Polyurethane End-Capped by Tetramethylpyrazine-Nitrone for Promoting Endothelialization Under Oxidative Stress.

Thrombus and restenosis are two main factors that cause the failure of vascular implants. Constructing a functional and confluent layer of endothelial cells (ECs) is considered an ideal method to prevent these problems. However, oxidative stress induced by the disease and implantation can damage ECs and hinder the endothelialization of implants. Thus, developing biomaterials that can protect ECs adhesion and proliferation from oxidative stress is urgently needed for the rapid endothelialization of vascular implants. In this work, a novel polyurethane (PU-TBN) is synthesized by employing tetramethylpyrazine-nitrone (TBN) as end-group to endow polymers with dual functions of antioxidant activity and promoting endothelialization. Common PU without TBN is also prepared to be control. Compared to PU, PU-TBN significantly promotes human umbilical vein endothelial cells (HUVECs) adhesion and proliferation, where cells spread well and a confluent endothelial layer is formed. PU-TBN also shows obvious free radical scavenging activity, and thus effectively attenuates oxidative stress to protect HUVECs from oxidative apoptosis. Moreover, PU-TBN exhibits enhanced antiplatelets effect, excellent biocompatibility, and similar mechanical properties to PU. These characteristics can endow PU-TBN with great potential to be used as vascular implants or coatings of other materials for rapid endothelialization under complex oxidative stress environment.

Selenium-containing polyurethane with elevated catalytic stability for sustained nitric oxide release.

Stable and controllable nitric oxide (NO) release at the physiological level from biomedical materials remains a challenge for NO-based therapy. NO-generating polymers have great potential to achieve this goal because they can catalytically decompose endogenous S-nitrosothiols (RSNOs) into NO. However, the current catalytic surfaces based on such polymers often suffer from loss of catalytic sites, which can influence the stability of NO release in their long-term application. In this work, we proposed a novel strategy to enhance the catalytic stability of NO-catalytic materials by incorporating catalytic sites into the polymer backbone. Selenium-containing polyurethane (PU-Se) was synthesized by using the catalyst 2,2'-diselenodiethanol (SeDO) as the chain extender. A series of PU/PU-Se blend films were prepared to investigate the effect of PU-Se content on the catalytic properties. The blend films exhibited excellent catalytic activity, and also showed outstanding catalytic stability in comparison with PU coated by diselenide/dopamine (PU-PDA-Se). Among these blend films, PU-Se-10 exhibited a stable NO release rate of 5.05 × 10-10 mol cm-2 min-1 after exposure to PBS buffer for 30 days. Moreover, the PU/PU-Se films exhibited decreased platelet activation/adhesion, low hemolysis ratio, excellent biocompatibility, and similar mechanical properties to PU. It is expected that the newly designed PU-Se has great potential in generating stable NO release at the physiological level for the long-term application of blood-contacting medical devices.