Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Department of Chemistry, University of Liège, Allée du 6 août 13, Building B6a, 4000 Liège, Belgium.
GIGA Cardiovascular Sciences - Laboratory of Cardiology, University of Liège, Avenue de l'Hôpital 11, Quartier Hôpital, Building B34, 4000 Liège, Belgium.
Biomacromolecules. 2024 Mar 11;25(3):1810-1824. doi: 10.1021/acs.biomac.3c01261. Epub 2024 Feb 15.
Polyurethanes (PUs) have adjustable mechanical properties, making them suitable for a wide range of applications, including in the biomedical field. Historically, these PUs have been synthesized from isocyanates, which are toxic compounds to handle. This has encouraged the search for safer and more environmentally friendly synthetic routes, leading today to the production of nonisocyanate polyurethanes (NIPUs). Among these NIPUs, polyhydroxyurethanes (PHUs) bear additional hydroxyl groups, which are particularly attractive for derivatizing and adjusting their physicochemical properties. In this paper, polyether-based NIPU elastomers with variable stiffness are designed by functionalizing the hydroxyl groups of a poly(propylene glycol)-PHU by a cyclic carbonate carrying a pendant unsaturation, enabling them to be post-photo-cross-linked with polythiols (thiol-ene). Elastomers with remarkable mechanical properties whose stiffness can be adjusted are obtained. Thanks to the unique viscous properties of these PHU derivatives and their short gel times observed by rheology experiments, formulations for light-based three-dimensional (3D) printing have been developed. Objects were 3D-printed by digital light processing with a resolution down to the micrometer scale, demonstrating their ability to target various designs of prime importance for personalized medicine. biocompatibility tests have confirmed the noncytotoxicity of these materials for human fibroblasts. hemocompatibility tests have revealed that they do not induce hemolytic effects, they do not increase platelet adhesion, nor activate coagulation, demonstrating their potential for future applications in the cardiovascular field.
聚氨基甲酸酯（PUs）具有可调节的机械性能，使其适用于广泛的应用领域，包括生物医学领域。历史上，这些 PUs 是由异氰酸酯合成的，而这些异氰酸酯化合物在处理时具有毒性。这促使人们寻找更安全、更环保的合成途径，最终导致了非异氰酸酯聚氨基甲酸酯（NIPUs）的生产。在这些 NIPUs 中，聚羟基脲（PHUs）具有额外的羟基，这对于衍生化和调整其物理化学性质特别有吸引力。在本文中，通过在带有支链不饱和基团的环状碳酸酯上对聚（丙二醇）-PHU 的羟基进行功能化，设计了具有可变刚度的基于聚醚的 NIPU 弹性体，使其能够与多硫醇（硫醇-烯）进行后光交联。得到了具有显著机械性能且可调节其刚度的弹性体。由于这些 PHU 衍生物具有独特的粘性特性及其流变学实验观察到的较短凝胶时间，因此开发了用于基于光的三维（3D）打印的配方。通过数字光处理进行了 3D 打印，分辨率可低至微米级，展示了它们针对个性化医学中非常重要的各种设计的能力。生物相容性测试证实了这些材料对人成纤维细胞无细胞毒性。血液相容性测试表明，它们不会引起溶血作用，不会增加血小板黏附，也不会激活凝血，这表明它们在心血管领域的未来应用中有潜力。
