Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

Cochlear implants (CIs) help to restore basic auditory function in patients who are deaf or have profound hearing loss. However, CI patients suffer from limited voice and tonal perception due to spatial separation between the stimulating CI electrode and the receptor spiral ganglion neurons (SGNs). Directed regeneration of proximate SGN axons may improve tonal performance and implant fidelity by decreasing the spatial separation between the CI electrode and the neural receptor. Additionally, fibrous scar tissue formation on the surface of implanted electrodes further decreases tonal perception through current attenuation and spreading resulting in late-term hearing loss. Thus, designing surfaces that induce favorable responses from neural tissues will be necessary in overcoming signal resolution barriers. In this work, the inherent spatial and temporal control of photopolymerization was used to functionalize surfaces with topographical and biochemical micropatterns that control the outgrowth of neural and other cell types. First, laminin, a cell adhesion protein was patterned using a photodeactivation process onto methacrylate polymer surfaces and was shown to direct the growth of spiral ganglion neurons (SGN), the primary auditory neural receptors. These protein patterns could even overcome low amplitude/high periodicity competing topographical cues. Additionally, glass substrates were patterned with linear zwitterionic polymers and fibroblasts, astrocytes, and Schwann cells all showed dramatically decreased cell adhesion on 100 µm precocity patterns. Further, SGN neurites showed excellent alignment to these same patterns. Next, poly(dimethyl siloxane) (PDMS) was coated with a crosslinked zwitterionic thin film using a single step photografting/photopolymerization process to covalently bind the hydrogel to PDMS. These coated surfaces showed dramatically lower levels of protein, cell, and bacterial adhesion. Finally, zwitterionic hydrogels were strengthened by changing the concentration of poly(ethylene glycol) diacrylate (PEGDA) and 2-hydroxyethyl methacrylate (HEMA) in the formulation. The direct relationship between changing zwitterionic hydrogel formulation to strengthen the hydrogel and the anti-fouling properties were established. The fundamental understanding and design of cochlear implant materials described herein serves as a foundation for the development of next generation neural prosthetics.

Quantum dots (QDs) of II-VI semiconductors (CdS, CdSe, and CdTe) in the size range of 1~12 nm have attracted great interest in both fundamental research and technical applications in recent years. Due to their tunable size-dependent emission with high photoluminescence quantum yields, their broad excitation spectra and narrow emission bandwidths, the semiconductor QDs have been intensively investigated in versatile applications, including thin-film light emitting devices (LEDs), low-threshold lasers, optical amplifier media for telecommunication networks and biological labels. Thus, constructing and fabricating highly ordered QDs are of great importance in the field of nanotechnology. The surface chemistry behavior of the TOPO-CdSe QDs and TOPO-(CdSe)ZnS QDs at the air-water interface was carefully examined by various physical measurements. The surface pressure-area isotherms of the Langmuir monolayers of both types of QDs gave the average diameter which matched the value determined by TEM measurements. Topographic study of the Langmuir monolayers of both QDs revealed the 2D aggregation during the early stage of the compression process. The stability of the Langmuir monolayer of the TOPO-(CdSe)ZnS QDs was measured by the compression/decompression cycle and the kinetic measurements, both of which indicated that TOPO capped (CdSe)ZnS QDs can form stable Langmuir monolayers at the air-water interface. Langmuir-Blodgett (LB) film of the TOPO-(CdSe)ZnS QDs were prepared on quartz slides at different surface pressures and characterized by photoluminescence (PL) spectroscopy. The linear increase of the PL intensity with the increase of the number of layers deposited onto the quartz slide implied a homogeneous deposition of the Langmuir monolayer. The conjugates of 10, 12-pentacosadiynoic acid (PDA) and short chain peptide was used to modify the surface of (CdSe)ZnS core-shell QDs. The PDA-peptide capped QDs formed stable Langmuir monolayer. After the photopolymerization of PDA-peptide-QDs/PDA-peptide system at the air-water interface, a more uniform and robust Langmuir monolayer was constructed. The 3-mercaptopropyltrimethoxysilane (MPS) was linked to (CdSe)ZnS QDs by ligand exchange method. The sol-gel process of the MPS capped QDs Langmuir monolayer was studied under various subphases of pH and reaction time. The fast sol-gel process under a subphase of pH 12.0 led the formation of a more homogeneous Langmuir monolayer. A smooth MPS-QDs LB film deposited under pH 12.0 was also observed by AFM measurements. The imaging of the aggregates of lysozyme using lysozyme/(CdSe)ZnS QDs conjugate as a PL label was investigated. The amyloid fibrils formed by lysozyme/lysozyme-QDs conjugate were observed by epifluorescence microscopy, atomic force microscopy (AFM) and transmission electron microscopy (TEM) measurements. The emission intensity of the QDs labeled lysozyme was increased about 3 fold after formation of amyloid. This approach, for the first time, provided a convenience method to image the amyloid fibrils by epifluorescence microscopy.

Photon energy upconversion (UC), a process that can convert two or more photons with low energy to a single photon of higher energy, has the potential for overcoming the thermodynamic efficiency limits of sunlight-powered devices and processes. An attractive route to lowering the incident power density for UC lies in harnessing energy transfer through triplet-triplet annihilation (TTA). To maximize energy migration in multicomponent TTA-assisted UC systems, triplet exciton diffusivity of the chromophores within an inert medium is of paramount importance, especially in a solid-state matrix for practical device integration. In this thesis, low-threshold sensitized UC systems were fabricated and demonstrated by a photo-induced interfacial polymerization within a coaxial-flow microfluidic channel and in combination with nanostructured optical semiconductors. Dual-phase structured uniform UC capsules allow for the highly efficient bimolecular interactions required for TTA-based upconversion, as well as mechanical strength for integrity and stability. Through controlled interfacial photopolymerization, diffusive energy transfer-driven photoluminescence in a bi-molecular UC system was explored with concomitant tuning of the capsule properties. We believe that this core-shell structure has significance not only for enabling promising applications in photovoltaic devices and photochromic displays, but also for providing a useful platform for photocatalytic and photosensor units. Furthermore, for improving photon upconverted emission, a photonic crystal was integrated as an optical structure consisting of monodisperse inorganic colloidal nanoparticles and polymer resin. The constructively enhanced reflected light allows for the reuse of solar photons over a broad spectrum, resulting in an increase in the power conversion efficiency of a dye-sensitized solar cell as much as 15-20 %.

Although stereolithography (SL) is a remarkable improvement over conventional prototyping production, it is being pushed aggressively for improvements in both speed and resolution. However, it is not clear currently how these two features can be improved simultaneously and what the limits are for such optimization. In order to address this issue a quantitative SL cure process model is developed which takes into account all the sub-processes involved in SL: exposure, photoinitiation, photopolymerizaion, mass and heat transfer. To parameterize the model, the thermal and physical properties of a model compound system, ethoxylated (4) pentaerythritol tetraacrylate (E4PETeA) with 2,2-dimethoxy-2-phenylacetophenone (DMPA) as initiator, are determined. The free radical photopolymerization kinetics is also characterized by differential photocalorimetry (DPC) and a comprehensive kinetic model parameterized for the model material. The SL process model is then solved using the finite element method in the software package, FEMLAB, and validated by the capability of predicting fabricated part dimensions. The SL cure process model, also referred to as the degree of cure (DOC) threshold model, simulates the cure behavior during the SL fabrication process, and provides insight into the part building mechanisms. It predicts the cured part dimension within 25% error, while the prediction error of the exposure threshold model currently utilized in SL industry is up to 50%. The DOC threshold model has been used to investigate the effects of material and process parameters on the SL performance properties, such as resolution, speed, maximum temperature rise in the resin bath, and maximum DOC of the green part. The effective factors are identified and parameter optimization is performed, which also provides guidelines for SL material development as well as process and laser improvement.

Disease processes that are currently among the leading causes of death now require much more than just a stethoscope for diagnosis and a pill for treatment. The next generation of therapeutics needs to possess a degree of intelligence; the ability to sense and respond to their environment. Biomedical hydrogels have the ability to sense and respond to external stimulus and with the advent of nanotechnology; these polymers can be fabricated on the same size scale as cellular and sub-cellular processes. Throughout the body gradients in pH are used at the cellular level to regulate processes such nutrient transport and to fight infection. Sites of damage or disease within the body are associated with both a change in pH and abnormal nanoporous vasculature. pH-Responsive microgels and nanogels are small enough to access these locations within the body, sense the change in environment, and locally release a therapeutic agent In this work heterogeneous, photoinitiated free radical polymerizations were developed to synthesize novel pH-responsive microgels and nanogels that could be loaded with macromolecular therapeutics and could respond to either a basic or acidic change in pH. A novel photo-dispersion polymerization scheme was developed to synthesize poly(ethylene glycol) grafted poly(methacrylic acid) (P(MAA-g-PEG)) polycomplexation gels for oral protein delivery. These ranged in size from 100- 300 nm in diameter and could swell up to a 17-fold increase in volume, in response to a rise in pH. This property allowed them to protect insulin at low pH and release the protein at neutral pH. In this way the carriers could be used to transport proteins through the stomach to the small intestine for absorption. A novel photo-emulsion polymerization scheme was developed to synthesize poly(ethylene glycol) grafted poly[2-(diethylamino)ethyl methacrylate] nanogels, between 70-150 nm in diameter. These could swell up to a 22-fold increase in volume, in response to a drop in pH. These nanostructures were able to successfully target clathrin-dependent endocytosis and deliver macromolecules to the cytosol. / text

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: John F. MacGregor. Includes bibliographical references (p. 138-152). Also available online.

Thesis (M. S.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Tolbert, Laren; Committee Member: Bunz, Uwe; Committee Member: Payne, Christine

Thesis (Ph.D.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Henderson, Cliff; Committee Member: Beckham, Haskell; Committee Member: Hess, Dennis; Committee Member: Koros, William; Committee Member: Tolbert, Laren.

A utilização de resinas compostas para restaurações em dentes anteriores e posteriores é bastante frequente na odontologia atual, pois suas propriedades mecânicas e estéticas são compatíveis a estrutura dental. O objetivo deste trabalho foi confeccionar e caracterizar uma resina composta para uso odontológico utilizando esmalte bovino como carga de reforço. Para confeccionar a resina composta a mesma matriz orgânica comumente utilizada nas resinas comerciais foi empregada. A carga de reforço foi obtida através da moagem de fragmentos de esmalte bovino, e posteriormente submetida a um tratamento superficial para que tornasse possível a união das partículas com a matriz orgânica. Foram confeccionadas resinas compostas nas concentrações de 60, 70 e 85% em peso de carga. Para fotopolimerização um dispositivo a base de LED com banda de emissão centrada em 470 nm com intensidade e 1000 mW/cm2 foi usado. Duas resinas comerciais Filtek Z-250 e Supreme XT (3M ESPE) ambas na cor A2 foram empregadas para comparação. A caracterização das resinas experimentais e comerciais foi realizada através de ensaios de compressão axial e diametral, grau de conversão, teste de dureza Vickers e fluorescência. No teste de fluorescência realizado em dentes humanos, a resina experimental com 85% de partícula de carga em peso apresentou valores de intensidade de fluorescência em escala de cinza ao redor de 34 (unid. arb.) sendo mais semelhante ao dente (41 unid. arb.) quando comparada com as resinas comerciais que obtiveram valores ao redor de 17 (unid. arb.). Baseado nos testes realizados, a resina experimental apresenta propriedades promissoras para utilização em restaurações. / The use of composite resins for restorative procedure at anterior and posterior cavities is highly common in the modern Dentistry because its mechanical and aesthetic properties are compatible with the remanescent dental structure. The aim of this study was the manipulation and characterization of a dental composite resin using bovine enamel as reinforcing filler. The same organic matrix of the commercially available resins was used for this experimental resin. The reinforcing filler was obtained after the gridding of bovine enamel fragments and a superficial treatment was performed to allow the adhesion of the filler particles with the organic matrix. The experimental resin was manipulated at the weight filler concentrations of 60%, 70%, and 85%. A LED-based light source with 1000 mW/cm2 centered at 470 nm was used for photopolimerization. Two commercial resins, Filtek Z-250 and Supreme XT at A2 shade, were used for comparison. The resin characterization was performed with tensile strength and diametral tensile strength tests, conversion degree, Vickers hardness, and fluorescence. In the fluorescent test performed at human teeth, the experimental resin with 85% particle weight showed fluorescence intensity values at gray scale, around 34 (arbitrary units), being more similar to the tooth (41 arb. units) when compared with commercial resins (17 arb. units). Based on the investigated tests, the present experimental resin shows promising properties to its use on dental restorations.