Microgels, colloidal networks of crosslinked water-soluble polymers with dimensions < 1 μm, have been demonstrated to be useful materials in a wide range of biomedical and environmental applications. In particular, temperature-responsive microgels based on poly(N- isopropylacrylamide) (PNIPAM) have attracted significant research interest in drug delivery applications. However, conventional precipitation-based PNIPAM microgels are functionally non-degradable, problematic for biomedical applications. To resolve this issue, a thermally- driven self-assembly approach based on hydrazide and aldehyde functionalized PNIPAM oligomers to form an acid-labile hydrazone bond was developed in the Hoare Lab to produce thermoresponsive, colloidally stable, monodisperse and degradable microgels. In this thesis, the internal structure of these self-assembled microgels was investigated using small and ultra-small angle neutron scattering and surface force experiments. Contrary to expectations based on the assembly technique, all these characterization strategies suggested that self-assembled microgels have a homogeneously cross-linked internal structure. It is anticipated that these well-defined degradable and homogeneous nanoscale gel networks offer opportunities for addressing challenges in drug delivery, biosensing, and optics by exploiting the predictable diffusive and refractive properties of the homogeneous microgel networks. In addition, the co-self-assembly of a moderately hydrophobic anti-inflammatory drug (dexamethasone) during the microgel self-assembly process was demonstrated to enable five-fold higher drug encapsulation (75-80%) relative to the conventional partition/diffusion- based drug loading processes. This result addresses a key challenge in delivering hydrophobic drugs using conventional precipitation-based microgel systems due to the inherent hydrophilicity of the crosslinked network. The potential of the self-assembly approach to fabricate multi-responsive smart microgels was demonstrated by incorporating pH-ionizable functional groups (via the copolymerization of acrylic acid and 2-dimethylaminoethylmethacrylate to introduce anionic and cationic charges respectively) into the hydrazide and aldehyde-functionalized precursor polymers prior to self-assembly. The self-assembled charged microgels showed the same pH- responsive swelling behaviours of conventional microgels, including amphoteric microgels that can be formed at any desired cationic:anionic charge density by simply mixing different ratios of cationic and anionic precursor polymers. Such microgels offer significant potential to improve the performance of microgels in applications demanding dual pH/temperature specific drug delivery. / Thesis / Master of Applied Science (MASc) / Medications can exist in many different forms. From pills to injections, existing drug delivery systems require a high frequency of drug administration and often result in low efficacy of drug once administered to the human body. Polymer-based drug delivery systems have the potential to improve this delivery. In particular, microgels, water-filled crosslinked polymer networks with a size less than one micron, offer promise as a drug delivery vehicle. The size and chemical composition of microgels can be tailored to enable their use in a wide array of drug delivery applications. In addition, microgels can be loaded with a therapeutic agent and transported in the blood stream to deliver drug at a rate and/or location tunable based on the internal structure of the microgel. “Smart” microgels have the particularly attractive ability to change their properties in response to certain environmental stimuli (i.e. temperature or pH). However, current smart microgel systems are non-degradable and would accumulate in the body, causing undesired side-effects. In this thesis, a new self-assembly approach has been used to produce degradable microgels with the potential to switch properties in response to both temperature and pH. Water-insoluble drugs can be encapsulated more efficiently with this method, and the dual-responsive behaviour is expected to improve our capacity to deliver drug at the rate and location desired in the body.

The chemistry of the non-covalent bond has developed rapidly over the last few decades. In particular, the successful construction of nanoscale assemblies by non-covalent forces has been described more frequently in the recent literature. This significant progress is largely due to transferring of concepts found in the biological systems (e.g., the tobacco mosaic virus and the DNA double helix) to the area of synthetic chemistry. As an example, the architecture of the double helix, perhaps the most well-known biological self-assembling structure, remarkably demonstrates the ability of biological systems to construct large supramolecules by multiple aggregations of relatively simple building blocks by means of hydrogen bonding. Scientists have begun to employ such synthetic strategy adopted in Nature to construct nanoscale systems. The use of pseudorotaxane assemblies formed between the suitably sized crown ethers and dipyridinium salts (paraquats) or dibenzylammonium ions is a viable synthetic strategy to construct non-covalent systems because of their selectivity and strong hydrogen bonding ability. We describe the syntheses and characterization of non-covalent assemblies of different sizes and shapes via the pseudorotaxane approach. A series of dendritic pseudorotaxanes were efficiently prepared from self-assembling complimentary building blocks, namely a triply charged ammonium ion and the 1st, 2nd, and 3rd generations of benzyl ether dendrons bearing dibenzo-24-crown-8 moiety. The wholly complexed self-assembling dendrimers were evidenced by 1H NMR spectroscopy and mass spectrometry. Linear supramolecular pseudorotaxane polymers were formed with reversible chain extension in solution by self-assembly of two complimentary homoditopic molecules with secondary ammonium ion and dibenzo-24-crown-8 moieties. The fraction of the cyclic dimer and the size of the linear suprastructures were determined in solution by 1H NMR spectroscopy as a function of concentration. Viscosity measurements corroborated the presence of aggregates of large hydrodynamic volume at high concentrations. The solid state samples of the supramolecular polymers, prepared by freeze-drying, were analyzed by DSC and optical microscopy and shown to be distinct from the starting materials and the cyclic dimer. Fibers and films were formed from high concentration solutions, corroborating the polymeric nature of the aggregates. Similarly, polymolecular arrays were formed in solution from a heteroditopic self-complimentary molecule, comprising bis-m-phenylene-32-crown-10 and a paraquat unit. Side-chain polypseudorotaxanes were prepared from spontaneous association of polymethacrylates bearing dibenzo-24-crown-8 and secondary ammonium ions. The complexation behavior in solution was investigated using 1H NMR spectroscopy. The solid state samples of side-chain polypseudorotaxanes, prepared by freeze-drying, showed noticeable changes in thermal behavior and morphology from the individual components. / Ph. D.

This research developed a novel, non-wire bond semiconductor interconnect technology, termed the Dimple Array interconnect (DAI), with significantly improved electrical, thermal and mechanical characteristics for power electronics applications. In the DAI structure, electrical connections onto the devices are achieved by solder bumps formed between the silicon device and arrays of dimples stamped on a metal sheet flex. This research first presents the design of the materials, electrical and thermal performance, reliability, and the fabrication process of the DAI. It was found that due to the use of solder material, the current handling capability and thermal management of Dimple Array interconnected devices are significantly better than those using wire bonds. In addition, the shorter and wider solder joints reduce parasitics, which is a serious problem in wire bond interconnects. The proposed fabrication process of the DAI is simpler than other developing integrated power packaging technologies, such as flip chip and deposited metallization integration. DAI was successfully demonstrated in a half-bridge power electronics module with much improved electrical characteristics. The study then focuses on the thermomechanical reliability of Dimple Array packages as compared to conventional controlled collapse bonding (CCB) flip chip packages. Experimental approaches, such as power cycling and temperature cycling tests, and numerical simulation with the help of finite element analysis (FEA) were used. The thermal cycling test shows that dimple solder joints display an eightfold reliability improvement over the conventional CCB solder joints. The power cycling test showed that the measured forward voltage can not reliably reflect the integrity of the solder joint interconnect. However, from metallographic cross-section images of these samples, it was concluded that the DAI solder joints are more reliable than the CCB solder joints under power cycling conditions. FEA results showed excellent correlation with experiments in predicting that the Dimple Array solder joints are more fatigue-resistant due to a reduced stress/strain concentration. Furthermore, failure mechanisms were explored using the mapped stress/strain distribution within the models. It was found that the CCB solder joint has a highly localized strain concentration at the device/solder interface, while strains are more uniformly distributed over the whole Dimple Array solder joint. / Ph. D.

Understanding the evolution of charter school legislation and the expectations of legislators adopting this legislation is important to school boards and school administrators in Virginia. The purpose of this research project was to delineate the historical development of charter school legislation in Virginia. A non-emergent research design was used with two steps of data collection. The first step was a review of all charter school legislation, which covered the General Assembly Sessions 1994-2000, and the second step was a series of open-ended interviews with legislators and others who participated in the charter school legislative development. This study addressed the following research questions: 1. What changes did charter school legislation undergo before members of the Virginia General Assembly finally approved it for implementation? 2. What were the expectations of the legislators who sponsored charter school legislation? 3. What, if anything, either internal or external to the Virginia General Assembly, influenced the presenters of charter school legislation? 4. Did the enacted legislation that was adopted meet the expectations of the legislator who initiated charter school legislation? 5. Are legislators and others satisfied with the current status of charter school development in Virginia? Charter school legislative bills and related amendments from 1994 to 2000 were analyzed. Purposive and snowball sampling identified certain legislators as primary respondents, who were interviewed. After the interviews, the data were transcribed and analyzed using QSR NUD·IST. A total of eight interviews were conducted, and all respondents gave permission to record the interviews. Six themes emerged from the interviews. These themes are 1) Partisan Politics, 2) Local Autonomy, 3) Accountability, 4) Choice, 5) Funding, and 6) Opposition. Charter school legislation is unique to each state. Also, one delegate individually championed charter school legislation in Virginia. There were some external influences (outside the Virginia General Assembly) opposing charter school legislation; primarily the National Association for the Advancement of Colored People (NAACP), the Virginia School Boards Association (VSBA), and the Virginia Education Association (VEA). Equally important, partisan politics and the opposition of the Black Caucus in the General Assembly were the two strongest internal factors in defeating early attempts at charter school passage. All interviewees reported being satisfied with the outcome of charter school legislation; however, several legislators indicated dissatisfaction with the apparent slow pace of school boards in each locality of holding public hearings to determine whether they will accept charter school applications. Additionally, accountability based upon student results, an alternative schooling opportunity for public school students, and a lottery method for student selection were important charter school characteristics for adoption. / Ed. D.

It is now well established that a substantial fraction of all galaxy assembly occurs in intense bursts of star formation and black hole accretion, but the role of these two modes and how much they affect one another remains unclear. We thus investigate this in three complementary studies. In the first, we assemble a sample of 513 quasars identified by the Sloan Digital Sky Survey with detections by Herschel. These objects span a redshift range of 0 < z < 4, and their SEDs give a mean SFR of ~1000M☉/year. When comparing these SFRs to the intrinsic properties of the quasars, we find no clear connections between the quasars and the ongoing star formation events in their hosts. We then look for evidence of AGN feedback in broad absorption line (BAL) quasars, as such features are indicative of outflowing material. We find that high-ionization BAL quasars have indistinguishable properties to those of classical quasars. In our second study, which describes an iron low-ionization BAL quasar, SDSS J121441.42-000137.8, our results are again consistent with no feedback. Thus, it seems unlikely that feedback plays a dominant role in quenching star formation at the extreme SFRs seen in our BAL objects. We lastly study the host of an optically-bright quasar, SDSS J160705.16+355358.6, with evidence of an ongoing merger. We create the Point Spread Function (PSF) using a star that is in the same part of the field as our object, a method which is relatively unexplored. By subtracting the PSF, we are able to extract some of the host properties. We compare two PSF creation methods and find the empirical approach to be superior. Fits to the SEDs of the two galaxies are consistent with both falling on or above the main sequence of star formation. It is additionally plausible that these two galaxies could coalesce into a single massive quiescent galaxy by z ~ 2, and thus serve as progenitors to this class of galaxy that has proven challenging to our understanding of galaxy assembly. / Doctor of Philosophy / Quasars are among some of the brightest objects in the Universe and are powered by supermassive black holes that are rapidly accreting new material. The light from these distant objects can be detected across the electromagnetic spectrum, with each wavelength regime offering new insight into their properties. Further, if we look at their spectra, the features appear redshifted, i.e. they are at longer wavelengths compared to the expected values on Earth. More distant objects have higher redshifts. This, coupled with the constant speed of light, tells us that light from a quasar that has reached us on Earth must have been emitted many years ago; in other words, quasars offer glimpses into the past and can be used study how our Universe has assembled over time. Star formation and quasar activity in galaxies have been shown to coexist across all redshifts. This suggests a deep connection between a galaxy's stellar and black hole mass assemblies. Both peak at z ~ 2, implying that a substantial amount of all galaxy assembly took place in high-redshift, dusty bursts of star formation and quasar activity. This dust absorbs light originally emitted at optical/UV wavelengths and reradiates it in the infrared, making infrared wavelengths the perfect regime in which to investigate the connection between the two processes. In this dissertation, I have focused specifically on quasars with detections at both optical and far-infrared (FIR) wavelengths to determine what effect, if any, quasars have on the galaxies in which they reside. The optical emission of these systems describes the properties of the quasars, while the FIR estimates star formation rates (SFRs) in their hosts. Many astronomers invoke something called feedback, in which the quasar regulates the host star formation, to align theory with observations. We search for evidence of this process in the very bright quasars located within extremely star-forming systems. We, however, find no such evidence. This could imply that, at the high luminosities of our systems, feedback is not the dominant effect in regulating star formation, but perhaps some host self-regulation is instead. It could also imply that the feedback timescale is much shorter than that of either quasar or extreme star formation activity, making direct observations of feedback difficult.

Identifying the processes and mechanisms that govern communities of organisms is the main goal of community ecology. Locally operating mechanisms such as environmental filtering, in which the environment determines what species are found in a given location, as well as regional processes such as dispersal have all been identified as potential drivers of community processes. However, the relative importance of these drivers may vary temporally and spatially. In dendritic stream networks, headwater streams are isolated when compared to more centrally located mainstem stream sections. I investigated the potential for stream networks to influence the relative influence of local and regional processes via a survey and field experiment based approaches. I found that headwater streams can influence mainstem stream communities, potentially as a result of the dispersal of organisms or abiotic materials. Additionally, I demonstrated that macroinvertebrate communities in headwater streams respond more strongly to manipulations of local environment than do mainstem streams, both in terms of community composition as determined taxonomically and as functional traits. These results indicate that headwater streams may be affected differently than mainstem streams by anthropogenic activity and as such, management strategies and restorations may need to be specifically tailored to address the relative influences of local and regional processes at varying points within a stream network. / Ph. D.

With the introduction of metacommunity theory, the field of community ecology expanded its scope to include patterns and processes beyond the scale of local communities. Dispersal, or the movement of organisms between sites, can play an influential role in generating patterns of community assembly and stability. However, little is known about the role of dispersal in structuring and stabilizing freshwater communities. For my dissertation, I conducted a literature review of dispersal in stream metapopulations and metacommunities. Our current knowledge of the movement of freshwater taxa is limited due to difficulties in accurately monitoring dispersal. We have inferred the role of dispersal based primarily on organismal-based and graph-based proxies, although the body of work in modeling and experimental research is growing. Future research should incorporate innovative methods to directly monitor dispersal at finer spatial and temporal scales. To address this knowledge gap, we experimentally manipulated dispersal mode (aerial and drift) alongside the magnitude of dispersal (network location as a proxy) to investigate the role of these components of dispersal in community assembly and multiple metrics of stability. The results of my experiment suggest both factors may play a role in community assembly and stability patterns in stream metacommunities. Lastly, I conducted a mesocosm experiment with zooplankton mesocosms to investigate if biodiversity can generate asynchronous patterns of community dynamics that contribute to stability. There was a positive biodiversity-asynchrony relationship that, in turn, generated higher levels of stability. This effect was strongest in communities connected via dispersal. Overall, my dissertation demonstrates that dispersal plays a role in the assembly and stability of freshwater communities. / Doctor of Philosophy / Freshwater ecosystems and the abundance and richness of life that they support are threatened under global environmental change. One factor that may help maintain the diversity of stream-dwelling species is dispersal, or the movement of organisms between sites within networks of freshwater communities. The influence of dispersal on the formation and stability of freshwater communities is poorly understood. To determine the state of the science, I conducted a literature review on the study of dispersal in stream networks. We have only recently developed a limited knowledge of the direct movement of freshwater species within networks. The majority of what we know is deduced from patterns of diversity, the traits of organisms, or theoretical modeling. More direct measures of dispersal are needed to understand the dispersal of freshwater organisms. To address this knowledge gap, I conducted an experiment with streamside flumes throughout a stream network where I manipulated how a macroinvertebrate could colonize, or join, a stream community. I found that both position in a network and the use of various methods of colonization affect patterns of diversity and how stable stream communities are. Finally, I conducted an experiment where I manipulated the number of zooplankton and environmental conditions to detect the influence of dispersal on community dynamics and stability. Communities connected via dispersal had the highest level of asynchrony in dynamics and these community dynamics, in turn, produced the greatest amount of community stability. Overall, these findings demonstrate the role of dispersal in the biodiversity and stability of freshwater communities.

We have developed a new biofabrication process in which the precise control of bacterial motion is used to fabricate customizable networks of cellulose nanofibrils. This work describes how the motion of Acetobacter xylinum can be controlled by electric fields while the bacteria simultaneously produce nanocellulose, resulting in networks with aligned fibers. Since the electrolysis of water due to the application of electric fields produces the oxygen in the culture media far from the liquid-air boundary, aerobic cellulose production in 3D structures is readily achievable. Five separate sets of experiments were conducted to demonstrate the assembly of nanocellulose by Acetobacter xylinum in the presence of electric fields in micro and macro environments. This work demonstrates a new concept of bottom up material synthesis by control of a biological assembly process. / Master of Science

Electrostatic self-assembly was used to fabricate several samples of polymers known to have non-linear optical behavior. These samples characteristics were measured with interferometry and their electro-optic coefficients determined to be on the order that of LiNbO3. The self-assembled samples are shown to have an enhanced polar order compared to that of more traditional poled polymers. Furthermore, this polar order is intrinsic and thus doesn't require electric field poling and does not decay with time. The self-assembly process is therefore shown to possess great potential for the fabrication of high-speed electro-optic modulators for commercial and military applications. / Master of Science

Nanocomposites of multilayer structures of zirconia/polymer thin-film coatings have been fabricated on quartz and single-crystal silicon substrates by the Ionically Self-Assembled Monolayer (ISAM) technique. Particle size distribution was measured to calculate the grain diameter of the zirconia particles. UV/Vis spectroscopy and ellipsometry were used to characterize the ISAM technique. SEM and AFM were used to observe the microscopic structure of the multilayer structures. Some mechanical properties were characterized by adhesion, abrasion, and nano-hardness tests. It was shown that an important distinction of this novel technique over conventional coating processes is the fabrication of excellent molecular-level uniform films with precise control of film thickness at the à ngström-level at ambient temperature and pressure conditions. It was also shown the maximum Vickers microhardness of ZrO2/polymer nanocomposite thin-film coatings prepared by this method was greater than 25 GPa. / Master of Science