Oxidatively Responsive Chain Extension to Entangle Engineered Protein Hydrogels.
Oxidatively Responsive Chain Extension to Entangle Engineered Protein Hydrogels.
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DOI：
10.1021/ma401684w
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发表时间：
2014-01-28
期刊：
影响因子：
5.5
通讯作者：
Olsen, Bradley D.
中科院分区：
文献类型：
--
作者：
Tang, Shengchang;Glassman, Matthew J.;Li, Shuaili;Socrate, Simona;Olsen, Bradley D.
用于医疗应用的人造蛋白质水凝胶需要精确控制其机械性能，包括生理环境中的刚度、韧性、延展性和稳定性。在这里，我们证明拓扑纠缠是一种有效的策略，可以稳健地提高基于卷曲线圈相互作用的瞬态水凝胶网络的机械可调性。通过耦合 N 端和 C 端附近的半胱氨酸残基来实现链延伸和缠结，并且发现所得的链分布与 Jacobson-Stockmayer 理论一致。通过利用二硫键的可逆性质，可以通过氧化还原刺激来打开和关闭缠结效应。由于存在缠结，水凝胶的抗蠕变性提高了 7.2 倍，侵蚀速率降低了 5.8 倍，使得凝胶在生理相关的开放系统中机械性能更加稳定。虽然几乎不影响材料刚度（仅导致平台模量增加 1.5 倍），但缠结显着导致水凝胶具有 65,000 J m-3 的韧性和约 3,000% 工程应变的延展性，从而能够制备坚韧而柔软的组织模拟物。这种机械性能的改进类似于双网络水凝胶，但是通过使用单个缔合网络和拓扑缠结来实现的。因此，氧化还原触发的链缠结为构建机械增强和响应性可注射水凝胶提供了一种有效的方法。
Engineering artificial protein hydrogels for medical applications requires precise control over their mechanical properties, including stiffness, toughness, extensibility and stability in the physiological environment. Here we demonstrate topological entanglement as an effective strategy to robustly increase the mechanical tunability of a transient hydrogel network based on coiled-coil interactions. Chain extension and entanglement are achieved by coupling the cysteine residues near the N- and C- termini, and the resulting chain distribution is found to agree with the Jacobson-Stockmayer theory. By exploiting the reversible nature of the disulfide bonds, the entanglement effect can be switched on and off by redox stimuli. With the presence of entanglements, hydrogels exhibit a 7.2-fold enhanced creep resistance and a suppressed erosion rate by a factor of 5.8, making the gels more mechanically stable in a physiologically relevant open system. While hardly affecting material stiffness (only resulting in a 1.5-fold increase in the plateau modulus), the entanglements remarkably lead to hydrogels with a toughness of 65,000 J m-3 and extensibility to approximately 3,000% engineering strain, which enables the preparation of tough yet soft tissue simulants. This improvement in mechanical properties resembles that from double-network hydrogels, but is achieved with the use of a single associating network and topological entanglement. Therefore, redox-triggered chain entanglement offers an effective approach for constructing mechanically enhanced and responsive injectable hydrogels.
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