RESUMEN
Improved living conditions have led to an increase in life expectancy worldwide. However, as people age, the risk of vascular disease tends to increase due to the accumulation and buildup of plaque in arteries. Vascular stents are used to keep blood vessels open. Biodegradable stents are designed to provide a temporary support vessel that gradually degrades and is absorbed by the body, leaving behind healed blood vessels. However, biodegradable metals can suffer from reduced mechanical strength and/or inflammatory response, both of which can affect the rate of corrosion. Therefore, it is essential to achieve a controlled and predictable degradation rate. Here, we demonstrate that the corrosion resistance of biodegradable Zn surfaces is improved by electroless deposition of zinc hydroxystannate followed by UV-grafting with silicone oil (PDMS). Potentiodynamic polarization, electrochemical impedance spectroscopy, respiratory kinetic measurements, and long-term immersion in three simulated body fluids were applied. Although zinc hydroxystannate improves the corrosion resistance of Zn to some extent, it introduces a high surface area with hydroxyl units used to UV-graft PDMS molecules. Our results demonstrate that hydrophobic PDMS causes a 3-fold reduction in corrosion of Zn-based materials in biological environments and reduces cytotoxicity through the uncontrolled release of Zn ions.
RESUMEN
Utilizing ionizing radiation for in situ studies in liquid media enables unique insights into nanostructure formation dynamics. As radiolysis interferes with observations, kinetic simulations are employed to understand and exploit beam-liquid interactions. By introducing an intuitive tool to simulate arbitrary kinetic models for radiation chemistry, it is demonstrated that these models provide a holistic understanding of reaction mechanisms. This is shown for irradiated HAuCl4 solutions allowing for quantitative prediction and tailoring of redox processes in liquid-phase transmission electron microscopy (LP-TEM). Moreover, it is demonstrated that kinetic modeling of radiation chemistry is applicable to investigations utilizing X-rays such as X-ray diffraction (XRD). This emphasizes that beam-sample interactions must be considered during XRD in liquid media and shows that reaction kinetics do not provide a threshold dose rate for gold nucleation relevant to LP-TEM and XRD. Furthermore, it is unveiled that oxidative etching of gold nanoparticles depends on both, precursor concentration, and dose rate. This dependency is exploited to probe the electron beam-induced shift in Gibbs free energy landscape by analyzing critical radii of gold nanoparticles.