Bridging Rigidity and Flexibility: Modulation of Supramolecular Hydrogels by Metal Complexation,Macromolecular Rapid Communications

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Bridging Rigidity and Flexibility: Modulation of Supramolecular Hydrogels by Metal Complexation
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2021-09-10 , DOI: 10.1002/marc.202100473
Oliver S Stach ₁ , Katharina Breul _{1,

2} , Christian M Berač _{1,

2} , Moritz Urschbach ₁ , Sebastian Seiffert _{1,

2} , Pol Besenius _{1,

2}

Affiliation

The combination of complementary, noncovalent interactions is a key principle for the design of multistimuli responsive hydrogels. In this work, an amphiphilic peptide, supramacromolecular hydrogelator which combines metal-ligand coordination induced gelation and thermoresponsive toughening is reported. Following a modular approach, the incorporation of the triphenylalanine sequence FFF into a structural (C₃^EG) and a terpyridine-functionalized (C₃^Tpy) C₃-symmetric monomer enables their statistical copolymerization into self-assembled, 1D nanorods in water, as investigated by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). In the presence of a terpyridine functionalized telechelic polyethylene glycol (PEG) cross-linker, complex formation upon addition of different transition metal ions (Fe²⁺, Zn²⁺, Ni²⁺) induces the formation of soft, reversible hydrogels at a solid weight content of 1 wt% as observed by linear shear rheology. The viscoelastic behavior of Fe²⁺ and Zn²⁺ cross-linked hydrogels are basically identical, while the most kinetically inert Ni²⁺ coordinative bond leads to significantly weaker hydrogels, suggesting that the most dynamic rather than the most thermodynamically stable interaction supports the formation of robust and responsive hydrogel materials.

中文翻译：

桥接刚性和灵活性：通过金属络合调节超分子水凝胶

互补、非共价相互作用的结合是设计多刺激响应水凝胶的关键原则。在这项工作中，报道了一种结合金属配体配位诱导凝胶化和热响应增韧的两亲性肽超大分子水凝胶剂。按照模块化方法，将三苯丙氨酸序列 FFF 并入结构 ( C ₃^EG ) 和三联吡啶官能化 ( C ₃^Tpy ) C ₃通过圆二色性 (CD) 光谱学和透射电子显微镜 (TEM) 研究，-对称单体使它们能够在水中统计共聚成自组装的一维纳米棒。在存在三联吡啶官能化遥爪聚乙二醇 (PEG) 交联剂的情况下，通过添加不同的过渡金属离子（Fe ²⁺、Zn ²⁺、Ni ²⁺）形成复合物，从而诱导在固体中形成柔软、可逆的水凝胶通过线性剪切流变学观察到的重量含量为 1 wt%。^{Fe 2+}和Zn ²⁺交联水凝胶的粘弹性行为基本相同，而动力学惰性最强的Ni ²⁺配位键导致水凝胶显着变弱，这表明最动态而不是最热力学稳定的相互作用支持形成坚固且响应迅速的水凝胶材料。

更新日期：2021-09-10

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