Doctor of Philosophy / Department of Chemistry / Stefan Bossmann / My thesis is divided into two parts. The first part is focused on studies of N-heterocyclic carbene (NHC) palladium(IV) intermediates, which are involved in oxidative addition mediated C-C, and C-O bond formation processes as well as in C-Cl bond forming reactions via a reductive elimination process. Bis-NHC-Pd(II) complexes have been reported as effective catalysts to mediate direct conversion of methane into methanol. However, a H-D exchange study revealed that the bis-NHC-Pd(II) complexes are not the active species responsible for the C-H bond activation reaction. This unexpected result implies that the high oxidation state bis- NHC-Pd(IV) species may be the real catalyst! The oxidative addition of methyl iodide to the bis- NHC-Pd(II)-Me2 complex led to the successful observation of the formation of a transient trimethyl bis-NHC-Pd(IV) intermediate by both 1H-NMR and 13C-NMR spectroscopy. Different oxidants such as O2, PhI(OAc)2, PhI(OTFA)2 and Cl2 reacted with the bis-NHC-Pd(II)-Me2 complex, and competitive C-C and C-O bond formations, as well as C-C and C-Cl bond formations were observed. Dioxygen triggered C-C bond formation under dry condition and both C-C and C-O bond formation in the presence of H2O gave strong indications that the bis-NHCPd( II)-Me2 complex can be oxidized to a bis-NHC-Pd(IV) intermediate by dioxygen. The reaction between the hypervalent iodine regents PhI(OAc)2 and PhI(OTFA)2 and the bis-NHCPd( II)-Me2 complex gave only reductive elimination products. Therefore, this system can act as a model system, which is able to providing valuable information of the product forming (functionalization) step of the C-H bond activation system. The reaction between chlorine and the bis-NHC-Pd(II)-Me2 complex resulted in a relatively stable bis-NHC-Pd(IV)-Cl4 complex, which was characterized by 1H-NMR spectroscopy and mass spectroscopy. The structure of bis- NHC-Pd(IV)-Cl4 was unambiguously established by X-ray crystallography. The second part of this thesis describes the synthesis of functionalized bimagnetic core/shell iron/iron oxide nanoparticles for the treatment of cancer. Biocompatible dopamineoligoethylene glycol functionalized bimagnetic core/shell Fe/Fe3O4 nanoparticles were prepared via ligand exchange, and purified by repeated dispersion/magneto-precipitation cycles. A porphyrin (TCPP) has been tethered to the stealth nanoparticles to enhance their uptake by tumor cells and (neural) stem cells. The stealth nanoparticles have been delivered in a mouse model to tumor sites intravenously by using the EPR (enhanced permeation and retention) effect. Magnetic hyperthermia proved to be very effective against B16-F10 mouse melanomas in Charles River black mice. After hyperthermia, the nanoparticles have shown a significant effect on the growth of tumor (up to 78% growth inhibition).

Doctor of Philosophy / Department of Chemistry / Duy H. Hua / The description of this thesis is divided into three chapters following the chronological events of my research development. In chapter one, a series of new 1,4-anthracenediones were synthesized via functionalizations of the methyl side chain of 6-methyl-1,4-anthracenedione. The new 1,4-anthracenediones were found to exhibit potent cytotoxic activities against human L1210 leukemic and HL-60 cell lines. A key intermediate, 6-bromomethyl-1,4- anthracenedione (1.44), was first synthesized through a sequence of reactions including a double Friedel-Crafts reaction, reductive quinone formation, and selective benzylic bromination. The bromide (1.44) was further converted to other 1,4-anthracenediones via hydrolysis, subsequent oxidation, and reductive amination or nucleophilic substitution. Chapter two deals with a continuous research project aiming at macropolycyclic cyclodecitycene or [10]beltene derivative using Diels-Alder reaction as the key strategy for cyclization. A tetraene, (4aR,5R,7S,7aS,11aR,12R,14S,14aR)-5,7,12,14-tetrahydroxy- 2,3,9,10-tetramethylene-1,4,4a,5,6,7,7a,8,11,11a,12,13,14,14a-tetradecahydro-6,13-obenzenopentacene (2.51), was synthesized by following previous work from this laboratory. Unfortunately, the Diels-Alder reaction of tetraene 2.51 with triptycene bisquinone showed predominantly polymerization over intramolecular cyclization. The use of double activated quinone such as 1,4,5,8-naphthodiquinone (2.64) and 1,2,4,5- tetraethoxycarbonyl-1,4-benzoquinone (2.70) as dienophiles gave monoadducts 2.67 and 2.71 respectively. However, they both failed to cyclize under high dilution conditions at elevated temperature, which may be rationalized by chair conformations adopted in six membered rings causing unfavorable twist for intramolecular cylization. Further study showed tetraene 2.51 underwent an unexpected furan ring forming reaction. In chapter three, an unprecedented substituted cyclododeciptycene, 2,4,6,8,10,12,14,16,18,20,22,24-dodecahydro-9,11,21,23-tetramethoxy-(2,14:4,16:6,18:8, 20:10,22:12,24)-hexa(o-benzeno)-[12]cyclacene-1,3,5,7,13,14,17,19-octaone (3.138), was successfully synthesized based on a successful intramolecular Diels-Alder reaction, which was developed from the above [10]beltene project and previously reported literature work. A series of all cis-iptycenequinones were synthesized as bisdienophile building blocks from a sequence of Diels-Alder reactions, separation of individual Diels- Alder adducts, enolization, and oxidative demethoxylation. It was found that each Diels- Alder adduct isomer shows distinguish [superscript]1HNMR signals inherent to its structure. The characteristic [superscript]1HNMR signals allow the identification of the structures of iptycenequinones derived from the above reactions. A bisdimethoxyanthracene, 6,8,15,17-tetramethoxy-7,16-dihydro-7,16-(o-benzeno)heptacene (3.56), was synthesized as bisdiene building block, which reacted with cis,cis-heptiptycene tetraquinone (3.23). The cycloadduct was transformed to cyclododeciptycene 3.138, whose structure was firmly established by a single-crystal X-ray analysis.

Doctor of Philosophy / Department of Chemical Engineering / Keith L. Hohn / Catalytic partial oxidation (CPO) has received considerable interest recently both as a way to utilize remote natural gas resources and to provide H[subscript]2 for a fuel cell. Studies on the reactions at lower temperatures and transient conditions were performed, which can provide insights on the mechanism of CPO at high reactions, particularly on the role of the chemical and physical state of the noble metal catalyst. In this work, ignition of methane CPO on Pt/Al[subscript]2O[subscript]3 and Rh/Al[subscript]2O[subscript]3 catalysts and methanol CPO on Pt/Al[subscript]2O[subscript]3 catalysts were studied using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The ignition mechanism study of CH4 on Pt/Al[subscript]2O[subscript]3 showed that oxygen mainly covers the surface until ignition. Competition between the two reactants is assumed. The heat of adsorption of oxygen is a key factor for ignition of the methane partial oxidation reaction on Pt/Al[subscript]2O[subscript]3. The ignition mechanism on Rh/Al[subscript]2O[subscript]3 was found to be different from Pt/Al[subscript]2O[subscript]3. The oxidation state of the catalyst changed significantly as the temperature was raised towards the ignition. An oxidized rhodium state, Rh[superscript]n+, progressively formed as the temperature was increased while Rh[superscript]0 decreased. In addition, a greater amount of Rh[supercript]n+ was found when the oxygen concentration in the feed was higher. From these results, it is hypothesized that ignition of methane CPO on Rh/Al[subscript]2O[subscript]3 is related to the accumulation of the Rh[superscript]n+ state. Dissociation adsorption of methanol occurs on both Al2O3 and Pt/Al[subscript]2O[subscript]3. It is suggested that formate was one of the important intermediates in the reaction pathway. Oxygen species play a key role in the formation of formate on the catalysts, and it also affects the product composition. Formate mainly decomposed into CO, which is the dominant source for CO[subscript]2 production in the reactions at higher temperatures.

Doctor of Philosophy / Department of Chemistry / Christer B. Aakeroy / We have shown that supramolecular synthons can be used to construct discrete two or three component co-crystals and 1-D inorganic-organic chains and dramatically influence the arrangement of nanoparticle assemblies. A collection of supramolecular reagents (SR's) have been designed and synthesised to carry out a systematic study into hydrogen bonding. In order to test Etter's guideline "the best proton donor and acceptor remaining after intramolecular hydrogen-bond formation will form an intermolecular hydrogen-bond" and to develop a hierarchy of interactions, a series of co-crystals between the supramolecular reagents and hydrogen-bond donors (carboxylic acids) have been synthesised. Co-crystals with pyrazole benzamide SR's have demonstrated the ability to fine-tune hydrogen-bond formation. By utilising a poor hydrogen-bond acceptor (pyrazole) the incoming carboxylic acid opts to form a heteromeric acid-amide dimer via N-H[three dots]O hydrogen bonds. Additionally, we have shown that the hydrogen-bond acceptor strength of the pyrazole can be turned up through simple covalent modifications (i.e. isomer change or addition of methyl groups to the pyrazole ring). Although the heteromeric acid-amide dimer is observed, O-H[three dots]N hydrogen bonds to the pyrazole are also observed in cases when more than one donor site is present (i.e. di-carboxylic acids and 4-hydroxybenzoic acid). Furthermore, co-crystals with picolyl-indazole and pyrimidine-pyrazole SR's agree with Etter's guideline. In all cases, the incoming carboxylic acid forms an O-H[three dots]N hydrogen bond to the best acceptor (pyridine and pyrazole, respectively). The homomeric amide-amide dimer has been used to construct inorganic-organic hybrid materials. The reaction between the pyrazole benzamide ligands with acac or "paddle-wheel" complex ions yielded 1-D chains. Furthermore, pyrimidine-bispyrazole and functionalised 1,3-bisbenzylpyrazole ligands have been utilised as chelating-ligands for reliable metal coordination. Finally, the power of supramolecular synthons to control the arrangement of much larger nanoparticle assemblies has been shown. Both homomeric (acid-acid, alcohol-alcohol) and heteromeric (acid-imidazole, alcohol-imidazole) hydrogen bonding cause significant changes in nanoparticle assemblies.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / This dissertation reports the colloidal synthesis of iron silicide, hafnium oxide core-gold shell and water soluble iron-gold alloy for the first time. As the first part of the experimentation, plasmonic and superparamagnetic nanoparticles of gold and iron are synthesized in the form of core-shell and alloy. The purpose of making these nanoparticles is that the core-shell and alloy nanoparticles exhibit enhanced properties and new functionality due to close proximity of two functionally different components. The synthesis of core-shell and alloy nanoparticles is of special interest for possible application towards magnetic hyperthermia, catalysis and drug delivery. The iron-gold core-shell nanoparticles prepared in the reverse micelles reflux in high boiling point solvent (diphenyl ether) in presence of oleic acid and oleyl amine results in the formation of monodisperse core-shell nanoparticles. The second part of the experimentation includes the preparation of water soluble iron-gold alloy nanoparticles. The alloy nanoparticles are prepared for the first time at relatively low temperature (110 oC). The use of hydrophilic ligand 3-mercapto-1-propane sulphonic acid ensures the aqueous solubility of the alloy nanoparticles. Next, hafnium oxide core-gold shell nanoparticles are prepared for the first time using high temperature reduction method. These nanoparticles are potentially important as a high κ material in semiconductor industry. Fourth, a new type of material called iron silicide is prepared in solution phase. The material has been prepared before but not in a colloidal solution. The Fe3Si obtained is superparamagnetic. Another phase β-FeSi2 is a low band gap (0.85 eV) semiconductor and is sustainable and environmentally friendly. At last, the iron monosilicide (FeSi) and β-FeSi2 are also prepared by heating iron-gold core-shell and alloy nanoparticles on silicon (111) substrate. The nucleation of gaseous silicon precursor on the melted nanoparticles results the formation of nanodomains of FeSi and β-FeSi2. A practical application of these nanoparticles is an important next step of this research. Further improvement in the synthesis of β-FeSi2 nanoparticles by colloidal synthetic approach and its application in solar cell is a future goal.

Doctor of Philosophy / Curriculum and Instruction Programs / Tweed R. Ross / John R. Staver / The purpose of this study was to research, develop and validate a one-semester course for the general education of university undergraduates in forensic chemical education. The course outline was developed using the research and development (R&D) methodology recommended by Gall, Borg, and Gall, (2003) and Dick and Carey, (2001) through a three step developmental cycle. Information was gathered and analyzed through review of literature and proof of concept interviews, laying the foundation for the framework of the course outline. A preliminary course outline was developed after a needs assessment showed need for such a course. Professors expert in the area of forensic science participated in the first field test of the course. Their feedback was recorded, and the course was revised for a main field test. Potential users of the guide served as readers for the main field test and offered more feedback to improve the course.

Doctor of Philosophy / Department of Chemistry / Duy H. Hua / Carbon nanotubes are allotropes of carbon comprising of one or more grapheme sheets seamlessly joined together to form a cylinder. They are classified as single-walled carbon nanotubes (SWNTs) or multi-walled carbon nanotubes (MWNTs). They have potential applications ranging from conductive and high reinforcement material components, nano interconnection in electronic devices to drug delivery in biological systems. Current methods of production are high temperature arc-discharge, laser ablation of graphitic materials and chemical vapor deposition. These methods give tubes that are impure and highly heterogeneous in length, diameter and chirality thus leading to mixture metallic and semiconducting tubes. Effective application of such carbon nanotubes requires cumbersome, harsh and expensive purification and sorting into like forms. Such treatments usually compromised the structural integrity of the tubes and hence their mechanical and electrical properties. Also pristine carbon nanotubes are insoluble in most solvents. Solubility in basic organic solvents is crucial prior to their application, which requires some level of chemical manipulation or functionalization on the tubes. Currently methods of functionalization are unpredictable and limited to few oxidation reactions. A novel rational synthetic chemical approach to [12, 12] arm-chair carbon nano tube with pre-defined diameter and length has been explored utilizing cheap and simple organic building blocks and results achieved so far have been presented in this dissertation. Two approaches were employed to form the carbon-rich beltene (32) before its final conversion to the target single-walled carbon nanotube (SWNT) 1. A survey on carbon nanotubes and their related structures including their potential applications and properties are presented in chapter 1. In the second chapter an iron template-assisted olefin metathesis via a ferrocene intermediate served as an anchor for an effective cyclization. In chapter 3, an un-assisted olefin metathesis pathway was explored. Both approaches use a series of benzyl halide carbonylation coupling and Diels-Alder reactions to synthesize some of the key intermediates. The protocol presented in this dissertation may be used to produce functionalized carbon nanotubes with predefined length and diameter tailored for specific applications to be produced in kilogram scale for the first time since its discovery in 1991. Such an approach is expected to address most if not all of the problems associated with the traditional methods of producing carbon nanotubes.

Doctor of Philosophy / Department of Chemical Engineering / Keith L. Hohn / Vanadium phosphorous oxide (VPO) is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO[4subscript][dot in middle of line]0.5H[2subscript]O (the precursor) followed by in-situ activation to produce (VO)[2subscript]P[2subscript]O[subscript]7 (the active phase). These catalysts considerably improve their performance when prepared as nanostructured materials and this study discusses an alternative synthesis method based on sol-gel techniques capable of producing nanostructured VPO. Vanadium(V) triisopropoxide oxide was reacted with ortho-phosphoric acid in tetrahydrofuran (THF). This procedure yielded a gel of VOPO[4subscript] with interlayer entrapped molecules. The gels were dried at high pressure in an autoclave with controlled excess and composition of THF-2-propanol mixtures. The surface area of the obtained materials was between 50 and 120 m[2superscript]/g. Alcohol produced by the alkoxide hydrolysis and incorporated along with the excess solvent reduced the vanadium during the drying step. Therefore, after the autoclave drying, the solid VOPO[4subscript] was converted to the precursor; and, non-agglomerated platelets were observed. Use of additional 2-propanol increased the amount of precursor in the powder but reduced its surface area and increased its crystallite size. In general, sol-gel prepared catalysts were significantly more selective than the traditionally prepared materials, and it is suggested that the small crystallite size obtained in the precursor influenced the crystallite size of the active phase increasing their selectivity towards maleic anhydride. The evaluation of these materials as catalysts for the partial oxidation of n-butane at 673 K under mixtures of 1.5% n-butane in air yielded selectivity of 40% at 50% conversion compared to 25% selectivity at similar level of conversion produced by the traditionally prepared catalysts. Variations in the catalytic performance are attributed to observed polymorphism in the activated materials, which is evidenced by remarkable differences in the intrinsic activity. All precursors and catalysts were characterized by IR, XRD, SEM and BET, and the products of the catalytic tests were analyzed by GC.

Doctor of Philosophy / Department of Chemical Engineering / Larry E. Erickson / Over the past decade, nanomaterials have been the subject of enormous interest. Their defining characteristic is a very small size in the range of 1-100 nm. Due to their nanometer size, nanomaterials are known to have unique mechanical, thermal, biological, optical and chemical properties, together with the potential for wide-ranging industrial applications. Here, we synthesized nanocrystalline metal oxides through the sol-gel process and used these materials as desulfurization adsorbents and photocatalysts. Deep desulfurization of fuels has received more and more attention worldwide, not only because of health and environmental consideration but also due to the need for producing ultra-low-sulfur fuels, which can only be achieved under severe operating conditions at high cost using hydrodesulfurization (HDS). Consequently, development of new and affordable deep desulfurization processes to satisfy the decreasing limit of sulfur content in fuels is a big challenge. Sol-gel derived Cu/Al[subscript]2O[subscript]3 and Zn/Al[subscript]2O[subscript]3 adsorbents have been demonstrated to be effective in the removal of thiophene from a model solution. Results showed that Cu[superscript]+ was the active site and thermal treatment under vacuum was critical for Zn/Al[subscript]2O[subscript]3 since a defective, less crystalline spinel led to stronger interaction between zinc ions and thiophene molecules in the adsorption process. The kinetic study suggested that most of the adsorption occurred in the first 30 min, and adsorption equilibrium was attained after 1.5 h. Both adsorbents showed good regenerative property. TiO2 is considered the most promising photocatalyst due to its high efficiency, chemical stability, non-toxicity, and low cost for degradation and complete mineralization of organic pollutants. However, the use of TiO[subscript]2 is impaired because it requires ultraviolet (UV) activation ([Lambda]<387 nm). The shift of optical response of TiO[subscript]2 from the UV to the visible light region would have a profound positive effect on the efficient use of solar energy in photocatalytic reactions. We shifted the optical response of TiO[subscript]2 and improved the photocatalytic efficiency through size modification and transition metal ion and nonmetal atom doping. Experimental results showed that C and V co-doped TiO[subscript]2 catalysts had much higher activity than commercial P25 TiO[subscript]2 towards the degradation of acetaldehyde under visible light irradiation. For the first time, we reported that activities were comparable in the dark and under visible light irradiation for co-doped TiO[subscript]2 with 2.0 wt% V. C and N co-doped TiO[subscript]2 exhibited higher activity for the degradation of methylene blue than pure TiO[subscript]2 under visible light and UV irradiation. Possible mechanisms were discussed based on the experimental results.

Master of Science / Department of Chemistry / Kenneth J. Klabunde / Although Degussia-Huls P-25 TiO[subscript]2 semiconductor photocatalyst has high photodegradation rate for organic molecules, it works only under ultra-violet (UV) light. Mesoporous metal doped V-MCM-48 silica was synthesized under ambient conditions for use as a visible-light photocatalyst to convert toxic probe molecules to innocuous products: CO[subscript]2 + H[subscript]2O. The synthesis employed a modified Stober metal doped MCM-48 silica method. Powder X-ray diffraction (XRD), diffuse-reflectance-ultra-violet-visible (DR-UV-vis) spectroscopy, and N[subscript]2 adsorption-desorpton analysis characterization methods were completed on V-MCM-48 mesoporous material. These characterization methods indicate V-MCM-48 structure had formed with visible light absorption and mesoporous properties. Photocatalysis studies were completed with V-MCM-48 under dark, visible, and UV-light illumination conditions for the following probe molecules: acetaldehyde, carbon monoxide, ethanol, acetone, 2-propanol, and acetonitrile. Acetaldehyde over V-MCM-48 was converted to CO[subscript]2 under dark, visible, and UV-light conditions. Carbon monoxide photooxidation occurred over V-MCM-48 under visible and UV-light. Ethanol and acetonitrile had smaller photodegradation activity over V-MCM-48. Acetone and 2-propanol had no activity photocatalytically. Under dark and visible light illumination, V-MCM-48 consumed approximately one-half acetaldehyde and produced one-third CO[subscript]2 concentration as compared with the P-25 TiO[subscript]2 under UV-light. V-MCM-48 produced two-thirds of the amount of CO[subscript]2 in comparison to nanoparticle Au/ZnO catalyst under UV-light. The results infer V-MCM-48 might be useful in gas and liquid phase photocatalysis including water-splitting due to a high oxidation state (V[superscript]5+), visible light absorption, and high surface area. In conclusion, an extended literature review has been completed and literature employed extensively throughout the thesis with potential methods to further the research on V-MCM-48/Si-MCM-48 in catalysis, chromatography, adsorption/gas separation, and solar collection/water-splitting.