THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

BLOCK COPOLYMERS CONTAINING A LOW-SURFACE-ENERGY BLOCK AND THEIR APPLICATIONS

This thesis reports the synthesis and/or applications of three types of block copolymers that each bear a low-surface-energy block. First, poly(dimethylsiloxane)-block-poly(2-cinnamoyloxyethyl acrylate) (PDMS-b-PCEA) was synthesized and characterized. Cotton coating using a micellar solution of this block copolymer yielded superhydrophobic cotton fabrics. X-ray photoelectron spectroscopy (XPS) and surface property analyses indicated that the PDMS block topped the polymer coating. Photocuring the cotton swatches crosslinked the underlying PCEA layer and yielded permanent coatings. More interestingly, hydrophilically patterned superhydrophobic cotton fabrics were produced using photolithography that allowed the crosslinking of the coating around irradiated fibers but the removal, by solvent extraction, of the coating on fibers that were not irradiated. Since water-based ink only permeated the uncoated regions, such patterned fabric was further used to print ink patterns onto substrates such as fabrics, cardboard, paper, wood, and aluminum foil. Then, another PDMS-based diblock copolymer poly(dimethylsiloxane)-block-poly(glycidyl methacrylate) (PDMS-b-PGMA) was prepared. Different from PCEA that photocrosslinked around cotton fibers, PGMA reacted with hydroxyl groups on cotton fiber surfaces to get covalently attached. Further, different PGMA chains crosslinked with each other. PDMS-b-PGMA-coated cotton fabrics have been used for oil-water separations. In addition, polymeric nanoparticles were grafted onto cotton fiber surface before PDMS-b-PGMA was used to cover the surfaces of the grafted spheres and the residual surfaces of the cotton fibers. These two types of fabrics, coated by the block copolymer alone or by the polymer nanospheres and then the copolymer, were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and water repellency analyses. A comprehensive comparative study was made of their performances in oil-water separation. Finally, a fluorinated ABC triblock copolymer poly(acrylic acid)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate) (PAA-b-PCEMA-b-PFOEMA) was used to iii encapsulate air nanobubbles. The produced air nanobubbles were thermodynamically stable in water and were some 100 times more stable than commercially available perfluorocarbon-filled microbubbles under ultrasound. These nanobubbles, due to their small sizes and thus ability to permeate the capillary networks of organs and to reach tumors, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound-regulated drug delivery.

Yielding Behaviour of Electron Beam Lithography and Focused Ion Beam Made Nanocrystalline Micro/Nanopillars

Electron beam lithography (EBL) and focused ion beam (FIB) methods were developed in house to fabricate nanocrystalline nickel micro/nanopillars so to compare the effect of fabrication on plastic yielding. EBL was used to fabricate 3 μm and 5 μm thick poly-methyl methacrylate patterned substrates in which nickel pillars were grown by electroplating with height to diameter aspect ratios from 2:1 to 5:1. FIB milling was used to reduce larger grown pillars to sizes similar to EBL grown pillars. X-ray diffraction, electron back-scatter diffraction, scanning electron microscopy, and FIB imaging were used to characterize the nickel pillars. The measured grain size of the pillars was 91±23 nm, with strong <110> and weaker <111> and <110> crystallographic texture in the growth. Load-controlled compression tests were conducted using a MicroMaterials nano-indenter equipped with a 10 μm flat punch at constant rates from 0.0015 to 0.03 mN/s on EBL grown pillars, and 0.0015 and 0.015 mN/s on FIB-milled pillars. The measured Young’s modulus ranged from 55 to 350 GPa for all pillars, agreeing with values in the literature. EBL grown pillars exhibited stochastic strain-bursts at slow loading rates, attributed to local micro yield events, followed by work hardening. Sharp yield points were also observed and attributed to the gold seed layer de-bonding between the nickel pillar and substrate due to the shear stress associated with end effects that arise from the substrate constraint. The onset of yield ranged from 108 to 1800 MPa, which is greater than bulk nickel, but within values given in the literature. FIB-milled pillars demonstrated stochastic yield behaviour at all loading rates tested, yielding between 320 and 625 MPa. Deformation was apparent at FIB-milled pillar tops, where the smallest cross-sectional area was measured, but still exhibited superior yield strength to bulk nickel. The gallium damage at the outer surface of the pillars likely aids in dislocation nucleation and plasticity, leading to lower yield strengths than for the EBL pillars. Thermal drift, substrate effects, and noise due to vibrations within the indenter system contributed to variance and inconsistency in the data.