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.

SELECTED ICONIC CHAMBER MUSIC WORKS WITH PIANO FROM THE NINETEENTH AND TWENTIETH CENTURIES

Chamber music repertoire featuring the piano blossomed from the mid-nineteenth through the early twentieth century. The quantity of works increased greatly during this time and the quality of these works reached the highest level. Among the many symbolic works that were composed were sonatas for a single string instrument with piano, piano trios, quartets: and quintets as well as two-piano works and four-hand duets. Being able to study and perform many of these iconic works before I graduated was one of the major goals I set for myself as a collaborative pianist. The abundance of repertoire has made it easy to choose works considered "iconic" for my dissertation's three recitals. Iconic is defined as "very famous or popular, especially being considered to represent particular opinions or a particular time" in the online Cambridge Advanced Leamer's Dictionary & Thesaurus © Cambridge University. The compositions featured in the recitals were composed from 1842 through 1941, including works by Schumann, Brahms, Faure, Rachmaninoff, Ravel, and Lutoslawski. Choosing the repertoire with my fellow performers in mind was an important part of this dissertation. In addition to trying to make balanced programs which include variety, working with different instruments and performers is one of the most fulfilling parts of the musical experience for me as a collaborative pianist. Joining me for the concerts were members of the Aeolus String Quartet (violinist Nicholas Tavani, violinist Rachel Shapiro, violist Greg Luce, and cellist Alan Richardson), pianist Hsiao-Ying Lin (a doctoral student from the Peabody Conservatory), and my colleagues from the Peabody Institute Preparatory Division (faculty violinist Dr. Christian Tremblay and cellist Alicia Ward), and Derek Smith, Associate Principal violist of the Annapolis Symphony Orchestras). The three recitals were performed in the Gildenhom and Ulrich Recital Halls at the University of Maryland, College Park, Maryland. They are recorded on CD and available on compact discs, which can be found in the Digital Repository at the University of Maryland (DRUM).