Hemocompatible Surfaces Through Surface-attached Hydrogel Coatings and their Functional Stability in a Medical Environment.

Blood compatible materials are a well-researched scientific field as such materials are required in a wide range of applications, for example, in heart-lung machines or ventricular assist devices. Surfaces coated with certain surface-bound neutral, water-swellable polymer networks have the ability to repel cells such as platelets and exhibit a significantly improved hemocompatibility. In this study, we investigate the interaction of platelets from whole blood with surfaces coated with photochemically generated surface-attached polymer networks based on polydimethyl acrylamide. As substrates medical-grade polyurethanes are used, and the networks are formed and attached to the substrate surfaces through C-H insertion reactions. The hydrogel-coated substrates are perfused with blood for extended periods of time. We show that the polymer coating prevents the adhesion of cells even at longer times of blood contact, regardless of the thickness of the coating employed. The surfaces can be sterilized following a standard autoclave procedure without any loss of function. Additionally, it is shown that the samples can be stored at least for 3 months under varying ambient conditions while retaining their functionality. The excellent blood compatibility, the possibility to coat even rather inert polymeric materials and the ability to handle the materials in an environment typical for a medical application make such coatings a promising candidate for future hemocompatible devices.

UV- and Thermally-Active Bifunctional Gelators Create Surface-Anchored Polymer Networks.

A versatile one-step synthesis of surface-attached polymer networks using small bifunctional gelators (SBG), namely 4-azidosulfonylphenethyltrimethoxysilane (4-ASPTMS) and 6-azidosulfonylhexyltriethoxysilane (6-ASHTES) is reported. A thin layer (≈200 nm) of a mixture comprising ≈90% precursor polymer and 10% of 4-ASPTMS or 10% 6-ASHTES on a silicon wafer is deposited. Upon UV irradiation (≈l-254 nm) or annealing (>100 °C) layers, sulfonyl azides (SAz) release nitrogen by forming singlet and triplet nitrenes that concurrently react with any C─H bond in the vicinity resulting in sulfonamide crosslinks. Condensation among tri-alkoxy groups (i.e., methoxy or ethoxy) in bulk connects the SBG units, which completes the crosslinking. Concurrently, when such functionalities react with hydroxyl groups at the surface, which enable the covalent attachment of the crosslinked polymer chains. A systematic investigation on reaction mechanism and gel formation using spectroscopic ellipsometry (SE) and Fourier-transform infrared spectroscopy in the attenuated total reflection mode (FTIR-ATR) is performed. Analogous thermally initiated gelation for both 4-ASPTMS and 6-ASHTES is found. The 6-ASHTES is UV inactive at ≈l-254 nm, while the 4-ASPTMS is active and forms gels. The difference is attributed to the aromatic nature of 4-ASPTMS that absorb UV light at ≈l-254 nm due to π-π* transition.