Technical University of Munich, Germany, TUM School of Natural Sciences, Department of Chemistry, WACKER-Chair of Macromolecular Chemistry, Lichtenbergstraße 4, 85748 Garching, Germany.
Technical University of Munich, Germany, TUM School of Engineering and Design, Department of Mechanical Engineering, Chair of Medical Materials and Implants, Munich Institute of Biomedical Engineering, Munich Institute of Integrated Materials, Energy and Process Engineering, Boltzmannstraße 15, 85748 Garching, Germany.
ACS Appl Mater Interfaces. 2024 Oct 30;16(43):58135-58147. doi: 10.1021/acsami.4c07860. Epub 2024 Oct 15.
Herein, the synthesis, characterization, and application of a novel synthetic hydrogel based on the photoinitiated cross-linking of poly(vinylphosphonates) is presented. First, statistical copolymers with adjustable ratios of the monomers diallyl vinylphosphonate (DAlVP) and diethyl vinylphosphonate (DEVP), as well as different molecular weights, were obtained via rare earth metal-mediated group-transfer polymerization (REM-GTP) while maintaining narrow polydispersities. The copolymers were cross-linked by applying photoinitiated thiol-ene click chemistry (λ = 365 nm). The network formation was monitored via oscillatory rheology coupled with UV-irradiation, revealing the high spatiotemporal control of the reaction. Moreover, the equilibrium storage moduli of poly(vinylphosphonate)-based hydrogels increased with a growing number of DAlVP units and upon application of a different cross-linker, which was additionally confirmed by nanoindentation experiments. In contrast, the water uptake of hydrogels decreased with higher DAlVP amounts in the corresponding hydrogels due to lower chain mobility and an overall increase in the hydrophobicity of the samples. Upon successful functionalization of P(DEVP--DAlVP) copolymers with sodium 3-mercaptopropane-1-sulfonate, as indicated via H DOSY NMR, the respective cross-linked materials displayed a remarkable increase in the water uptake; thus, presenting highly hydrophilic gels with an apparent interplay between water uptake, cross-linking density, and functionalization degree. Finally, the purified hydrogels showed cytocompatibility and enabled cell adhesion of human umbilical artery smooth muscle cells (HUASMCs) after direct seeding. The materials further allowed the adhesion and growth of an endothelial layer, triggered no pro-inflammatory response as evidenced by cytokine release of M0 macrophages, and exhibited antibacterial properties toward and .
本文介绍了一种基于聚（膦酸酯）的光引发交联的新型合成水凝胶的合成、表征和应用。首先，通过稀土金属介导的基团转移聚合（REM-GTP）获得了具有可调节单体比例的二烯丙基乙烯基磷酸酯（DAlVP）和二乙基乙烯基磷酸酯（DEVP）以及不同分子量的统计共聚物，同时保持了较窄的多分散性。通过应用光引发的硫醇-烯点击化学（λ = 365nm）交联共聚物。通过与紫外辐射耦合的动态流变学监测网络形成，揭示了反应的高时空控制。此外，基于聚（膦酸酯）的水凝胶的平衡储能模量随着 DAlVP 单元数量的增加而增加，并且在应用不同的交联剂时也会增加，这通过纳米压痕实验得到了进一步证实。相比之下，由于链迁移率降低和样品整体疏水性增加，水凝胶的吸水率随着相应水凝胶中 DAlVP 含量的增加而降低。在成功地将 P(DEVP-DAlVP)共聚物与 3-巯基丙磺酸钠进行功能化后，如通过 H DOSY NMR 所示，相应的交联材料的吸水率显著增加；因此，呈现出高亲水性凝胶，其具有吸水率、交联密度和功能化程度之间的明显相互作用。最后，纯化的水凝胶表现出细胞相容性，并允许人脐动脉平滑肌细胞（HUASMCs）直接接种后的细胞黏附。这些材料进一步允许内皮层的黏附和生长，如 M0 巨噬细胞的细胞因子释放所证明的那样，不会引发促炎反应，并且对 和 具有抗菌性能。
