Physical Sciences and Mathematics Commons^™

From Flasks To Applications: Design And Optimization Of Giant Quantum Dots Using Traditional And Automated Synthetic Methods, Christina J. Hanson

Nanoscience and Microsystems ETDs

Semiconducting nanocrystals, also known as quantum dots (QDs), that emit light with near-unity quantum yield and are extremely photostable are attractive options as down-conversion and direct electricity-to-light materials for a variety of applications including solid-state lighting, display technologies, bio-imaging and optical tracking. Standard QDs with a core/thin shell structure display fluorescence intermittency (blinking) and photobleaching when exposed to prolonged room temperature excitation for single dot measurements, as well as significant reabsorption and energy transfer when densely packed into polymers or at high solution concentrations.

We have developed thick shell “giant” QDs (gQDs), ultra-stable photon sources both at the ensemble and …

Preparation Of Polymeric Materials From Bio-Renewable Sources, Jason Douglas Smith

Theses and Dissertations

The focus of this project was to develop methodologies for the preparation of novel polymeric materials from bio-renewable sources. In order to complete this task we needed (a) unfettered access to bio-based materials and ways to convert them to value needed chemicals, as well as, (b) reaction protocols that would allow greater diversity during the synthesis of polymeric compounds so as to affect the properties of these materials.

Our research group has a background in converting plant-based materials like cellulose into value added chemicals employing catalytic reactions. The polymerization of these monomers was then conducted utilizing the Baylis-Hillman reaction. The …

Systematic Size Control In The Synthesis Of Zero-Valent Iron Nanoparticles, Grant C. Bleier

Chemistry and Chemical Biology ETDs

A novel synthetic method for the production of highly magnetic, low size-dispersity nanoparticles through reversible magnetic agglomeration is introduced and studied in detail. Initially, a weakly coordinating surfactant (3-octadecyl-2,4-pentanedione) is employed to produce a wide range of nanoparticle sizes ranging from 8 to 20 nm in diameter. The kinetics faced in these reactions by cheap and widely available iron complex precursors can be avoided in this method with the introduction of thermodynamic control, which occurs in the form of a magnetic precipitation event that essentially halts nanoparticle growth. Utilizing this synthetic method, the length of the alkyl chain on the …

Toward Better Keys For Lectin Locks: Glycoconjugates Versus Glycomimetics, Peng Wen

Wayne State University Dissertations

As one of the four major classes of macromolecule in living systems, the roles of carbohydrates as energy storage substances and structural components have long been recognized. However, the unique role of carbohydrates in cellular recognition processes has only been scrutinized since the 1960s, thanks to the progress in the research in both cell surface carbohydrates and carbohydrate-binding proteins (lectins). The advances in the research of such process demand the use of carbohydrates as basic tools. Therefore, the primary goal of glycochemistry has been to obtain complex carbohydrates and their analogs effectively. One common approach to the problem involves the …

An Interdisciplinary Approach To The Target Elucidation Of Novel Antibiotic 31g12, Larissa A. Walker

Graduate Student Theses, Dissertations, & Professional Papers

Staphylococcus aureus is a Gram-positive bacterial pathogen responsible for nosocomial and community-acquired infections that can quickly acquire antibiotic resistance. We have identified a novel triazole antimicrobial 31G12 based on the natural product core of nonactin isolated from the fermentation of Streptomyces griseus, that is active against many Gram-positive bacteria as well as antibiotic resistant methicillin-resistant S. aureus and vancomycin-resistant Enterococcus. The synthesis and characterization indicate that 31G12 exists as a mixture of two rotamers at room temperature and displays bacteriostatic activity against S. aureus with moderate mammalian cell toxicity. We have currently identified potential protein targets of 31G12 in …

Design, Synthesis, Characterization, And Applications Of Matrix Free Polymer Nanocomposites, Yucheng Huang

Theses and Dissertations

This dissertation focuses on the design, synthesis, characterization and application of matrix free polymer nanocomposites. Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to synthesize block copolymers and polymer grafted silica nanoparticles with precise control over architectures.

In the first chapter, thermoplastic elastomer (TPE) grafted nanoparticles were prepared by grafting block copolymer poly(styrene-block-(n-butyl acrylate)) onto silica nanoparticles (NPs) (~15nm) via surface initiated RAFT polymerization. The effects of polymer chain length and graft density on the mechanical properties were investigated using films made solely from the grafted NPs. The ultimate tensile stress and elastic modulus increased with the increase of PS …

Synthesis And Characterization Of A Novel Platinum Ligand Complex ((Κ-N,C,N- 2,6-Bis(Diethylaminomethyl)Phenyl)(4- Tert-Butylphenyl) Platinum(Ii)), Carly Roleder

CMC Senior Theses

A novel platinum ligand complex (NCN)PtAr, ((κ-N,C,N- 2,6-bis (diethylaminomethyl)phenyl)(4- tert-butylphenyl) platinum(II)), was synthesized. A reaction of 1-Bromo-4-tert-butylbenzene Grignard with (NCN)PtCl, (where NCN = 2,6-bis(diethylaminomethyl)phenyl) yielded the (NCN)PtAr (where Ar = 4-tert­-butylphenyl). The product was then characterized with NMR spectra through ¹H NMR, ¹³C NMR, COSY, HSQC, and HMBC to verify it structure.

The Effect Of Oxidation, Thionation, And Dimerization On The Self-Assembly And Photophysical Properties Of Novel Discotic Materials, Katie M. Psutka

Theses and Dissertations (Comprehensive)

This thesis aims to increase understanding of the relationship between molecular structure and liquid crystalline temperature range by exploring the effects of oxidation, thionation, and dimerization on the self-assembly and properties of novel discotic materials. First, two alkoxy-substituted dibenzanthracenequinones were prepared by oxidation of the corresponding dibenzanthracenes. The quinone induced a liquid crystalline phase in the hexaalkoxy dibenzanthracene derivative, but not in the tetralkoxy derivative. However, both of the resulting materials were un-reactive to any further synthetic modifications that could be used to improve their properties. In comparison, two heteroaromatic dithienoanthracenedicarboximides were successfully prepared, although the addition of the thiophene …

Synthesis And Characterization Of Polydiene-Grafted Nanoparticles, Zaid Mohammed Abbas Alajeeli

Theses and Dissertations

This dissertation presents the design, synthesis, and characterization of polydiene grafted nanoparticles as a way to tailor nanocomposite interfaces and properties via interface design. The polymerization of dienes was done via reversible addition fragmentation chain transfer (RAFT) polymerization. The grafting of polymer chains on the surface of silica nanoparticles can be controlled through the molecular design of the RAFT agents attached to the nanoparticles surface. The properties of the nanocomposites largely depended on the interface between the particles and the polymer matrix. In the first part of this work, the polymerization of diene monomers was done on 15 nm diameter …

Exploration Of Zirconium-Catalyzed Intermolecular Hydrophosphination With Primary Phosphines: Photocatalytic Single And Double Hydrophosphination, Christine Anne Bange

Graduate College Dissertations and Theses

Catalytic hydrophosphination has enormous potential in the selective preparation of value-added organophosphines, despite the challenge of the reaction. This dissertation aims to address the hurdles in catalytic hydrophosphination with respect to substrate scope, selectivity, and reaction conditions using [қ5 –N,N,N,N,C– (Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1).

Compound 1 readily engages with a suite of primary phosphines. These are challenging substrates for this reaction, but 1 readily provides high conversions with these substrates. Increasingly large primary phosphines, including chiral phosphines, undergo catalysis with 1. Furthermore, a variety of underreported unsaturated substrates can be functionalized in catalytic hydrophosphination with 1. Alkynes are underreported substrates, but 1 …

Block-Copolymer Assisted Fabrication Of Anisotropic Plasmonic Nanostructures, Calbi J. Gunder

MSU Graduate Theses

The anisotropic nanostructures of noble metals are of great interest for plasmonic applications due to the possibility of tuning the localized surface plasmon resonance (LSPR) across the UV-VIS-NIR without sacrificing the linewidth as well as to achieve larger local field enhancement. Here, we report a simple and promising fabrication method of anisotropic gold nanostructures film using polystyrene-b-2vinylpyridine (PS-b-P2VP) block copolymers (BCP) as a template. In this approach, PS-b-P2VP spherical micelles were first synthesized as a template followed by selective deposition of Au precursor inside P2VP core of the micelles using ethanol solution of Au salt. Subsequently, heat treatment of the …

Synthesis Of Small-Molecule Fluorescent Probe And Polymers For Bioapplication: Bioimaging And Enzyme Stabilization, Yanmei Xu

Theses and Dissertations

In chapter one, we designed, synthesized and characterized two cysteine sensors CCPAP and CCPAN, with improved water solubility, cell penetration ability, and potential targeting selectivity. Two types of positive charged groups, i.e. triphenylphosphonium and pyridinium were introduced respectively to the frame structure CCP by coupling carboxylic acid with amine to improve the cell permeability and cysteine selectivity. ESI-MS, NMR and IR were employed to characterize the molecular structures of the two novel probes. These probes have better water solubility than the parent molecule DCP, and better cell penetration capability than CEP, which could further distinguish the cysteine concentration differences in …

Synthesis And Reactivity Of Carborane Backbone Pincer Complexes, Bennett J. Eleazer

Theses and Dissertations

In organometallic chemistry, boron-centered ligand systems represent a powerful synthetic strategy for the promotion of a variety of catalytic transformations. These ligands offer a versatile array of bonding motifs, which can function as borane, boratrane, boryl, borate, or borylenes type ligands, and are likely the strongest σ-donors in the anionic series of ligands based on boron, carbon, nitrogen, and oxygen. Carboranes, which are icosahedral boron clusters of the type C2B10H12, offer unique potential as metal ligands, such as their bonding to exohedral metal centers being dominated by two-center-two-electron σ-bond interactions, their three-dimensional cluster structure providing considerable steric shielding to a …