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

An Effective Dispersant for Oil Spills Based on Food-Grade Amphiphiles

Synthetic dispersants such as Corexit 9500A were used in large quantities (∼2 million gallons) to disperse the oil spilled in the ocean during the recent Deepwater Horizon event. These dispersant formulations contain a blend of surfactants in a base of organic solvent. Some concerns have been raised regarding the aquatic toxicity and environmental impact of these formulations. In an effort to create a safer dispersant, we have examined the ability of food-grade amphiphiles to disperse (emulsify) crude oil in seawater. Our studies show that an effective emulsifier is obtained by combining two such amphiphiles: lecithin (L), a phospholipid extracted from soybeans, and Tween 80 (T), a surfactant used in many food products including ice cream. Interestingly, we find that L/T blends show a synergistic effect, i.e., their combination is an effective emulsifier, but neither L or T is effective on its own. This synergy is maximized at a 60/40 weight ratio of L/T and is attributed to the following reasons: (i) L and T pack closely at the oil–water interface; (ii) L has a low tendency to desorb, which fortifies the interfacial film; and (iii) the large headgroup of T provides steric repulsions between the oil droplets and prevents their coalescence. A comparison of L/T with Corexit 9500A shows that the former leads to smaller oil droplets that remain stable to coalescence for a much longer time. The smaller size and stability of crude oil droplets are believed to be important to their dispersion and eventual microbial degradation in the ocean. Our findings suggest that L/T blends could potentially be a viable alternative for the dispersion of oil spills