Rovers Maritza M, Rogkoti Theodora, Bakker Bram K, Bakal Kalpit J, van Genderen Marcel H P, Salmeron-Sanchez Manuel, Dankers Patricia Y W
Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, Eindhoven, 5600 MB, The Netherlands.
Department of Biomedical Engineering, Laboratory of Chemical Biology, Eindhoven University of Technology, P.O. Box 513, Eindhoven, 5600 MB, The Netherlands.
Adv Mater. 2024 Dec;36(50):e2405868. doi: 10.1002/adma.202405868. Epub 2024 Oct 27.
Microgels show advantages over bulk hydrogels due to convenient control over microgel size and composition, and the ability to use microgels to modularly construct larger hierarchical scaffold hydrogel materials. Here, supramolecular chemistry is used to formulate supramolecular polymer, dynamic microgels solely held together by non-covalent interactions. Four-fold hydrogen bonding ureido-pyrimidinone (UPy) monomers with different functionalities are applied to precisely tune microgel properties in a modular way, via variations in monomer concentration, bifunctional crosslinker ratio, and the incorporation of supramolecular dyes and peptides. Functionalization with a bioactive supramolecular cell-adhesive peptide induced selectivity of cells toward the bioactive microgels over non-active, non-functionalized versions. Importantly, the supramolecular microgels can also be applied as microscale building blocks into supramolecular bulk macrogels with tunable dynamic behavior: a robust and weak macrogel, where the micro- and macrogels are composed of similar molecular building blocks. In a robust macrogel, microgels act as modular micro-building blocks, introducing multi-compartmentalization, while in a weak macrogel, microgels reinforce and enhance mechanical properties. This work demonstrates the potential to modularly engineer higher-length-scale structures using small molecule supramolecular monomers, wherein microgels serve as versatile and modular micro-building units.
微凝胶相比于块状水凝胶具有优势，这是因为可以方便地控制微凝胶的尺寸和组成，并且能够使用微凝胶以模块化方式构建更大的分级支架水凝胶材料。在此，超分子化学被用于制备超分子聚合物，即仅通过非共价相互作用结合在一起的动态微凝胶。具有不同功能的四重氢键脲嘧啶酮（UPy）单体通过改变单体浓度、双功能交联剂比例以及引入超分子染料和肽，以模块化方式精确调节微凝胶的性质。用生物活性超分子细胞粘附肽进行功能化处理，可诱导细胞对生物活性微凝胶的选择性高于非活性、未功能化的微凝胶。重要的是，超分子微凝胶还可以作为微观构建单元应用于具有可调动态行为的超分子块状大凝胶中：一种强凝胶和弱凝胶，其中微凝胶和大凝胶由相似的分子构建单元组成。在强凝胶中，微凝胶充当模块化微观构建块，引入多室结构，而在弱凝胶中，微凝胶增强并改善机械性能。这项工作展示了使用小分子超分子单体模块化设计更高长度尺度结构的潜力，其中微凝胶作为通用且模块化的微观构建单元。
