Designing Hydrogels that Transform their Shape in Response to Molecular Cues

There has been considerable interest in developing shape-changing soft materials for potential applications in drug delivery, microfluidics and biosensing. These shape- changing materials are inspired by the morphological changes exhibited by plants in nature, such as the Venus flytrap. One specific class of shape-change is that from a flat sheet to a folded structure (e.g., a tube). Such “self-folding” materials are usually composed of polymer hydrogels, and these typically fold in response to external stimuli such as pH and temperature. In order to develop these hydrogels for the previously described applications, it is necessary to expand the range of triggers. The focus of this dissertation is the advancement of shape-changing polymer hydrogels that are sensitive to uncommon cues such as specific biomolecules (enzymes), the substrates for such enzymes, or specific multivalent cations. First, we describe a hybrid gel that responds to the presence of low concentrations of a class of enzymes known as matrix metalloproteinases (MMPs). The hybrid gel was created by utilizing photolithographic techniques to combine two or more gels with distinct chemical composition into the same material. Certain portions of the hybrid gel are composed of a biopolymer derivative with crosslinkable groups. The hybrid gel is flat in water; however, in the presence of MMPs, the regions containing the biopolymer are degraded and the flat sheet folds to form a 3D structure. We demonstrate that hydrogels with different patterns can transform into different 3D structures such as tubes, helices and pancakes. Furthermore, this shape change can be made to occur at physiological concentrations of enzymes. Next, we report a gel with two layers that undergoes a shape change in the presence of glucose. The enzyme glucose oxidase (GOx) is immobilized in one of the layers. GOx catalyzes the conversion of glucose to gluconic acid. The production of gluconic acid decreases the local pH. The decrease in local pH causes one of the layers to swell. As a result, the flat sheet folds to form a tube. The tube unfolds to form a flat sheet when it is transferred to a solution with no glucose present. Therefore, this biomolecule- triggered shape transformation is reversible, meaning the glucose sensing gel is reusable. Furthermore, this shape change only occurs in the presence of glucose and it does not occur in the presence of other small sugars such as fructose. In our final study, we report the shape change of a gel with two layers in the presence of multivalent ions such as Ca2+ and Sr2+. The gel consists of a passive layer and an active layer. The passive layer is composed of dimethylyacrylamide (DMAA), which does not interact with multivalent ions. The active layer consists of DMAA and the biopolymer alginate. In the presence of Ca2+ ions, the alginate chains crosslink and the active layer shrinks. As a result, the gel converts from a flat sheet to a folded tube. What is particularly unusual is the direction of folding. In most cases, when flat rectangular gels fold, they do so about their short-side. However, our gels typically fold about their long-side. We hypothesize that non-homogeneous swelling determines the folding axis.

Design of Nanophotonic Antireflection Coatings for III-V Thin-Film Photovoltaics

Thin-film photovoltaics have provided a critical design avenue to help decrease the overall cost of solar power. However, a major drawback of thin-film solar cell technology is decreased optical absorption, making compact, high-quality antireflection coatings of critical importance to ensure that all available light enters the cell. In this thesis, we describe high efficiency thin-film InP and GaAs solar cells that utilize a periodic array of nanocylinders as antireflection coatings. We use coupled optical and electrical simulations to find that these nanophotonic structures reduce the solar-weighted average reflectivity of InP and GaAs solar cells to around 1.3 %, outperforming the best double-layer antireflection coatings. The coupling between Mie scattering resonances and thin-film interference effects accurately describes the optical enhancement provided by the nanocylinders. The spectrally resolved reflectivity and J-V characteristics of the devices under AM1.5G solar illumination are determined via the coupled optical and electrical simulations, resulting in predicted power conversion efficiencies > 23 %. We conclude that the nanostructured coatings reduce reflection without negatively affecting the electronic properties of the InP and GaAs solar cells by separating the nanostructured optical components from the active layer of the device.

Ionospheric Turbulence Near the Upper Hybrid Layer: Theory and Experiment

The thesis presents experimental results, simulations, and theory on turbulence excited in magnetized plasmas near the ionosphere’s upper hybrid layer. The results include: The first experimental observations of super small striations (SSS) excited by the High-Frequency Auroral Research Project (HAARP) The first detection of high-frequency (HF) waves from the HAARP transmitter over a distance of 16x10^3 km The first simulations indicating that upper hybrid (UH) turbulence excites electron Bernstein waves associated with all nearby gyroharmonics Simulation results that indicate that the resulting bulk electron heating near the upper hybrid (UH) resonance is caused primarily by electron Bernstein waves parametrically excited near the first gyroharmonic. On the experimental side we present two sets of experiments performed at the HAARP heating facility in Alaska. In the first set of experiments, we present the first detection of super-small (cm scale) striations (SSS) at the HAARP facility. We detected density structures smaller than 30 cm for the first time through a combination of satellite and ground based measurements. In the second set of experiments, we present the results of a novel diagnostic implemented by the Ukrainian Antarctic Station (UAS) in Verdansky. The technique allowed the detection of the HAARP signal at a distance of nearly 16 Mm, and established that the HAARP signal was injected into the ionospheric waveguide by direct scattering off of dekameter-scale density structures induced by the heater. On the theoretical side, we present results of Vlasov simulations near the upper hybrid layer. These results are consistent with the bulk heating required by previous work on the theory of the formation of descending artificial ionospheric layers (DIALs), and with the new observations of DIALs at HAARP’s upgraded effective radiated power (ERP). The simulations that frequency sweeps, and demonstrate that the heating changes from a bulk heating between gyroharmonics, to a tail acceleration as the pump frequency is swept through the fourth gyroharmonic. These simulations are in good agreement with experiments. We also incorporate test particle simulations that isolate the effects of specific wave modes on heating, and we find important contributions from both electron Bernstein waves and upper hybrid waves, the former of which have not yet been detected by experiments, and have not been previously explored as a driver of heating. In presenting these results, we analyzed data from HAARP diagnostics and assisted in planning the second round of experiments. We integrated the data into a picture of experiments that demonstrated the detection of SSS, hysteresis effects in simulated electromagnetic emission (SEE) features, and the direct scattering of the HF pump into the ionospheric waveguide. We performed simulations and analyzed simulation data to build the understanding of collisionless heating near the upper hybrid layer, and we used these simulations to show that bulk electron heating at the upper hybrid layer is possible, which is required by current theories of DAIL formation. We wrote a test particle simulation to isolate the effects of electron Bernstein waves and upper hybrid layers on collisionless heating, and integrated this code to work with both the output of Vlasov simulations and the input for simulations of DAIL formation.