High-valent transition metal-oxo intermediates play essential roles as active oxidizing species in enzymatic and biomimetic catalytic systems. Extensive research has been conducted on a variety of transition metal catalysts being studied as models for the ubiquitous cytochrome P450 enzymes. In doing so, the production of enzyme-like oxidation catalysts and probing studies on the sophisticated oxygen atom transfer mechanism are taking place. In this work, visible-light irradiation of highly-photo-labile corrole-manganese(IV) bromates and chlorates was studied in two corrole systems with differing electronic environments, i.e. 5,10,15-trisphenylcorrole (H3TPC) and 5,10,15- tris(pentafluorophenyl)corrole (H3TPFC). In both systems, homolytic cleavage of the O- Br and O-Cl bonds in the ligands was observed to result in one-electron photo-oxidation to afford the corrole-manganese(V)-oxo species as determined by their distinct UV-vis spectra. Kinetics of oxygen atom transfer (OAT) reactions by each photo-generated [MnV(Cor)O] species with various substrates were conducted in two solvents, CH3CN and CH2Cl2. It was found that [MnV(Cor)O] exhibits noteworthy solvent and ligand effects on its reactivity and spectroscopic behavior. In the more electron-withdrawing TPFC species in polar CH3CN solvent, MnV-oxo corrole returned to MnIII corrole following oxidation of substrate. However, the TPFC species in the less polar CH2Cl2 solvent, and in both solvents for the TPC system, MnIV product was formed instead of MnIII. An inverted reactivity pattern, i.e. TPC > TPFC, for the MnV-oxo corroles was observed. These spectral and kinetic results were rationalized by a multiple oxidation pathway model, where either a two-electron oxidation for oxygen atom transfer reactions takes place or a disproportionation reactive takes place forming the elusive manganese(VI)-oxo as the true oxidant. The preferred pathway is highly dependent on the nature of the corrole ligand and the solvent. Furthermore, a variety of [MnIV(Cor)Cl] complexes were investigated as biomimetic catalysts for the selective catalytic oxidation of the organic sulfide with mild sacrificial oxidant PhI(OAc)2. It was found that catalytic activity was affected by the oxidation state and electron environment of the catalyst. It was also found that in the same TPC system, [MnIV(TPC)Cl] was more reactive than [MnIII(TPC)], presumably due to the MnIV-corrole having easier access to the active metal-oxo intermediates than MnIII-corrole. In the same oxidation state, catalytic sulfoxidation of thioanisole resulted in a slower reaction rate for corrole species with more electron withdrawing ligands. In addition to thioanisole, [MnIV(TPC)Cl] was tested for its reactivity under catalytic conditions for eight other substrates. In most cases, quantitative conversions and excellent selectivity for sulfoxide were achieved.

Success of newly discovered chemistry in academia is often scored in terms of its novelty and level of scholarship. In industrial settings, cost, safety and quality are often times the ruler by which new processes are measured. Our group has identified that there is a gap between these two measures of success and has sought to develop principles in order formalize an approach to synthetic strategy and developing ready-to-implement manufacturing processes for molecules, simple and complex. Some of these principles include (1) the development and application of new chemical methods and reactor technologies (2) recognition of globally amenable chemical environments for each chemical step to consolidate unit operations and obviate the need for purification (3) vertical integration of starting materials to generate complexity from the most elementary building blocks in a chemical supply space and (4) the development of new materials that allow for recovery and reuse. These principles are iteratively scored and redeveloped through various metrics that our group has identified as effective tools in maximizing efficiency such as cost of goods (CoG), process mass intensity (PMI) and volume-time output (VTO). The intended benefits of this approach is that these processes become not only cost effective but sustainable and impactful in the manufacturing landscape and increase access of these products to consumers.

Colloidal, metallic nanoparticles have myriad applications, but they are most ideal when they are monodisperse, and demonstrate maximum catalytic utility when they are small (< 5 nm) and uncoated; because their surface area is accessible and maximized. Laser- assisted metal nanoparticle synthesis is a ‘green’ method that has become a topic of active research because it is able to produce uncoated or ‘naked’ products. The nanoparticles synthesized in this work were formed through the reduction of metal salts in aqueous solutions; but the reducing agent is an electron-dense microplasma generated by the laser pulse interacting with the media. Because no chemical reducing agents or stabilizers are needed, the products have no surfactants. The underlying reaction mechanisms that drive this type of synthesis are generally understood, however, there is insufficient detail that would allow control over the formation of ultimate product morphologies and size distributions. The metals examined in this thesis are: gold, whose formation follows an autocatalytic rate law; and silver, whose formation follows a first-order rate law. Through my research, I was able to explore the effects that physical parameters (such as laser pulse settings) and chemical parameters (such as radical scavenger addition) have on laser-assisted gold or silver nanoparticle synthesis. My research, outlined in this thesis, is therefore focused on elucidating such details and distilling them into methods of control in order to better predict and tune nanoparticle products.

acase@tulane.edu

Particulate matter in the atmosphere emitted from various natural and anthropogenic sources is important due to their effects on the chemical balance of the atmosphere, the Earth's climate, human health and biogeochemical cycles. Although there have been many studies performed to understand the above effects, there still remains substantial uncertainty associated with processes involved and thus it is difficult for current atmospheric chemistry and climate models to reconcile model results with field measurements. Therefore, it is important to have better agreement between models and observations as the accuracy of future atmospheric chemistry and climate predictions depends on it. In this research, a greater understanding of the role of mineral dust chemistry was pursued through focused laboratory studies in order to better understand fundamental processes involved. In particular, studies to further understand the photochemistry of adsorbed nitrate, an important inorganic ion associated with particulate matter exposed to gas-phase nitrogen oxides, were conducted using Al2O3, TiO2 and NaY zeolite to represent non-photoactive components, photoactive components and aluminosilicate respectively, present in mineral dust. These studies reveal that photochemistry of nitrate adsorbed on mineral dust is governed by wavelength of light, physicochemical properties of dust particles and adsorption mode of nitrate. Gas phase NO2, NO and N2O are the photolysis products of nitrate on oxide particles under dry conditions. In contrast, nitrate adsorbed on zeolite is converted mainly to adsorbed nitrite upon irradiation. This nitrite yield is decreased with increasing relative humidity. Gas phase N2O is the main photolysis product of nitrate adsorbed in zeolite in the presence of co-adsorbed ammonia. Water adsorbed on semiconducting TiO2 can be photochemically converted to hydroxyl radicals. These hydroxyl radicals can be involved in surface mediated as well as gas phase oxidation reactions in the presence of cyclohexane. Another focus of this dissertation was to investigate the oxidation of sulfur dioxide oxidation in the presence of mineral aerosol, particularly, coal fly ash (FA), γ-Fe2O3 and Arizona test dust (AZTD), a model for mineral dust aerosol. Depending on the temporal evolution of Fe(II), we proposed that S(IV) oxidation in the presence of FA and γ-Fe2O3 initially occurs through a heterogeneous pathway and a homogeneous pathway is also possible over later time scales. S(IV) oxidation in the presence of AZTD appears to be mostly heterogeneous and does not lead to iron dissolution. Overall, these studies suggest that the rate, extent and products of atmospheric S(IV) oxidation can be highly variable and heavily dependent upon the nature of aerosol sources, thereby precluding simple generalizations about this reaction when modeling atmospheric processes involving diverse mineral dust aerosols. With the recent development in nanotechnology, nanoparticles are becoming a major fraction of atmospheric particulate matter. These particles can undergo aging under ambient conditions at any stage of their life cycle. This impacts the fundamental properties of these materials and therefore the behavior in the environment and interactions with biomolecules and biological systems. ZnO and CuO nanoparticles form adsorbed carbonate phases upon exposure to CO2 and water vapor. These carbonates become more solvated as the relative humidity is increased. Presence of carbonate phases on ZnO particles increases their water solubility. Thus, overall the work reported in this dissertation provides insights into heterogeneous and multiphase atmospheric chemical reactions in the presence of mineral aerosol and atmospheric aging of nanoparticles.

Le delta du Rhône est une vaste plaine alluviale recouverte d’étangs et de lagunes, parsemée de cultures diverses, principalement du riz (21’100 ha en 2009, Centre Français du Riz, 2010). Des herbicides répandus en avril (pré levée, prétilachlor) et en juin (poste levée, bentazone ; MCPA et dichlorprop) sont utilisés dans la riziculture pour lutter contre les mauvaises herbes. L’étang de Vaccarès, qui est classé «réserve de biosphère» par l’UNESCO pour sa grande richesse biologique reçoit des pesticides directement issus des rizières par les canaux de drainage. D’un point de vue scientifique, peu d’études sont consacrées au devenir des pesticides dans les eaux estuariennes. En outre, la plupart de ces études ont été focalisées sur la photochimie bien que la biodégradation soit impliqué dans l’atténuation des pesticides. Alors le but de ce travail de thèse est de comprendre le devenir des herbicides de riziculture en évaluant le rôle de la photochimie direct et indirect et de la biodégradation. Nous avons développé donc un modèle capable de décrire la transformation de molécules organique par la voie photochimique dans les eaux estuariennes. Enfin nous avons déterminé les processus principaux impliqués dans l'atténuation rapide des herbicides de riziculture en Camargue. / The Ile de Camargue basin is the central part of the Rhône Delta in the south of France included between the two branches of the river. The higher parts of this area are agricultural lands, mainly rice fields, whereas the lower parts are lagoons and natural wetlands of international importance for biodiversity preservation.Bentazone, dichlorprop, and MCPA are post-emerging herbicides applied in rice fields from mid April to mid June. Rice fields grown under flooded conditions represent an environment where these conditions increase the potential for pesticides to transport in runoff from rice fields to non- target surface waters.To predict their fate in the surface waters of the Camargue and to asses their risk, it is necessary to understand their chemical reaction under environmental conditions.Reactive photoinduced species (RPS, hydroxyl radical HO., singlet oxygen 1O2 and dissolved organic matter triplet state) in estuarine waters (Vaccarès lagoon) were characterized experimentally to estimate the role of photochemistry in rice paddy. We then developed a kinetic model describing the solar photo-transformation of xenobiotic organic compounds induced by the three different photooxidants RPS. Sunlight photodegradation of bentazone, dichlorprop (DCPP), MCPA and alachlor (used as a surrogate for the similar Pretilachlor, pre-emergence herbicide) and microbial transformation were conducted experimentally to estimate near-surface half-lives in surface water. Parallel to the experimental study, an assessment of the elimination rates of those herbicides by sorption and sedimentation, and volatilization were obtained by the model MASAS (Modelling of Anthropogenic Substances in Aquatic Systems).The half-lives of the herbicides obtained experimentally were then compared with those obtained from field data. This allowed to assessing the main processes involved in the attenuation of herbicide concentrations.

Abstract not available

Charge transfer (CT) complexes have been used in a number of radiation polymerisation processes including grafting and curing. The complexes studied include donor (D) monomers like vinyl ethers and vinyl acetate (VA) with acceptor (A) monomers such as maleic anhydride (MA). Both UV and EB have been utilised as radiation sources. The complexes are directly grafted to these substrates in the presence of radiation. The complexes yield novel copolymers when radiation cured with concurrent grafting improving the properties of the finished product. The term cure grafting has been proposed for this concurrent grafting process. Studies in basic photografting work to complement the cure grafting have been proposed. The role of solvent in grafting is discussed, particularly the effect of aromatics in photografting to naturally occurring trunk polymers like wool and cellulose. The effect of the double bond molar ratio (DBMR) of the DA components in grafting is examined. The ultraviolet (UV) conditions for gel formation during photografting, hence the importance of homopolymer yields in these processes is reported. A plausible mechanism to explain the results from this photografting work is proposed. The significance of these photografting studies in the related field of curing, especially in UV and ionising radiation (EB) systems, is discussed. EB curing and cure grafting of charge transfer (CT) monomer complexes is investigated. The EB results are compared with UV curing and cure grafting of the same complexes. The work has been extended to include EB/UV curing and cure grafting of thiolene systems. The significance of these results in the potential commercial application of these complexes is discussed. Variables affecting the UV/EB curing and cure grafting of thiolenes on cellulose have been studied. These include effect of varying the type of olefin, increasing the functionality of the thiol, use of acrylate monomers and oligomers in hybrid systems, altering the surface structure of the cellulose and finally the role of air in these processes particularly with EB. Photopolymerisation of the thiol-enes in bulk has also been investigated. The thesis content is based on the published work of 14 research papers over the course of the project. / Doctor of Philosophy (PhD)

Thesis (Ph. D.)--University of Hong Kong, 2007. / Title proper from title frame. Also available in printed format.

In this dissertation, I present electronic spectroscopy of a few biologically relevant species and their complexes with solvent molecules in the gas phase using a variety of techniques, including resonantly enhanced multiphoton ionization (REMPI), laser induced fluorescence (LIF), and zero kinetic energy (ZEKE) photoelectron spectroscopy. My work on several methylated uracils and thymines and thymine-water complexes alludes to a new interpretation with regard to the origin of the photostability of our genetic code. I believe that it is the water solvent that stabilizes the photophysical and photochemical behavior of these bases under UV irradiation. For systems that demonstrate vibrational resolution in the first electronically excited state (S₁) and the cationic state, I performed vibrational analysis of both states with the aid of ab initio and density functional calculations. These observations are explained in terms of the structural changes from the ground state to S₁ and further to the cation. To bridge results from the gas phase to the solution phase, I also report studies of supersonically cooled water complexes of the three isomers of aminobenzoic acid. Density functional theory calculations are carried out to identify structural minima of water complexes in the ground state. The solvation mechanism is investigated based on vibrational analysis of the S₁ state of the neutral complex and the shift of ionization thresholds with increasing water content. / Graduation date: 2005