The fabrication and study of stimuli-responsive microgel-based modular assemblies
Clarke, Kimberly C.
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This dissertation describes the development of temperature and pH-responsive interfaces, where the emphasis is placed on tuning the responsivities within a physiological temperature range. This tuning is achieved through the utilization of polymeric building blocks, where each component is specifically synthesized to have a unique responsivity. The assembly of these components onto surfaces permits the fabrication of stimuli-responsive interfaces. In addition, this dissertation explores the use of a self-assembling peptide as a modular building block to modify the interface of hydrogel microparticles, resulting in the formation of a new biosynthetic construct. Hydrogels are three-dimensional, crosslinked polymer networks that swell in water. Over the years, hydrogels have been extensively explored as biomaterials due to their high water content, tunable mechanics, and chemical versatility. Two areas where hydrogels have received considerable interest are drug delivery and extracellular matrices. Unfortunately, developing structurally and functionally complex hydrogels from the top down is challenging because many parameters cannot be independently tuned in a bulk material. An alternative route would be to develop a library of building blocks, where each is tailored for a given function, and assemble these components into composite structures. The building block synthesized and utilized in this dissertation is a microgel. Microgels are a colloidal dispersion of hydrogel microparticles, ranging in size from 100 to 1000 nm in diameter. The microgels were prepared from environmentally responsive polymers, sensitive to both temperature and pH. Microgels have been used in the fabrication of polyelectrolyte layer-by-layer films, where the microgel serves as the polyanion and a linear polycation is used to “stitch” the particles together. In Chapters 3 and 4, stimuli-responsive interfaces are prepared from environmentally responsive microgel building blocks. In particular, Chapter 3 demonstrates tuning of the film response temperature by preparing several different microgels with differing ratios of two thermoresponsive polymers. Chapter 4 evaluates the influence of the pH environment on the thermoresponsivity of microgel films. While the pH environment was found to substantially affect some films, it is possible to prepare microgel films that behave independently of pH. The swelling/de-swelling of the films was also investigated by atomic force microscopy (AFM) as a function of both pH and temperature. It was determined that the AFM imaging parameters can drastically affect the measured film thicknesses (Appendix A) due to the soft, deformable nature of microgel films. The studies in these chapters illustrate the advantages of preparing composite structures from discrete components, where the functionality of the composite is dictated by the constituent particles. In Chapter 5, attention is placed on modifying the surface of microgel particles. Many of the traditional routes used to modify microgels involve the incorporation of co-monomers into the network or the addition of polymer shells. However, a new core/shell construct is presented, where a microgel core is coated with a self-assembling peptide shell. In this scenario, the peptide shell serves as a modular scaffold, where surface-localized functional groups can participate in reactions. Although there are still a number of questions remaining in regard to the assembly process and stability of the construct, initial experiments suggests that this is an interesting and promising structure to study. Finally, a discussion of future directions and possible experiments is provided in Chapter 6. Hopefully, this will serve as a guide for further exploration of the research presented herein. Microgels remain a rich class of materials to study and employ. While their synthesis is rather straightforward, their use often results in complex behavior and interesting phenomena. Understanding their behavior is a crucial step in realizing their full potential.