A parallel-plate capacitively-coupled plasma deposition system was designed and built for the growth of polyethylene glycol-like films. Deposition rate, bonding structure and dissolution and swelling behavior was characterized as a function of input RF power, reactor pressure and substrate temperature to provide information on the relationship between input plasma parameters and film properties. For the conditions studied in this thesis, deposition rates increased at increasing input powers and operating pressures and decreasing substrate temperatures. The PEG-like coatings resembled higher molecular weight solution-polymerized PEG films with a higher crosslinked structure. Manipulation of plasma deposition conditions allowed control of film crosslink density and resulted in tunable dissolution and swelling properties of the PEG-like polymer. At higher applied powers, lower operating pressures, and higher substrate temperatures, films had a higher crosslink density, thus leading to slower dissolution rates and smaller extents of swelling. Void space openings of swelled-state, PEG-like films were determined using electrophoretic drift and diffusion-controlled transport of fluorophore-tagged PAMAM dendrimers into the bulk of the coating. PAMAM dendrimers were used because of their well-defined sizes and negatively-charged succinamic acid surface groups as a means to probe pore sizes of the plasma films. It was estimated that the upper bound of pore size diameters in the plasma polymer was approximately equal to ~5.5-6.0 nm. Positron annihilation lifetime spectroscopy was used to determine average pore sizes and was estimated to equal ~0.60-0.65 nm.

Atherosclerosis is the number one cause of death in the United States and one of the most common treatments is the implantation of a stent. In order to eliminate the two most common complications - restenosis and thrombosis - a novel covered stent is investigated. A covered stent membrane should be able to undergo large stretch, prevent restenosis, and be relatively non-thrombogenic. Polyvinyl alcohol (PVA) cryogels are examined as a candidate material for covered stent membranes. Mechanical testing included uniaxial tensile testing, puncture testing, and the fabrication and expansion of PVA cryogel covered stents. Uniaxial testing showed PVA cryogels to have sufficient ultimate stretch which was similar to bare metal stents during deployment. Puncture testing revealed that PVA cryogels are not likely to puncture in vivo. No tears were seen in the PVA cryogel membrane after expansion of the covered stents. Finite element analysis was used to determine a PVA cryogel membrane's effect on artery wall stress. PVA cryogel covered stents reduced both artery wall stress and tissue prolapse when compared to equivalent uncovered stents. Migration assays were used to determine if PVA cryogels are able to block the smooth muscle cell migration seen during restenosis. PVA cryogels significantly reduced cellular migration in modified Boyden chambers - suggesting that they would be able to prevent restenosis in vivo. Thrombogenicity was tested in vitro with a gravity-fed flow loop using porcine blood and in vivo with a sheep model. PVA cryogels were found to be less thrombogenic than polyester controls with the flow loop system. The sheep study demonstrated the feasibility of implanting PVA cryogel covered stents and good early patency. After explantation, the PVA cryogel membranes were intact - providing in vivo evidence for the durability of PVA cryogel covered stents. Overall, this work provides evidence that covered stents made with PVA cryogels are a feasible device in terms of their mechanics, ability to prevent restenosis, and low thrombogenicity. This work represents a major advancement in the development of PVA cryogel covered stents and provides necessary safety and feasibility data for future clinical trials.

The interface between tendon/ligament and bone tissue is a complex transition of biochemical, cellular, and mechanical properties. Investigating computational and tissue engineering models that imitate aspects of this interface may supply critical design parameters for designing future tissue replacements to promote increased biochemical and mechanical integration between tendon/ligament and bone. Strategies for modeling this tissue have typically focused on the development of heterogeneous structures to create gradients or multiphasic materials that mimic aspects of the transition. However, further work is required to elucidate the role of specific mechanical and material stimuli in recapitulating features of the tendon/ligament-bone insertion. In particular, in constructs that exhibit variation in both mechanical and biochemical properties, the interplay of mechanical, material, and chemical signals can complicate understanding of the particular factors at work in interface formation. Thus, the overall goal of this dissertation was to provide insight into the role of mechanical strain and scaffold degradability on cell behavior within heterogeneous biomaterials. Specifically, a method for determining cell vertical position within a degradable gel through a laminated interface was developed. A computational model was created to examine possible variation in local mechanical strain due to heterogeneity in mechanical properties and different interface geometries. Finally, the influence of biomaterial degradability on changes in encapsulated human mesenchymal stem cell morphology under response to cyclic mechanical strain was explored. Together, these studies provide insight into mechanical and material design considerations when devising tissue engineering strategies to regenerate the tendon/ligament-bone interface.

Indiana University-Purdue University Indianapolis (IUPUI) / Both quaternary ammonium bromide (QAB) and furanone derivatives were synthesized, characterized and formulated into dental resin composites for improved antibacterial properties. Compressive strength (CS) and S. mutans viability were used to evaluate the mechanical strength and antibacterial activity of the restoratives. The effects of chain length, loading, saliva and aging on CS and S. mutans viability were investigated. Chapter 2 describes how we studied and evaluated the formulated antibacterial resin composites by incorporating the synthesized QAB-containing oligomers into the formulation. The results show that all the QAB-modified resin composites showed significant antibacterial activity and mechanical strength reduction. Increasing chain length and loading significantly enhanced the antibacterial activity but dramatically reduced the CS as well. The 30-day aging study showed that the incorporation of the QAB accelerated the degradation of the composite, suggesting that the QAB may not be well suitable for development of antibacterial dental resin composites or at least the QAB loading should be well controlled. Chapter 3 describes how we studied and evaluated the formulated antibacterial resin composite by incorporating the synthesized furanone derivative into the formulation. The results show that the modified resin composites showed a significant antibacterial activity without substantially decreasing the mechanical strengths. With 5 to 30% addition of the furanone derivative, the composite kept its original CS unchanged but showed a significant antibacterial activity with a 16-68% reduction in the S. mutans viability. Further, the antibacterial function of the new composite was found not to be affected by human saliva. The aging study indicates that the composite may have a long-lasting antibacterial function. In summary, we have developed a novel QAB- and furanone-containing antibacterial system for dental restoratives. Both QAB- and furanone-modified resin composites have demonstrated significant antibacterial activities. The QAS-modified experimental resin composite may not be well suitable for development of antibacterial dental resin composites due to its accelerated degradation in water unless the QAB loading is well controlled. The furanone-modified resin composite shows nearly no reduction in mechanical strength after incorporation of the antibacterial furanone derivative. It appears that the furanone-modified resin composite is a clinically attractive dental restorative that can be potentially used for long-lasting restorations due to its high mechanical strength and permanent antibacterial function.

Indiana University-Purdue University Indianapolis (IUPUI) / In recent years, magnesium alloys, due to their high strength and biocompatibility, have attracted significant interest in medical applications, such as cardiovascular stents, orthopedic implants, and devices. To overcome the high corrosion rate of magnesium alloys, coatings have been developed on the alloy surface. Most coating methods, such as anodic oxidation, polymer coating and chemical conversion coating, cannot produce satisfactory coating to be used in human body environment. Recent studies demonstrate that micro-arc oxidation (MAO) technique can produce hard, dense, wear-resistant and well-adherent oxide coatings for light metals such as aluminum, magnesium, and titanium. Though there are many previous studies, the understanding of processing conditions on coating performance remains elusive. Moreover, previous tests were done in simulated body fluid. No test has been done in a cell culture medium, which is much closer to human body environment than simulated body fluid. In this study, the effect of MAO processing time (1 minute, 5 minutes, 15 minutes, and 20 minutes) on the electrochemical behaviors of the coating in both conventional simulated body fluid and a cell culture medium has been investigated. Additionally a new electrolyte (12 g/L Na2SiO3, 4 g/L NaF and 4 ml/L C3H8O3) has been used in the MAO coating process. Electrochemical behaviors were measured by performing potentiodynamic polarization and electrochemical impedance spectroscopy tests. In addition to the tests in simulated body fluid, the MAO-coated and uncoated samples were immersed in a cell culture medium to investigate the corrosion behaviors and compare the difference in these two kinds of media. The results show that in the immersion tests in conventional simulated body fluid, the 20-minute MAO coated sample has the best resistance to corrosion due to the largest coating thickness. In contrast, in the cell culture medium, all MAO coated samples demonstrate a similar high corrosion resistance behavior, independent of MAO processing time. This is probably due to the organic passive layers formed on the coating surfaces. Additionally, a preliminary finite element model has been developed to simulate the immersion test of magnesium alloy in simulated body fluid. Comparison between the predicted corrosion current density and experimental data is discussed.

Indiana University-Purdue University Indianapolis (IUPUI) / Dicalcium phosphate dihydrate (DCPD) cements have been used for bone repair due to its excellent biocompatibility and resorbability. However, DCPD cements are typically weak and brittle. To overcome these limitations, the sodium citrate used as a setting regulator and the coating of poly-L-lactide acid (PLLA) technique have been proposed in this study. The first purpose of this thesis is to develop composite PLLA/DCPD scaffolds with enhanced toughness by PLLA coating. The second purpose is to examine the biocompatibility of the scaffolds. The final purpose is to investigate the degradation behaviors of DCPD and PLLA/DCPD scaffolds. In this experiment, DCPD cements were synthesized from monocalcium phosphate monohydrate (MCPM) and 𝛽-tricalcium phosphate (𝛽 –TCP) by using deionized water and sodium citrate as liquid components. The samples were prepared with powder to liquid ratio (P/L) at 1.00, 1.25 and 1.50. To fabricate the PLLA/DCPD composite samples, DCPD samples were coated with 5 % PLLA. The samples were characterized mechanical properties, such as porosity, diametral tensile strength, and fracture energy. The mechanical properties of DCPD scaffolds with and without PLLA coating after the in vitro static degradation (day 1, week1, 4, and 6) and in vitro dynamic degradation (day 1, week 1, 2, 4, 6, and 8) were investigated by measuring their weight loss, fracture energy, and pH of phosphate buffer solution. In addition, the dog bone marrow stromal stem cells (dBMSCs) adhesion on DCPD and PLLA/DCPD composite samples were examined by scanning electron microscopy. The cell proliferation and differentiation in the medium conditioned with DCPD and PLLA/DCPD composite samples were studied by XTT (2,3-Bis(2-methoxy-4- nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide inner salt), and alkaline phosphatase (ALP) assay, respectively. The addition of sodium citrate and PLLA coating played a crucial role in improving the mechanical properties of the samples by increasing the diametral tensile strength from 0.50 ± 0.15 MPa to 2.70 ± 0.54 MPa and increasing the fracture energy from 0.76 ± 0.18 N-mm to 12.67 ± 4.97 N-mm. The DCPD and PLLA/DCPD composite samples were compatible with dBMSCs and the cells were able to proliferate and differentiate in the conditioned medium. The degradation rate of DCPD and PLLA/DCPD samples were not significant different (p > 0.05). However, the DCPD and PLLA/DCPD composite samples those used sodium citrate as a liquid component was found to degrade faster than the groups that use deionized water as liquid component