Radical-Mediated Degradation of Thiol-Maleimide Hydrogels.
Radical-Mediated Degradation of Thiol-Maleimide Hydrogels.
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DOI：
10.1002/advs.202402191
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发表时间：
2024-04
期刊：
影响因子：
15.1
通讯作者：
T. S. Hebner;Bruce E. Kirkpatrick;Benjamin D Fairbanks;Christopher N. Bowman;K. Anseth;Danielle S. W. Benoit
中科院分区：
文献类型：
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作者：
T. S. Hebner;Bruce E. Kirkpatrick;Benjamin D Fairbanks;Christopher N. Bowman;K. Anseth;Danielle S. W. Benoit
巯基和马来酰亚胺功能化分子之间的Michael加成是一种长期以来用于生物偶联、水凝胶交联和其他高级材料功能化的方法。虽然这种化学的简单性使水凝胶的合成变得容易，但在许多情况下，网络降解也是可取的。本文报道了巯基-马来酰亚胺键对自由基介导的降解的敏感性。在水凝胶和线性聚合物中使用光引发和化学引发的自由基证明了交联材料的不可逆降解。降解的程度取决于引发剂的浓度。利用线性聚合物模型，阐明了自由基介导的降解机制，其中硫代琥珀酰亚胺交联转化为琥珀酰亚胺和带有引发剂片段的新硫醚。利用激光立体光刻技术，展示了对交联凝胶降解的高保真时空控制。最终，这项工作为巯基-马来酰亚胺水凝胶的可控、自由基介导的降解建立了一个平台，进一步扩大了它们作为功能材料的多功能性。
Michael addition between thiol‐ and maleimide‐functionalized molecules is a long‐standing approach used for bioconjugation, hydrogel crosslinking, and the functionalization of other advanced materials. While the simplicity of this chemistry enables facile synthesis of hydrogels, network degradation is also desirable in many instances. Here, the susceptibility of thiol–maleimide bonds to radical‐mediated degradation is reported. Irreversible degradation in crosslinked materials is demonstrated using photoinitiated and chemically initiated radicals in hydrogels and linear polymers. The extent of degradation is shown to be dependent on initiator concentration. Using a model linear polymer system, the radical‐mediated mechanism of degradation is elucidated, in which the thiosuccinimide crosslink is converted to a succinimide and a new thioether formed with an initiator fragment. Using laser stereolithography, high‐fidelity spatiotemporal control over degradation in crosslinked gels is demonstrated. Ultimately, this work establishes a platform for controllable, radical‐mediated degradation in thiol–maleimide hydrogels, further expanding their versatility as functional materials.