguild interactions and their consequences on nests have not been examined explicitly. The aims of this study were to (i) develop a three-species, ordinary differential equation model (ii) implement a sensitivity analysis to understand the influence of facilitation and other factors in driving species richness and abundance and (iii) characterize the dynamic interactions between intraguild predators and their effects on a shared resource. Interactions between ghost crabs and sea turtle eggs and facilitation can yield a wide variety of species abundance responses and were influential factors in the model. I found that high secondary sea turtle egg depredation and low facilitated predation by raccoons led to three species co-existence regions in the model. Controlling for nest predators at higher abundance levels showed that ghost crabs had a larger negative effect on sea turtle egg abundance responses when compared to raccoons. This suggests that interactions between sea turtle eggs and ghost crabs appear to be important and potential sea turtle nest management implications are discussed such as the use of ghost crab exclusion devices.

<p> The photochemistry of 1,1-diphenylsilacyclobutane has been studied by steady-state and nanosecond laser flash photolysis (NLFP) techniques in order to investigate the mechanism of reaction of a transient silene with alcohols. NLFP of 1,1-diphenylsilacyclobutane (I) in acetonitrile solution at 325 nm results in the formation of 1,1-diphenylsilene (II) derived from excited-state [2+2]-cycloreversion of the silacyclobutane. The transient has a lifetime of 100 ns - 1.2 μS in acetonitrile solution at room temperature, depending on the presence of water in the solvent. Steady-state photolysis in the presence of various σ-bonded nucleophiles such as methanol results in the generation of a single product in each case, consistent with addition of the nucleophile to the silene (II). Absolute rate constants (kq) have been determined by NLFP techniques for reactions of the silene with water, methanol, ethanol, tert-butyl alcohol, 2-propanol, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoroisopropanol, and glacial acetic acid. The rate constants (kq) illustrate the following characteristics: linear quenching plots characteristic of second order kinetics, observation of small but detectable deuterium kinetic isotope effects, and an inverse Arrhenius temperature dependence. Two possible mechanisms will be discussed based on these results. (See Mechanisms in Thesis)</p> / Thesis / Master of Science (MSc)

<p> This thesis describes a study of the photosolvolysis of N-benzoyl-5-bromo-7-nitroindoline. The investigation was instigated because N-acyl-5-bromo-7-nitroindolines have been considered as potential photoprotecting groups for the photolithographic formation of charge-mosaic membranes. However, no kinetic data, and only scant mechanistic information, has been reported for the photofragmentation process.</p> <p> Both absorption and emission spectra of N-benzoyl-5-bromo-7-nitroindoline were obtained. Based on the electronic spectra, it would seem that the two lowest energy singlet excited states are nearly isoenergetic and their relative energies are a function of the solvent medium.</p> <p> The distribution of photoproducts obtained from irradiation of N-benzoyl-5-bromo-7-nitroindoline in various solvent systems was investigated. It was shown that the photosolvolysis reaction is a function of the solvent properties. Thus 5-bromo-7-nitroindoline and benzoic acid were the only photoproducts formed in acetonitrile. In acetonitrile-water, 5-bromo-7-nitrosoindole as well as 5-bromo-7-nitroindoline and benzoic acid were identified. A correlation between solvent polarity, ET(30), and 5-bromo-7-nitrosoindole formation was observed.</p> <p> The mechanism of the fragmentation mode was examined. The presence of a free radical intermediate is suggested from the photoproduct distribution in tetrahydrofuran (THF). Observation of an electron spin resonance (e.s.r.) spectrum during irradiation of N-benzoyl-5-bromo-7-nitroindoline in an e.s.r. spectrometer cavity, 18_0 incorporation into benzoic acid, and a linear free energy relationship with sigma dot (σ•) corroborated the intermediacy of a free radical in the fragmentation process.</p> <p> Quantum yields of N-benzoyl-5-bromo-7-nitroindoline disappearance in different solvents and quenchers were measured in order to establish the reactive excited state and the effect of the medium on the efficiency of the transformation process. A solvent dependency on both the excited state lifetime and photosolvolysis reaction efficiency was noted. The results were indicative of a change in mechanism with a variation in solvent polarity and/or hydrogen bonding ability.</p> <p> A mechanism compatible with experimental results and applicable to previously reported N-acyl-2-nitroaniline photofragmentations is proposed.</p> / Thesis / Doctor of Philosophy (PhD)

<p> Dicobalt octacarbonyl reacts with a wide variety of molecules containing trichloromethyl functionalities to yield carbynyl tricobalt nonacarbonyl clusters of the general formula R-CCo 3 (CO) 9 . While these clusters have been shown to undergo many reactions, mechanistic studies on these systems are sparse. In particular, their rather facile decarbonylation processes are not well understood. </p> <p> Complexes of the type Ar-CO-CCo 3 (CO)9 readily lose CO to produce the corresponding Ar-CCo 3 (C0) 9 clusters but the origin of the carbon monoxide extruded was not known . Speculation had focussed on two possibilities: firstly, direct elimination of the ketonic carbonyl - perhaps via radical intermediates - and, secondly, via initial loss of a cobalt carbonyl ligand (to produce a 16-electron cobalt vertex) with subsequent migration of the original ketonic group onto the coordinatively unsaturated cobalt center. These two mechanistic possibilities are differentiable by labelling either the cobalt carbonyl sites or the ketonic position with carbon-13 and then examining the decarbonylated product to locate the isotopically enriched positions by 13c NMR spectroscopy. It is shown that the carbon monoxide initially eliminated is a cobalt carbonyl and the ketonic CO migrates from its apical position onto a cobalt atom. </p> <p> A second project involves the synthesis and characterization of a cobalt cluster derived from the reaction of dicobalt octacarbonyl with the insecticide DDT . This cluster contains the bis(4-chlorophenyl)methylcarbynyl capping group which is so bulky that it has the potential to stop the rotation of the carbynyl ligand and also prevent carbonyl exchange on the metal triangle. The DDT-tricobalt cluster was characterized by X-ray crystallography. The compound crystallizes in the space group P21/n: the monoclinic cell has dimensions a = 13.083 A, b = 14.222 A, c = 14.165 A, B = 95.871 degrees and Z = 4. The molecule adopts almost Cs symmetry except that the phenyl rings are twisted slightly so as to destroy the potential mirror plane. At low temperature, the cobalt carbonyl ligands are non-equivalent on the NMR time-scale and the possible causes for this behaviour are discussed. </p> / Thesis / Master of Science (MSc)

<p> A detailed study of the photoaddition of 3-phenylcyclohex- 2-enone and 2,3-dimethylbut-2-ene was undertaken in order to gain mechanistic information of the photochemistry of this enone. Photoadditions of this enone with cyclopentene, norbornene, and but-2-ene were also studied. Sensitization experiments showed that photoaddition with 2,3-dimethylbut-2-ene occurs when triplet sensitizers such as Michler's ketone or 2-acetonaphthone are used. The sensitized reactions are less efficient than the direct irradiation, except at infinite 2,3-dimethylbut-2-ene concentration, when the quantum yields for direct and sensitized processes are the same. This quantitative result may be explained by (a) inefficiency in the energy-transfer process from the sensitizer to enone 0 or (b) two excited states of enone being involved in the direct and sensitized processeso There are evidences that the excited state involved in the direct irradiation could possibly be the second triplet of the enoneo The presence of a higher enone tTiplet (T2) was established by the observed dimerization of norbornene. Cis-trans isomerization of but-2-ene was observed during photoaddition, which could also be attributed to a higher triplet, or to a 1,4-diradical intermediates Quenching studies provided an estimate of the lifetime of the reactive excited state in the direct irradiation. The energies of the electronic states of the enone were estimated from spectroscopic and chemical measurements. The formation of an enoneoolefin 1,4-diradical has been proposed to explain the effect of olefin concentration on the photoaddition. </p> / Thesis / Doctor of Philosophy (PhD)

The current study is an experimental and analytical investigation of JIB within the nucleate and transition boiling regimes. This study focuses on studying JIB within the stagnation zone of a free water jet. An experimental setup has been designed and built at the Thermal Processing Laboratory (TPL) with the capability of carrying out boiling experiments at heat fluxes up to 12 MW/m2. The JIB curves have been obtained under steady-state conditions for a wide range of jet conditions, higher than those considered during previous JIB studies. The effect of jet velocity, up to 3.8 m/s, and degree of subcooling, up to 49 °C, on the JIB curve has been studied. The results showed that both jet velocity and degree of subcooling have a weak effect on the nucleate boiling regime and significantly affect the transition boiling regime. Bubble dynamics under the impinging jet within the nucleate boiling regime and the stability of the vapor layer within the transition boiling regime have been investigated. An analytical mechanistic model, based on force balance and thermal balance equations, has been developed to predict the bubble growth rate and the BDD. The developed model was validated using current experimental data. The model gave a relative deviation of 17.8 %. Results of the mechanistic model within the stagnation zone showed that, amongst the three heat transfer mechanisms that affect bubble growth (i.e., the microlayer evaporation, the heat from the superheated layer, the convection heat loss to subcooled liquid), the microlayer evaporation is the most significant contributor to the rate of bubble growth. The current work conducted within the transition boiling regime was focused on the determination of the total wall heat flux within the stagnation zone, both experimentally and analytically. Steady-state experiments have been carried out during which the vapor layer stability was examined. The vapor layer breakup frequency was measured using a fiber-optic probe. Experiments were conducted at a jet velocity of 1 m/s and degrees of subcooling between 11 and 49 ºC. / Thesis / Doctor of Philosophy (PhD)

Yes / Nanocrystalline hydroxyapatite (nanoHA) is the main hard component of bone and has potential to be used to promote osseointegration of implants and to treat bone defects. Here, using active pharmaceutical ingredients (APIs) like ibuprofen, we report on the prospects of combining nanoHA with biologically active compounds to improve the clinical performance of these treatments. In this study we designed and investigated the possibility of API attachment to the surface of nano-HA crystals via the formation of a hydrogen-bonded complex. The mechanistic studies of an ibuprofen/nanoHA complex formation have been performed using a holistic approach encompassing spectroscopic (FT-IR and Raman) and X-ray diffraction techniques as well as quantum chemistry calculations (DFT), while comparing the behaviour of the ibuprofen/nanoHA complex with that of a physical mixture of the two components. Whereas ibuprofen exists in dimeric form both in solid and liquid state, our study showed that the formation of the ibuprofen/nanoHA complex most likely occurs via the dissociation of the ibuprofen dimer into monomeric species promoted by ethanol, with subsequent attachment of a monomer to the HA surface. An adsorption mode for this process is proposed; this includes hydrogen bonding of the hydroxyl group of ibuprofen to the hydroxyl group of the apatite, together with the interaction of the ibuprofen carbonyl group to an HA calcium centre. Overall, this mechanistic study provides new insights into the molecular interactions between APIs and the surfaces of bioactive inorganic solids and sheds light on the relation between the non-covalent bonding and drug release properties. / Authors would like to acknowledge funding support from EPSRC (EP/L027011/1, EP/K029592/1). This research was performed in part at the MIDAS Facility, at the University of Sheffield, which was established with support from the Department of Energy and Climate Change.