<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.

Hydroxyapatite (HAp) is an ideal bioactive material that is used in orthopedics. Chemical composition and crystal structure properties of HAp are similar to the natural bone hence it promotes bone growth. However, its mechanical properties of synthetic HAp are not sufficient for major load-bearing bone replacement. The potential of improving the mechanical properties of synthetic hydroxyapatite (HAp) by incorporating carboxyl functionalized single walled carbon nanotubes (CfSWCNT) and polymerized ɛ-caprolactam (nylon) is studied. The fracture toughness, tensile strength, Young’s modulus, stiffness and fracture energy were studied for a series of HAp samples with CfSWCNT concentrations varying from 0 to 1.5 wt. % without, and with nylon addition. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Differential Scanning Calorimetry (DSC) were used to characterize the samples. The fracture toughness and tensile test was performed under the standard protocol of ASTM D5045 and ASTM D638-02a respectively. Reproducible maximum values of (3.60 ± 0.3) MPa.m1/2 for fracture toughness and 65.38 MPa for tensile strength were measured for samples containing 1 wt. % CfSWCNT and nylon. The Young’s modulus, stiffness and fracture energy of the samples are 10.65 GPa, 1482.12 N/mm, and 644 J/m2 respectively. These values are comparable to those of the cortical bone. Further increase of the CfSWCNT content results to a decreased fracture toughness and tensile strength and formation of a secondary phase. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2016. / FAU Electronic Theses and Dissertations Collection

Artificial tissue expansion is required to generate new skin prior to reconstructive surgery, in order to compensate for a deficit of healthy tissue. Hydrogel tissue expanders, which expand anisotropically, show great promise in overcoming clinical limitations in the field, thus allowing the technique to be used in a wider range of surgeries. These devices consist of pellets of dry poly(methyl methacrylate-co-vinylpyrrolidone), compressed into discs through a hot compression moulding process. However, a number of significant problems still exist in these devices, and this thesis aims to address these issues. To date, there has been a lack of investigation of the factors governing the behaviour of anisotropic swelling. For this reason, a range of different compression ratios have been investigated, with particular focus on the relationship between the material flow during compression and the swelling behaviour of the resulting device. It was found that samples of the same initial size expand to the same reference swelling dimensions, regardless of compression ratio. During hot pressing, the material flow was found to be governed by slip-stick behaviour at the interface between the hot press and the device, affecting the properties and swelling behaviour of the devices. Based on these findings, devices were developed which could expand from a disc into a non-prismatic shape (dome or wedge). Such devices could reduce complication rates and allow the growth of new tissue with anisotropic resting tension. The devices were tested in a small in vivo trial, where it was shown that there were no adverse effects on the tissue produced, and that the shape of the expander (dome) was retained. As devices are being produced for medical use, understanding the effect of sterilization by &gamma;-irradiation is essential, but to date this has been overlooked in the literature. It was found that γ-irradiation caused an increase in cross-linking in the P(MMA-co-NVP). Whilst this produced little change in swelling behaviour for isotropic devices, in the case of anisotropic devices it caused a change in the shape of expansion, reducing the area of new skin which could be generated by the device. It was found that by reducing the concentration of impurities (residual molecules from the polymer synthesis) the impact of &gamma;-irradiation could be greatly reduced. Finally, controlling the rate of expansion is essential in order to avoid clinical complications. In order to control the rate of expansion, particularly during the initial period of swelling, semi-permeable PDMS coatings were applied to the compressed devices. Coatings of thickness greater than 0.375mm were found to effectively control the rate of swelling, for both cylindrical and non-prismatic shapes. As the coating thickness increased, the maximum swelling size decreased. However, it has been shown that change in height (the parameter which governs the area of skin produced) is affected less than the change in mass or diameter.

Cam-type Femoro-Acetabular Impingement (FAI) is a common cause of hip osteoarthritis (OA). In this condition a bony abnormality at the head-neck junction of the femoral head, called the “cam”, abuts against the acetabulum causing labral damage and articular cartilage delamination, which in turn may lead to progressive degeneration and OA. The understanding of the damage mechanism is currently at a conceptual level. The aim of the thesis is to develop a more detailed understanding of the underlying mechanism so as to improve methods of detection and treatment of cam-type FAI and thus to help prevent hip OA. A geometric-kinematic model combining hip joint motion and hip joint geometry was cre- ated to determine what motions, activities or cam shapes give rise to cam-type impingement, which was quantified by the proximity of the acetabular and femoral bony surfaces. Five normal subjects and five symptomatic cam-type FAI patients were modelled. The FAI patients experienced early impingement during the impingement test but did not have impingement during common functional activities. The early impingement was possibly due to the larger coverage and protrusion of their cams and the smaller overall proximity in their hip joints. A 2D finite element (FE) model was created to simulate cam-type FAI. As idealised 2D rectangular and circular geometries did not reproduce the damage seen clinically, subject- specific geometry, loads, and motions were introduced. Under some circumstances, as the cam entered the hip joint, large shear strains developed near the cartilage-bone interface of the acetabulum which would result in cartilage delamination. In vitro experiments were undertaken to validate the FE model and verify the damage mech- anism by which cam-type FAI leads to cartilage delamination. Porcine cartilage-bone samples were loaded under conditions similar to those generated by a cam (shear and compression). A validation FE model was created that used the same material and contact representations and analysis framework as the impingement FE model but mimicked the experimental setup. The cartilage shear strains assessed with a video-based method were similar to predicted FE results. In vitro damage experiments demonstrated that delamination can be caused by repetitive shear and compressive loading that lead to large shear strains near the cartilage-bone interface. The impingement FE model was used to further explore the effect of cam anatomy. In hips with low clearance, cams with large protrusions (75% hip joint clearance) would not enter into the hip joint, but caused high shear strains in the labrum, which would result in labral tears. A narrower cam caused damage to the labral tip, whereas a wider cam caused damage to the labral-bone junction. In contrast, cams with small protrusion (25% hip joint clearance) were able to enter the joint and caused damage at the articular cartilage-bone interface, which would result in cartilage delamination. The wider the cam, the further into the hip joint the damage was initiated. The FE model was used to explore the effect of different labral anatomy and of reshaping surgery. A labrum connected to the articular cartilage resulted in shear strains of up to five times greater in the articular cartilage and labrum compared to an unconnected labrum and was more likely to cause articular cartilage delamination. For a cam that damages the articular cartilage, surgical removal of the cam reduced shear strains. For a cam that abuts the labrum, surgical removal of the cam eliminated labral abutment and increased the range of motion of the hip, but resulted in greater shear strains in the articular cartilage. It is not known whether these shear strains are normal or could possibly be damaging. Also, reshaping the head to be spherical resulted in slightly reduced shear strains in the articular cartilage compared to the current surgical practice of cutting deeper into the femoral head when removing the cam. This study has, for the first time, using a validated FE model demonstrated the mechanism by which a cam can cause articular cartilage delamination and labral tearing. Further analysis using the geometric and FE model should help identify cam deformities that would be likely to cause OA and the best way to treat them surgically so as to prevent OA.