Yang Ruibo, Liu Wenkai, Wang Ao, Deng Xiaobo, Feng Yuan, Zhang Qiao, Li Zhen, Luo Feng, Li Jiehua, Tan Hong
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Med-X Center for Materials, Sichuan University, Chengdu 610065, China.
Department of Neurosurgery, West China Hospital, Sichuan University, Chengdu 610065, China.
J Mater Chem B. 2022 Nov 9;10(43):8918-8930. doi: 10.1039/d2tb01681h.
Shape memory polymers (SMPs) with multiple functionalities have great potential in implantable biomedical devices, especially vascular stents. However, stents made of SMPs are generally faced with the problem of insufficient radial support due to the sharp decline of the modulus after shape recovery. Therefore, it is necessary to improve the modulus of SMPs after opening the narrow part by other means. In this study, the novel SMPs available for vascular stents were developed with impressive water-induced stiffening when shape recovered in a physiological environment. Herein, a series of shape memory polyurethanes (SMPUs) containing full hard segments on the main chains and bearing hydrophilic tertiary amine soft segments on the side chains were synthesized. When immersed in water, the soft segments were dramatically separated from the hard segments, which were aggregated more to form densely packed hard domains with stronger hydrogen bonding and higher crystallinity. Both Young's modulus and the shape recovery ratio were thus promoted due to the segmental rearrangement in water. At the same time, hydrophilic side chains migrated to the surface driven by the segmental rearrangement in water, which promotes the adhesion and growth of vascular endothelial cells and inhibits the activation of the coagulation system. The ingenious structural design provided SMPUs with adequate mechanical strength and hemocompatibility to qualify for potential applications in self-expanding vascular stents.
具有多种功能的形状记忆聚合物(SMP)在可植入生物医学装置尤其是血管支架方面具有巨大潜力。然而,由SMP制成的支架通常面临形状恢复后模量急剧下降导致径向支撑不足的问题。因此,有必要通过其他方式提高SMP在狭窄部分打开后的模量。在本研究中,开发了可用于血管支架的新型SMP,其在生理环境中形状恢复时具有令人印象深刻的水致硬化性能。在此,合成了一系列主链上含有全硬段且侧链带有亲水性叔胺软段的形状记忆聚氨酯(SMPU)。当浸入水中时,软段与硬段显著分离,硬段进一步聚集形成具有更强氢键和更高结晶度的紧密堆积硬区域。由于在水中的链段重排,杨氏模量和形状恢复率均得到提高。同时,亲水性侧链在水中链段重排的驱动下迁移到表面,这促进了血管内皮细胞的粘附和生长,并抑制了凝血系统的激活。这种巧妙的结构设计为SMPU提供了足够的机械强度和血液相容性,使其有资格在自膨胀血管支架中潜在应用。