archives@tulane.edu / Metalloenzymes containing copper or molybdenum have attracted considerable attention during the past several decades, as they play significant roles in a variety of biological and chemical areas. In those enzymes, their active sites exhibit unique structural features for fundamental studies in coordination chemistry and for applications in various catalytic reactions. The work described in this dissertation focuses on systematic syntheses of organometallic complexes for use in enzymatic systems as nitrous-oxide reductases (N2OR), acetyl-CoA (acetyl coenzyme A) synthases, or carbon monoxide dehydrogenases (ACS/CODH). Synthesis of diaminobisthiolate (N2S2) ligands with phenyl-connected sulfur and nitrogen atoms are introduced in Chapter 1. The importance of the N2S2 donor atoms in functionalizing the overall enzyme active sites are discussed in Chapter 1. Compared to the previously reported procedures, the new routes in this work allow for improved synthetic control, resulting in enhanced synthetic yields under mild reaction conditions. In Chapter 2, we focus on the synthesis, characterizations and applications of Ni(N2S2) complexes. We start with a new Ni complex with a tetradentate diaminobisthiolate ligand which is a continuation of one of the focuses in the previous chapter. The differences between the new Ni(N2S2) complex and other previously reported complexes with similar structures are discussed. We use both theoretical method (density functional theory calculation) and electrochemical measurements to explore the structural-property characteristics of those complexes. Chapter 3 details the synthesis of several multi-copper clusters for assembling in CuZ active-site analogues for nitrous oxide reduction. In those complexes, tetradentate diaminobisthiolate (N2S2) is used as a backbone ligand. Those complexes exhibit unique redox features due to the mixed valence of the CuI/CuII couple. Their structures are characterized by detailed X-ray crystallography measurements. In chapter 4, we extend the studies in synthesizing analogues in molybdenum- dependent carbon monoxide dehydrogenases (Mo-CODH) active site. Two different synthetic routes are explored to yield a number of Mo- and Cu-based complexes. Electrochemical characterizations are used to investigate the redox features of those complexes. / 1 / bo Wang

X-ray imaging scintillators and detectors play a critical role in numerous everyday life applications, including medical radiography, high-energy physics research, and security inspections. Despite its importance, current X-ray imaging technologies are not fully equipped to meet the growing demands for flexible, cost-efficient, and environment-friendly solutions. To overcome the limitations associated with traditional imaging scintillators, recent research efforts have focused on developing lead-free luminescent materials. Of particular interest are Cu(I) complexes, which exhibit excellent photoluminescence behavior, a facile synthesis process, and a high atomic number, making them an ideal candidate for X-ray imaging applications. Our work focuses on developing a low-dimensional Cu(I) organometallic halide and utilizing it as an imaging scintillator for real-life X-ray imaging. By utilizing the 0D Cu(I)-based imaging scintillators, we successfully obtained detailed images of both biological and non-biological objects, with a low detection limit of 458.3 nGy/s and high resolution of 16.8 lp/mm. This study not only provides a design roadmap for Cu(I) luminescent materials, but also highlights their potential for high-impact real-life X-ray imaging applications. Overall, our findings represent a significant step forward for X-ray imaging technology and its widespread applications in fields such as medicine and security.

Mon doctorat se focalise sur la synthèse, la caractérisation et les applications de matériaux poreux à base de silice, dioxyde de titane et zéolite. La silice poreuse, le dioxyde de titane et les zéolites ont été synthétisés en utilisant des méthodologies différentes. Des matériaux de silice fonctionnalisés ont été utilisés pour des applications en adsorption de colorant, ce qui est utile pour le traitement de l'eau. Un nouveau système réticulé et un nouveau dispositif ont été créés pour améliorer la capacité d'adsorption et pour le traitement d’une grande quantité d'eau. En tirant parti des pores, une nouvelle méthode de formation de clusters de Cu (0) a été établie. Les propriétés photophysiques ont été étudiées, en utilisant plusieurs sources de cuivre et différents matériaux poreux. L'utilisation du confinement pour la détection de petites molécules biologiques tels que les neurotransmetteurs a été démontrée. Plusieurs applications ont été développées sur la base de ces récepteurs de neurotransmetteurs artificiels. Un matériau de titane mésoporeux multifonctionnalisé a été utilisé pour les applications en biologie. En comparaison avec la silice, plus couramment utilisée, sa photoactivité pourrait apporter des avantages supplémentaires. Finalement, de nouveaux types de matériaux de type organotitanes hybrides ont été développés, et leurs propriétés photo-catalytiques ont été démontrées. / My PhD research focus on the synthesis, characterization and applications of silica, titania and zeolite based porous materials. Porous silica, titania and zeolite have been synthesized using different methodologies. Functionalized silica materials have been used for dye adsorption application which is useful for water treatment. A new cross-linked system and device have been created to enhance the adsorption ability and for large quantity of water treatment. By taking advantage of the pores, new method for Cu(0) cluster formation have been established. The photophysics of the Cu(0) clusters reduced from different copper source in different porous materials has been investigated. The use of the confinement for sensing has been demonstrated for small bio molecules, such as neurotransmitters. Several applications have been developed based on this artificial neurotransmitter receptors. Multi-functionalized mesoporous titania material has been used for bio-applications. Compare to the widely used silica material, its photoactivity could bring extra advantages. Finally, new types of hybrid organotitanium materials have been developed and their photocatalytic properties have been investigated.

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