<p> A new paradigm in biomedical engineering calls for biologically active implants that are absorbed by the body over time. One popular application for this concept is in the engineering of endovascular stents that are delivered concurrently with balloon angioplasty. These devices enable the injured vessels to remain patent during healing, but are not needed for more than a few months after the procedure. Early studies of iron- and magnesium-based stents have concluded that magnesium is a potentially suitable base material for such a device; alloys can achieve acceptable mechanical properties and do not seem to harm the artery during degradation.</p><p> Research done up to the onset of research contained in this dissertation, for the most part, failed to define realistic physiological corrosion mechanisms, and failed to correlate degradation rates between <i>in vitro</i> and <i>in vivo</i> environments. Six previously published works form the basis of this dissertation. The topics of these papers include (1) a method by which tensile testing may be applied to evaluate biomaterial degradation; (2) a suite of approaches that can be used to screen candidate absorbable magnesium biomaterials; (3) <i>in vivo-in vitro</i> environmental correlations based on mechanical behavior; (4) a similar correlation on the basis of penetration rate; (5) a mid-to-late stage physiological corrosion mechanism for magnesium in an arterial environment; and (6) the identification of corrosion products in degradable magnesium using transmission electron microscopy.</p>

<p> Inspired by the Sandcastle Worm, biomimetic of the water-borne adhesive was developed by complex coacervation of the synthetic copolyelectrolytes, mimicking the chemistries of the worm glue. The developed underwater adhesive was designed for sealing fetal membranes after fetoscopic surgery in twin-to-twin transfusion syndrome (TTTS) and sealing neural tissue of a fetus in aminiotic sac for spina bifida condition.</p><p> Complex coacervate with increased bond strength was created by entrapping polyethylene glycol diacrylate (PEG-dA) monomer within the cross-linked coacervate network. Maximum shear bond strength of ~ 1.2 MPa on aluminum substrates was reached. The monomer-filled coacervate had complex flow behavior, thickening at low shear rates and then thinning suddenly with a 16-fold drop in viscosity at shear rates near 6 s^-1. The microscale structure of the complex coacervates resembled a three-dimensional porous network of interconnected tubules. This complex coacervate adhesive was used in vitro studies to mimic the uterine wall-fetal membrane interface using a water column with one end and sealed with human fetal membranes and poultry breast, and a defect was created with an 11 French trocar. The coacervate adhesive in conjunction with the multiphase adhesive was used to seal the defect. The sealant withstood an additional traction of 12 g for 30&minus;60 minutes and turbulence of the water column without leakage of fluid or slippage. The adhesive is nontoxic when in direct contact with human fetal membranes in an organ culture setting. </p><p> A stable complex coacervate adhesive for long-term use in TTTS and spina bifida application was developed by methacrylating the copolyelectrolytes. The methacrylated coacervate was crosslinked chemically for TTTS and by photopolymerization for spina bifida. Tunable mechanical properties of the adhesive were achieved by varying the methacrylation of the polymers. Varying the amine to phosphate (A/P) ratio in the coacervate formation generated a range of viscosities. The chemically cured complex coacervate, with sodium (meta) periodate crosslinker, was tested in pig animal studies, showing promising results. The adhesive adhered to the fetal membrane tissue, with maximum strength of 473 &plusmn; 82 KPa on aluminum substrates. The elastic modulus increased with increasing methacrylation on both the polyphosphate and polyamine within the coacervate. Photopolymerized complex coacervate adhesive was photocured using Eosin-Y and treiethanolamine photoinitiators, using a green laser diode. Soft substrate bond strength increased with increasing PEG-dA concentration to a maximum of ~90 kPa. The crosslinked complex coacervate adhesives with PEG networks swelled less than 5% over 30 days in physiological conditions. The sterile glue was nontoxic, deliverable through a fine cannula, and stable over a long time period. Preliminary animal studies show a novel innovative method to seal fetal membrane defects in humans, <i>in utero</i>. </p>

Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006. / Source: Dissertation Abstracts International, Volume: 68-02, Section: B, page: 1237. Adviser: Russell D. Jamison. Includes bibliographical references. Available on microfilm from Pro Quest Information and Learning.

Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2006. / Source: Dissertation Abstracts International, Volume: 68-02, Section: B, page: 1239. Adviser: Russell D. Jamison. Includes bibliographical references. Available on microfilm from Pro Quest Information and Learning.

<p> Aortic valve disease (AVD) is a large contributor to health costs in the United States affecting 2.8% of the population greater than 75 years old. With a growing elderly population due to medical advances, AVD will continue to rise in prevalence over time. Current treatments for AVD are insufficient due to a lack of preventative therapies and the bioprosthetic valves used for surgical replacement have major limitations. Tissue engineered heart valves (TEHVs) present an ideal solution to current AVD needs because of their biocompatibility, capability to integrate with the host&rsquo;s tissue, and ability to utilize the natural repair mechanisms of the body. To achieve this goal, we designed synthetic environments with specific cell phenotypes and scaffold properties in order to direct cellular behavior and tissue growth <i> in vitro</i>. In this work cell subpopulations, mechanical stiffness of the substrate, and material surface charge were all studied to understand how the primary cells of the aortic valve, valvular interstitial cells (VICs), were affected by specific environmental cues. These studies were then translated from monolayer culture into a three-dimensional hydrogel system for the study of VICs in a more physically relevant cell culture system.</p><p>

Semiconductor quantum dots (QDs) and gold nanoparticles (AuNPs) have gained tremendous attention in the last decade as a result of their size-dependent spectroscopic properties. These nanoparticles have been a subject of intense study to bridge the gap between macroscopic and atomic behavior, as well as to generate new materials for novel applications in therapeutics, biological sensing, light emitting devices, microelectronics, lasers, and solar cells. One of the most promising areas for the use of these nanoparticles is in biotechnology, where their size-dependent optical properties are harnessed for imaging and sensing applications. However, these nanoparticles, as synthesized, are often not stable in aqueous media and lack simple and reliable means of covalently linking to biomolecules. The focus of this work is to advance the progress of these nanomaterials for biotechnology by synthesizing them, characterizing their optical properties and rendering them water-soluble and functional while maintaining their coveted optical properties. QDs were synthesized by an organometallic chemical procedure that utilizes coordinating solvents to provide brightly luminescent nanoparticles. The optical interactions of these QDs were studied as a function of concentration to identify particle size-dependent optimal concentrations, where scattering and indirection excitation are minimized and the amount light observed per particle is maximized. Both QDs and AuNPs were rendered water-soluble and stable in a broad range of biologically relevant conditions by using a series of ligands composed of dihydrolipoic acid (DHLA) appended to poly(ethylene glycol) methyl ether. By studying the stability of the surface modified AuNPs, we revealed some interesting information regarding the role of the surface ligand on the nanoparticle stability (i.e. solubility in high salt concentration, resistance to dithiothreitol competition and cyanide decomposition). Furthermore, the nanoparticles were functionalized using a series of bifunctional ligands that contain a dithiol group (DHLA) for surface binding, a PEG segment to instill water-solubility and a terminal functional group for easy bioconjugation (i.e. NH2, COOH, or biotin). Finally, a sensing application was demonstrated to detect the presence of microbial DNA (unmethlylated CpG) by using Toll-like receptor 9 proteins as the recognition components and the QDs as the transduction elements via Förster Resonance Energy Transfer.

Thesis (Ph. D.)--University of Illinois at Urbana-Champaign, 2007. / Source: Dissertation Abstracts International, Volume: 68-11, Section: B, page: 7610. Adviser: Jennifer A. Lewis. Includes bibliographical references. Available on microfilm from Pro Quest Information and Learning.