In the design of the food irradiation process, the knowledge of the radiation resistance of the target organism in a specific food commodity is required. The D10-value, the radiation dose needed to inactivate 90% of the microbial load in the food medium, is used to relate the amount of absorbed energy to the surviving bacterial population. Numerous experimental studies have been performed to determine the D10 values of several food-borne microorganisms irradiated under various conditions. Nevertheless, accurate predictions of D10 values of the pathogens in food products that have not been empirically examined cannot be made due to insufficient understanding of the biological response to radiation exposure. A theoretical model for the derivation of the D10-value has been proposed in this study to mechanistically assess the production of radiation-induced DNA damage by energetic electrons. The step-by-step Monte-Carlo simulation technique, which employs the detailed histories of the ionizing particles and the radiolytic species, was utilized. The effects of selected parameters including the genomic sequence, the type of DNA double strand break, the DNA damaging agents, the radical scavengers, the degree of dispersion of DNA molecules, and the number of genome equivalents were hypothetically investigated. The developed computational methodology as well as the results presented can be used as an analytical tool to evaluate the impact of ionizing radiation on cell survival.

Pecan nuts might become contaminated with foodborne pathogens, such as Salmonella and E. coli., through birds and other potential sources of contamination that can lead to serious illness or even death, as well as financial losses. For example, the outbreak of Salmonella in pecan products in Texas caused major product recalls in 2010. Irradiation with electron beams could be an effective method of preventing potential outbreaks without changing the pecans' taste, color and flavor and without causing any risk of recontamination before the product reaches the consumer. However, when irradiation is applied alone, the shelf life of the product is decelerated because of the detrimental effect of lipid oxidation. Therefore, to extend the shelf of the pecans while assuring their safety, irradiation of pecans under modified atmosphere packing (MAP) conditions could be a viable option. This research showed that when treated with electron beams, surrogates of Escherichia coli (a cocktail of BAA-1427, BAA-1428, and BAA-1430), and Salmonella (S. Typhimurium LT2) were more resistant to ionizing radiation (higher D10 values) when packed under vacuum (VP) than under air or other MAP conditions. This research also showed that lipid oxidation in pecans (due to exposure to ionizing radiation) shows a lag phase, probably due to the antioxidants present in pecan nuts. The lag phase represents a delay period before the pecan nuts start to get rancid (increase in PV formation), and it is best described by a modified Gompertz model. Kinetic evaluation of the lipid oxidation reaction suggests that the dose level has a more drastic effect in PV formation than the type of package used during the irradiation treatment, e.g., vacuum packed versus nitrogen-packed. Moreover, accelerated shelf life studies (4 weeks at 48.9oC) showed that vacuum-packed (VP) pecans can be stored at -25 degrees C up to three years, while irradiated (at 3.0 kGy) VP pecans can be stored only for eight months, without the detrimental effects of lipid oxidation. Therefore, irradiation of pecans under air at 3.0 kGy reduces the shelf life of the nuts in terms of rancidity, but vacuum-packaging can be used to extend their shelf-life. Irradiation in oxygen packaging increases rancidity and the oxidation reaction rate accelerates with increasing dose. Irradiation under nitrogen packaging requires lower doses to achieve the almost same number of log reductions in microbial population. The use of nitrogen packaging also inhibits the oxidative reaction leading to rancidity in pecans. Although there are some drawbacks to the application of nitrogen packaging in an irradiation plant (special machinery and packaging films (permeability specifications for N2 gas)), the savings induced by avoiding recalls may make this technology worthy of consideration.

L’objectif de ce travail fut la synthèse de ligands fonctionnels de type N,N'-diphosphanyl-NHC (NHC = carbènes N-hétérocycliques) et l’étude de leur chimie de coordination. La synthèse du nouveau ligand tridentate, stable et rigide, N,N'-diphosphanyl-imidazol-2-ylidene a permis des études expérimentales et théoriques et l’accès à des complexes mono-, di-, tri-, penta-, et hexanucléaires des métaux du groupe 11 (Cu, Ag et Au) originaux et aux propriétés structurales uniques. Les complexes mono- et dinucléaires avec un ou deux atomes de phosphore libres ont permis d’accéder à des complexes hétérotrinucléaires à interactions d10-d10 qui sont luminescents. La transmétallation partielle ou totale des complexes homotrinucléaires de Cu ou d’Ag avec des réactifs contenant du Pd(0) ont conduit à des complexes hétérotrinucléaires à interactions d10-d10. En plus de son comportement pontant, ce ligand peut se agir en chélate dans des complexes du palladium et du chrome. Dans le cas du Cr(III), ils montrent une activité catalytique en oligomérisation de l’éthylène supérieure à celle des complexes du Cr(II) et conduisent principalement à des oligomères. / The purpose of this work was the synthesis of N,N'-diphosphanyl-functionalized NHC ligands andtheir coordination chemistry. The novel stable and rigid tridentate N,N'-diphosphanyl-imidazol-2-ylidene was synthesized and experimental and computational information on its stability weregained. It served as a unique platform for the synthesis of novel mono-, di-, tri-, penta-, hexanuclear complexes with the coinage metals (Cu, Ag and Au), exhibiting rare structural features. The mono- and dinuclear complexes with one or two dangling P-donors provided rational access to heterotrinuclear complexes. All these coinage metal complexes have short metal-metalseparations, indicating the presence of d10-d10 interactions, and display excellent luminescentproperties. Partial or complete transmetallation of the homotrinuclear Cu or Ag complexes withPd(0) precursors led to hetero-trinuclear complexes with d10-d10 interactions. In addition to itsbridging behavior, this ligand also showed its chelating behavior in Pd or Cr(III) complexes. Thelatter displayed superior performance in ethylene oligomerization than the Cr(II) complexes andgave mostly oligomers.

Les travaux décrits dans cette thèse ont porté sur l'application de méthodes de la chimie quantique à l'étude de différents types et familles de composés chimiques, à savoir, des clusters encapsulant des anions et des complexes inorganiques de métaux de transition. On s'est particulièrement intéressé à la structure géométrique, la structure électronique et aux relations structures-propriétés optiques de systèmes moléculaires stables et bien caractérisés. / The work reported in this manuscript deals with the applications of quantum chemistry tools on several types and families of chemical compounds, i. e., clusters entrapping anions and transition metals inorganic complexes. We have mainly focused our attention on the geometrical structure, the electronic structure and on the relationship between structure and optical properties of stable molecules which have been synthesized and characterized.

Computational chemistry has gained interest as a characterization tool to predict photoluminescence, reactivity and structural properties of organic and transition metal complexes. With the rise of methods including relativity, these studies have been expanded to the accurate modeling of luminescence spectra of complexes with considerable spin-orbit splitting due to heavy metal centers as well as the reaction pathways for these complexes to produce natural products such as hydrogen gas. These advances have led to the synthesis and utility of more effective catalysis as well as the development of more effective organic light emitting diodes (OLEDs) through the incorporation of organometallic complexes as emitters instead of typical organic emitters. In terms of significant scientific advancement presented in this work is in relation to the discovery of significant spin-orbit splitting in a gold(I) alkylphosphine complex, where the splitting results in the states that emit in different colors of the visible region of the electromagnetic spectrum. This work also reveals the discovery both computationally and experimentally, of a genuine polar-covalent bond between two-closed shell metals. This work highlights a complex with an incredibly short gold(I) – copper(I) intermetallic distance leading to a vibrational frequency and dissociation energy that is on par with those of other systems with single-bonded metal centers. Lastly, this work outlines a strategy for the production of hydrogen gas through the use of trinuclear cyclic coinage metal complexes as catalysis to split hydrohalic acids.

Le cuivre est un élément essentiel à tout être vivant, il intervient en tant que cofacteur dans de nombreux processus biologiques. Cependant, en excès, il est toxique pour l'organisme et peut impliquer des réactions de type Fenton. Sa concentration dans les cellules est donc régulée par des protéines qui permettent son transport et son élimination. La maladie de Wilson est due à une anomalie au niveau d'une de ces protéines (l'ATP7B). C'est une maladie génétique, dont les deux parents sont porteurs sains. Elle entraîne une accumulation du cuivre dans le foie, le cerveau et les yeux. Cette maladie orpheline (1/30 000 à 1/100000) présente des symptômes nombreux et souvent peu spécifiques à la maladie de Wilson. Les traitements actuels visent à diminuer l'absorption intestinale ou à augmenter l'excrétion urinaire du cuivre et doivent être suivis à vie. Ils ne visent absolument pas le foie qui est le premier organe touché et sont peu sélectifs du cuivre. Actuellement, il n'existe pas de traitement capable d'éliminer le cuivre directement au niveau du foie qui est le premier organe touché. Une molécule capable d'éliminer le cuivre en excès contenu dans les cellules du foie (hépatocytes) serait donc très utile pour soulager les malades. Pour cela, nous avons conçu des vecteurs comportant une partie ciblante pour pouvoir cibler le foie et une partie chélatante pour complexer le cuivre(I). Cette partie chélatante présente une forte affinité pour le cuivre(I) et une forte sélectivité Cu+/Zn2+. Ainsi, deux modèles de parties chélatantes basés sur deux et trois cystéines ont été synthétisés et des études de complexation du cuivre(I) mais aussi d'autres métaux divalents de configuration d10 ont été réalisés. Enfin, la vectorisation de ces modèles a été réalisée et des tests cellulaires ont été faits afin d'évaluer la complexation des ces vecteurs pour le cuivre(I) intracellulaire.

The research developed a UV Taylor Couette reactor for disinfecting milk as a model opaque fluid. The principal of the reactor was to generate laminar vortices to support efficient mixing and homogenous UV photon distribution. The UV reactor parameters were optimized to generate laminar vortices that were stabilized by modification of the unit with baffles. A model was developed to predict the UV dose required to inactivate model microbes in milk. Through verification trials it was noted the predicted UV dose underestimated that required to support a 5 log cfu reduction of microbes. It was subsequently identified that the deviation from predicted values could be attributed to fat content that enhances the UV inactivation of microbes in milk with proteins providing protection to microbes. In conclusion, the UV Taylor Couette reactor has strong potential for disinfecting opaque fluids although matrix effects need to be considered when undertaking validation trials.

Synthesis of d10 complexes of monovalent coinage metals, copper(I) and gold(I), with dithiophosphinate/diphosphine ligands -- along with their targeted characterization and screening for inorganic or organic light emitting diodes (LEDs or OLEDs, respectively) -- represents the main scope of this dissertation's scientific contribution in inorganic and materials chemistry. Photophysical studies were undertaken to quantify the phosphorescence properties of the materials in the functional forms required for LEDs or OLEDs. Computational studies were done to gain insights into the assignment of the phosphorescent emission peaks observed. The gold(I) dinuclear complexes studied would be candidates of OLED/LED devices due to room temperature phosphorescence, visible absorption/excitation bands, and low single-digit lifetimes -- which would promote higher quantum yield at higher voltages in devices with concomitant lower roll-off efficiency. The copper(I) complexes were not suited to the OLED/LED applications but can be used for thermosensing materials. Crystallographic studies were carried to elucidate coefficients of thermal expansion of the crystal unit cell for additional usage in materials applications besides optoelectronic devices. This has uncovered yet another unplanned potential application for both copper(I) and gold(I) complexes herein, as both types have been found to surpass the literature's threshold for "colossal" thermal expansion coefficients. Two other investigations represent contribution to the field of chemistry education have also been accounted for in this dissertation. First, a 12-week advanced research discovery experiment for inorganic chemistry has been designed to help students develop application-based content expertise, as well as to introduce students to research experiences that are similar to those found in academia, industry, and government research laboratories. Students are expected to develop a novel research project through conducting a literature search to find suitable reaction protocols, incorporating synthetic techniques, collecting data, characterizing products and applications of those products, and presenting their results. This multi-week research discovery experiment is centered on applications of inorganic synthetic techniques to design, analyze, and screen d10 coinage metal complexes for possible LED/OLED-based applications that were presented in chapter 3 of the dissertation. The second chemistry education contribution pertains to designing a pilot research study to investigate undergraduate chemistry majors' perceptions of environmental sources/influences, self-efficacy, outcome expectations, career interests, and career choice goals in the lab designed in chapter 4 of the dissertation. Specifically, this research aims to gauge students' perceptions of their ability to perform synthetic and analytical methods for the creation of materials that were used in a novel research experiment in the context of an inorganic chemistry laboratory. This research study used a survey to collect data on students' motivation, self-efficacy, career interests, and career goals upon graduation, along with their perceived barriers within the course. This research study is guided by the following research question: How does an inorganic chemistry laboratory course, following a research discovery model, impact undergraduate students' (a) confidence with techniques and skills, (b) perception of ability to conduct research, and (c) interest in pursuing careers involving chemistry?