Rial-Hermida M Isabel, Costa Dora C S, Jiang Lan, Rodrigues João M M, Ito Kohzo, Mano João F
CICECO-Aveiro Institute of Materials, Chemistry Department, University of Aveiro, 3810-193 Aveiro, Portugal.
Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, Kashiwa-shi 277-8561, Chiba, Japan.
Gels. 2023 Jan 19;9(2):85. doi: 10.3390/gels9020085.
Adaptable hydrogels have been used in the biomedical field to address several pathologies, especially those regarding tissue defects. Here, we describe unprecedented catechol-like functionalized polyrotaxane (PR) polymers able to form hydrogels. PR were functionalized with the incorporation of hydroxypyridinone (HOPO) moieties into the polymer backbone, with a degree of substitution from 4 to 22%, depending on the PR type. The hydrogels form through the functionalized supramolecular systems when in contact with a Fe(III) solution. Despite the hydrogel formation being at physiological pH (7.4), the HOPO derivatives are extremely resistant to oxidation, unlike common catechols; consequently, they prevent the formation of quinones, which can lead to irreversible bounds within the matrix. The resulting hydrogels demonstrated properties lead to unique hydrogels with improved mechanical behavior obtained by metallic coordination crosslinking, due to the synergies of the sliding-ring PR and the non-covalent (reversible) catechol analogues. Following this strategy, we successfully developed innovative, cytocompatible, oxidative-resistant, and reversible crosslinked hydrogels, with the potential of being used as structural self-materials for a variety of applications, including in the biomedical field.
适应性水凝胶已被应用于生物医学领域，以解决多种病理问题，尤其是那些与组织缺损相关的问题。在此，我们描述了一种前所未有的能够形成水凝胶的类儿茶酚功能化聚轮烷（PR）聚合物。通过将羟基吡啶酮（HOPO）部分掺入聚合物主链对PR进行功能化，取代度为4%至22%，具体取决于PR的类型。当与Fe(III)溶液接触时，这些功能化超分子体系会形成水凝胶。尽管水凝胶在生理pH值（7.4）下形成，但与普通儿茶酚不同，HOPO衍生物具有极强的抗氧化性；因此，它们可防止醌的形成，而醌会导致基质内形成不可逆的键。由于滑动环PR和非共价（可逆）儿茶酚类似物的协同作用，所得水凝胶表现出通过金属配位交联获得的具有独特机械性能的独特水凝胶特性。按照这一策略，我们成功开发出了创新的、具有细胞相容性、抗氧化且可逆交联的水凝胶，有潜力用作多种应用的结构自材料，包括生物医学领域。
