Muñoz-Sánchez Silvia, Gong Jue, de la Mata Francisco Javier, Gillies Elizabeth R, García-Gallego Sandra
Department of Organic and Inorganic Chemistry and Research Institute in Chemistry ″Andrés M. Del Río″ (IQAR), University of Alcalá, 28805 Madrid, Spain.
Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Chem Mater. 2025 Jul 18;37(15):5814-5824. doi: 10.1021/acs.chemmater.5c01006. eCollection 2025 Aug 12.
In the biomedical field, the design of materials with controlled degradation is highly desired. Herein, we present a family of dendritic hydrogels accomplished through copper-assisted azide-alkyne cycloaddition click reaction between dendritic cross-linkers and complementary linear polymers. As cross-linkers, an innovative family of bifunctional carbosilane dendrimers was designed for this purpose, bearing multiple alkyne groups available for network formation as well as pendant hydroxyl groups for postfunctionalization. Additionally, different azide-pendant polymers were employed, including difunctional poly-(ethylene glycol) with cleavable and noncleavable nature, as well as poly-(ethyl glyoxylate) with and without self-immolative behavior. The rational design of the dendritic hydrogels, through the careful selection of these two components, enabled an accurate manipulation of properties like swelling and mechanical properties. The network degradation could be tuned from a few hours, for a traditional ester-cleavable dendritic hydrogel, to several days under pH-controlled conditions, for the self-immolative hydrogel (SIH). The impact of network degradation on the release of curcumin as a model drug was also confirmed. This work showcased the potential of dendritic SIHs for biomedical applications.
在生物医学领域，人们非常希望设计出具有可控降解性的材料。在此，我们展示了一族通过树枝状交联剂与互补线性聚合物之间的铜辅助叠氮-炔环加成点击反应制备的树枝状水凝胶。作为交联剂，为此设计了一族创新的双功能碳硅烷树枝状大分子，其带有多个可用于形成网络的炔基以及用于后功能化的侧链羟基。此外，还使用了不同的叠氮侧基聚合物，包括具有可裂解和不可裂解性质的双功能聚乙二醇，以及具有和不具有自牺牲行为的聚乙醛酸乙酯。通过仔细选择这两种组分对树枝状水凝胶进行合理设计，能够精确调控诸如溶胀和机械性能等性质。网络降解可以从传统的可酯裂解树枝状水凝胶的几小时，调节到在pH控制条件下自牺牲水凝胶（SIH）的几天。还证实了网络降解对作为模型药物的姜黄素释放的影响。这项工作展示了树枝状自牺牲水凝胶在生物医学应用中的潜力。
