Physical Sciences and Mathematics Commons^™

Design And Synthesis Of Polymer-Based Advanced Nanomaterials Using Raft Polymerization And Click Reaction, Junting Li

Theses and Dissertations

This research focuses on exploring new synthetic approaches to prepare polymer-based advanced nanomaterials using highly efficient chemical tools, such as reversible addition-fragmentation chain transfer (RAFT) polymerization and click reactions.

In the first project, novel synthetic routes to produce fullerene-based polymers were designed. First, mono-alkynyl functionalized fullerene was prepared starting with pristine fullerene (C₆₀). Methyl methacrylate and 6-azido hexyl methacrylate were then randomly copolymerized via RAFT polymerization with well-controlled molecular weights and copolymer compositions. Finally, the two moieties were covalently assembled into a series of well-defined side-chain fullerene polymers (SFP's) via the copper-catalyzed click reaction. The TGA and UV-vis …

New Ruthenium And Osmium Carbonyl Cluster Complexes With Main Group Bridging Ligands Having Unusual Structures And Bonding, Yuwei Kan

Theses and Dissertations

The reaction of IrRu3(CO)13(µ-H), 2.1 with HSnPh3 in hexane solvent at reflux has provided the new mixed metal cluster compounds Ir2Ru2(CO)11(SnPh3)(µ-H)3, 2.2 and IrRu3(CO)11(SnPh3)3(µ-H)¬4, 2.3 containing SnPh3 ligands. Compound 2.2 which was obtained in low yield (3%) contains a closed cluster having two iridium and two ruthenium atoms, one SnPh3 ligand and three bridging hydride ligands. Compound 2.3 has a butterfly structure for the four metal atoms with three SnPh3 ligands and four bridging hydride ligands around the periphery of the cluster. When compound 2.3 was heated to 97 oC for 30min, IrRu3(CO)9(μ-η2-C6H5)(μ4-SnPh)2(μ-SnPh2), 2.4 was formed by cleavage of phenyl …

Single Crystal To Single Crystal Polymerization Of A Columnar Assembled Diacetylene Macrocycle, Weiwei Xu

Theses and Dissertations

Organic tubular materials have attracted lots of attentions for their potential applications as nanoscale fluidic transport systems, specific ion sensors, molecular sieves and confined molecular reaction containers. While conjugated polymers, due to delocalized Pi electrons, exhibit interesting solar cells and sensors applications. In this thesis, we developed a conjugated polymer which combines the attributes of conjugated polymers with tubular materials, which should have great potential to work as a sensing material.

We reproduced and scaled-up the synthesis of a polymerizable macrocycle 1 that contains two rigidly separated diacetylene units. We found that, through hydrogen bonding, 1 can assemble into columnar …

Iridium-Ruthenium/Osmium-Gold Cluster Complexes: Unique Structures And Properties, Qiang Zhang

Theses and Dissertations

Chapter Two

The first Ir-Ru cluster complex was synthesized was the electron-rich, anionic, planar cluster complex [PPN][IrRu6(CO)23], 2.5, (PPN=Bis(triphenylphophoranylidene)-ammonium) which obtained from the reaction of [PPN][IrRu3(CO)13] with one equivalent ruthenium carbonyl (Ru3(CO)12) at 66 oC (THF reflux) for 12h. Compound 2.5 could also be synthesized by using the mono-Iridium compound [PPN][Ir(CO)4] reacts with two equivalent of ruthenium carbonyl. In compound 2.5, all seven metal atoms lie in a plane (max deviation = 0.043(1) Å) with the iridium atom in the center circumscribed by a hexagonal ring of six ruthenium atoms. The anion 2.5 contains 104 valence electrons while both the …

Investigations Of The Non-Covalent Ch-Π Interactions Using Molecular Torsional Balances, Chen Zhao

Theses and Dissertations

Several bicycle N-arylimide based molecular balances were designed to study aliphatic CH-pi interactions and aromatic CH-pi interactions (edge-to-face arene-arene interactions). In each case, the geometries of the interactions were characterized in the solid-state via X-ray analysis, and the strengths of interactions were characterized in solution by their folded/unfolded ratios, as measured by integration of their 1H NMR spectra.

The balances are very sensitive to variations in the strengths of weak non-covalent interactions. Several different aspects of the CH-pi interactions were studied, such as sterics, conformational entropy, cooperativity, deuterium isotope effect, substitution effects, and solvent effects. It showed that due to …

Silylation-Based Kinetic Resolution Of Α-Hydroxy Carbonyl Compounds And Synthesis Of Chiral Isothiourea Catalysts, Yan Zhang

Theses and Dissertations

The thesis describes the silylation-based kinetic resolution for α-hydroxy carbonyl compounds catalyzed by isothiourea catalyst as well as our effort to make novel chiral isothiourea catalyst.

In Chapter 1, general background will be introduced, including chirality, general methods to obtain enantiopure compounds and kinetic resolution. In Chapter 2, the mechanism of the chiral recognition was discussed and a novel isothiourea catalyst was design to investigate the mechanism. The synthesis of the new catalyst was also described in this chapter.

In Chapter 3, the silylation-based kinetic resolution for α-hydroxy carbonyl compounds will be discussed. Since silylation-based kinetic resolution have already been …

Biomaterial-Induced Osteogenesis Of Mesenchymal Stem Cells By Surface Roughness And Functionalization, Pongkwan Sitasuwan

Theses and Dissertations

For tissue engineering and regenerative medicine, it is important to understand factors directing the stem cell fate, including self-renewal, proliferation, differentiation, and apoptosis. Bone marrow derived mesenchymal stem cells (BMSCs) have the potential to differentiate into osteoblasts, chondrocytes, adipocytes, and smooth muscle cells. Specifically, in the field of bone tissue engineering, BMSCs are commonly used for in vitro osteogenesis studies. However the mechanisms and signaling pathways that these cells recognize material surface and utilize to differentiate are still unclear. This dissertation focuses on investigating the effect of surface nanotopography and functionalization on the promotion of osteogenic differentiation of BMSCs. Surface …

Functional Block Copolymers For Applications In Advanced Materials, Energy Storage, And Lithography, Christopher George Hardy

Theses and Dissertations

Block copolymers spontaneously self-assembly into a wide variety of ordered nanostructures on the length scale of 5 - 100 nm due to the thermodynamic immiscibility between the covalently linked, chemically distinct polymer chains. Incorporating desirable functional groups into block copolymer systems can lead to confinement of the functional group to a specific domain upon microphase separation of the block copolymer. The resulting materials display desirable characteristics of the functional group in a well-ordered nanostructure. Such systems have been utilized in a wide variety of applications including catalysis, ceramic materials, and membranes. This dissertation is focused on the synthesis, characterization, self-assembly …

Plant Virus Based Materials For Cell Alignment And Differentiation, Elizabeth Balizan

Theses and Dissertations

This research focused on developing and using plant virus based scaffolds to understand substrate control over cell alignment and differentiation. The first part of this work centered on development of virus based patterns that were then used to align and elongate aortic smooth muscle cells (SMCs). Virus patterns were generated in capillary tubes via a simple drying method. Three experimental parameters were used to control pattern formation: (1) protein concentration, (2) salt concentration, and (3) hydrophobicity of the pre-deposition surface. By controlling these parameters several aspects of the final virus patterns were controlled. First, virus orientation was controlled. Patterns were …