Star-Polymer-DNA Gels Showing Highly Predictable and Tunable Mechanical Responses
Star-Polymer-DNA Gels Showing Highly Predictable and Tunable Mechanical Responses
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星形聚合物 DNA 凝胶表现出高度可预测和可调节的机械响应
DOI：
10.1002/adma.202108818
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发表时间：
2022
影响因子：
29.4
通讯作者：
Li Xiang
中科院分区：
文献类型：
--
作者：
Ohira Masashi;Katashima Takuya;Naito Mitsuru;Aoki Daisuke;Yoshikawa Yusuke;Iwase Hiroki;Takata Shin‐ichi;Miyata Kanjiro;Chung Ung‐il;Sakai Takamasa;Shibayama Mitsuhiro;Li Xiang
动态交联凝胶对于需要依赖时间的机械响应的应用来说是很有吸引力的材料。DNA双链化合物是构建这种凝胶的理想交联剂，因为它们具有良好的序列可寻址性和灵活的键能可调性。然而，大多数DNA凝胶的机械反应是复杂和不可预测的。在这里，通过使用一对星形聚合物- DNA前体和预模拟的显示两态转变的DNA序列，证明了具有高度均匀凝胶网络和良好可预测力学行为的DNA凝胶。DNA凝胶的熔融曲线分析表明，DNA交联剂的热力学势与DNA计算器的预模拟值具有良好的对应关系。应力松弛试验和解离动力学测量表明，DNA凝胶的宏观松弛时间大约等于DNA交联剂的寿命，从0.1-2000秒超过4个数量级。此外，一系列耐久性测试发现，DNA凝胶在反复温度和机械刺激后具有无迟滞性和自愈性。这些结果证明了星形聚合物- dna前体在构建具有可预测和可调粘弹性特性的凝胶方面的巨大潜力，适用于应力响应细胞外基质、可注射固体和软机器人等应用。
Dynamically crosslinked gels are appealing materials for applications that require time‐dependent mechanical responses. DNA duplexes are ideal crosslinkers for building such gels because of their excellent sequence addressability and flexible tunability in bond energy. However, the mechanical responses of most DNA gels are complicated and unpredictable. Here, a DNA gel with a highly homogeneous gel network and well predictable mechanical behaviors is demonstrated by using a pair of star‐polymer–DNA precursors with presimulated DNA sequences showing the two‐state transition. The melting curve analysis of the DNA gels reveals the good correspondence between the thermodynamic potentials of the DNA crosslinkers and the presimulated values by DNA calculators. Stress‐relaxation tests and dissociation kinetics measurements show that the macroscopic relaxation time of the DNA gels is approximately equal to the lifetime of the DNA crosslinkers over 4 orders of magnitude from 0.1–2000 s. Furthermore, a series of durability tests find the DNA gels are hysteresis‐less and self‐healable after the applications of repeated temperature and mechanical stimuli. These results demonstrate the great potential of star‐polymer–DNA precursors for building gels with predictable and tunable viscoelastic properties, suitable for applications such as stress‐response extracellular matrices, injectable solids, and soft robotics.