标题： 通过关联交换在超分子水凝胶中解耦动力学和交联稳定性 显示英文标题

标题： Decoupling dynamics and crosslink stability in supramolecular hydrogels using associative exchange

摘要： 具有机械坚固性和动态可重构性的水凝胶的设计仍然是一个基本挑战，因为增加交联解离速率会损害网络完整性。 这一限制通过在基于DNA的超分子水凝胶中引入关联性交联交换得到解决，从而实现了网络弛豫行为与交联稳定性的解耦。 这些水凝胶由酶合成的单链DNA构建，通过互补区域之间的杂交自组装形成。 这些交联可以通过解离熔化或关联链置换反应重新组织，产生具有可调弛豫时间尺度的网络，跨度超过三个数量级。 流变测量和热力学建模证实，关联交换促进了有效的应力耗散，而不会降低断裂强度或热稳定性。 相反，解离系统本质上会以机械强度的减弱为代价来增加动态性。 这种解耦是通过由样品组成控制的催化重组途径实现的，与交联强度无关。 这些发现确立了重组机制作为工程结合韧性和响应性的自适应软材料的关键设计参数。 显示英文摘要

摘要： The design of hydrogels that combine mechanical robustness with dynamic reconfigurability remains a fundamental challenge, as increasing crosslink dissociation rates compromise network integrity. This limitation is addressed through the incorporation of an associative crosslink exchange into DNA-based supramolecular hydrogels, enabling the decoupling of network relaxation behavior from crosslink stability. The hydrogels are constructed from enzyme-synthesized single-stranded DNA that self-assembles via hybridization between complementary domains. These crosslinks can reorganize through dissociative melting or associative strand displacement reaction, yielding networks with tunable relaxation timescales spanning over three orders of magnitude. Rheological measurements and thermodynamic modeling confirm that associative exchange facilitates efficient stress dissipation without diminishing rupture strength or thermal stability. In contrast, dissociative systems inherently trade increased dynamics with mechanical weakening. This decoupling is achieved through the implementation of a catalytic reorganization pathway governed by the composition of the sample, independently of crosslink strength. These findings establish the mechanism of reorganization as a key design parameter for engineering adaptive soft materials that combine resilience and responsiveness.