Chemistry Commons^™

Supramolecular Biopolymeric Composite Materials: Green Synthesis, Characterization And Applications, Tamutsiwa Moven Mututuvari

Dissertations (1934 -)

Macrocycles, such as crown ethers (CRs) and resorcinarenes (RESs), exhibit selective complexation of heavy metal ions and organic pollutants respectively. Consequently, they have been investigated for their suitability in adsorbing these aqueous pollutants. However, they are difficult to handle and recycle for reuse because, by themselves, they can only be fabricated in powder form. To alleviate this challenge, we developed a method to encapsulate these macrocycles into film-forming polysaccharides--cellulose (CEL) and chitosan (CS). This was achieved by using a green and recyclable solvent, an ionic liquid, to dissolve both macrocycles and polysaccharides and regenerate corresponding composites in water. Resultant composites …

Resonant Two-Photon Ionization Studies Of Non Covalent Interactions In Halo Aromatic Clusters And Spin-Orbit Coupling Modeling In Mono-Halocarbenes, Silver Nyambo

Dissertations (1934 -)

Non-covalent interactions in halobenzenes (PhX) (X=F, Cl, Br) and phenylamine (C₆ H₅ NH₂ ) have been studied here using resonance two-photon ionization (R2PI) spectroscopy combined with a linear TOF-mass spectrometer. Their interaction with polar molecules in form of ammonia (NH ₃ ) and trifluorohalomethanes (CF₃ X) has also been studied. DFT and TD-DFT calculations using M06-2X functionals were carried out on different cluster conformations to compliment experimental results. A general trend of broadness in homogenous dimers (PhX)₂ , has been attributed to mainly the presence of multiple cluster isomers and Frank-Condon activity in the low …

Investigations Of Synthetic Models Of Mononuclear Nonheme Iron Dioxygenases, Michael Bittner

Dissertations (1934 -)

Ring cleaving dioxygenases, such as o-aminophenol dioxygenase (APDO) and extradiol catechol dioxygenases (CatD), play an important role in human metabolism and the degradation of aromatic pollutants, yet questions still remain concerning the enzymatic mechanisms. One area of the catalytic cycle that remains controversial is the geometric and electronic structure of the intermediate formed after O₂ binding to the Fe(II) centers. Synthetic model systems can be useful for studying enzyme active sites, as they are easier to modify and characterize than the enzymes themselves. However, synthetic models of APDOs have been relatively rare thus far. We prepared several monoiron(II) complexes …

Synthesis, Characterization And Reactivity Studies Of Fe(Ii) Complexes With Relevance To The Radical Sam Enzymes, Xixi Hong

Master's Theses (2009 -)

It is well-established that S-adenosylmethionine (SAM) serves as the methyl group donor in methylations of DNA, hormones, neurotransmitters and signal transduction systems. However, a new class of enzymatic reactions involving SAM has recently attracted considerable attention. In these systems, SAM initiates radical-based reactions at the active sites of enzymes via formation of an adenosyl radical, which further abstracts a H-atom from the substrate to initiate a radical-based mechanism. However, modeling studies of radical SAM enzymes have been hindered, by difficulties in preparing adequate synthetic [Fe4S4] clusters. We prepared a novel series of Fe(II) complexes with tripodal tris(2-hydroxybenzyl)amine ligands, which replicate …

Photochemical Elimination Reactions That Proceed Via Triplet Excited State Electrocyclic Ring Closures, Himali Devika Jayasekara

Master's Theses (2009 -)

Cage compounds have become an important tool for the study of biological processes. The research focuses on new cage compounds that can unmask functional groups present in biologically important molecules such as proteins, peptides, and oligonucleosides. The project focuses on certain functional groups that are often difficult to release photochemically. These are the thiolate groups present in cysteine residues of proteins and peptides. Thiolate groups are fairly basic leaving groups, unlike the more labile groups such as the carboxylates that are present in proteins and peptides, or the phosphate groups present in nucleosides. The research takes advantage of the ability …

Generation Of Diverse Molecular Complexity From Cyclooctatetraene, Mohamed Fawzy El Mansy

Dissertations (1934 -)

ABSTRACT

GENERATION OF DIVERSE MOLECULAR COMPLEXITY

FROM CYCLOOCTATETRAENE

Mohamed F. El Mansy, B.Sc, M.Sc.

Marquette University, 2014

The use of simple hydrocarbons as starting materials for the synthesis of complex molecules relies on efficient methods for oxidation, functionalization or rearrangement. For example, various researchers have explored cyclopentadiene or cycloheptatriene as precursors for the preparation of a wide variety of drug candidates, natural products and synthetic products. The purpose of this research is to explore methods to transform the simple hydrocarbon, cyclooctatetraene (COT) into complex target molecules.

Tricarbonyl (cyclooctatetraene)iron, readily prepared from COT, reacts with a variety of electrophiles to form …