In Situ and Real-Time Visualization of Mechanochemical Damage in Double-Network Hydrogels by Prefluorescent Probe via Oxygen-Relayed Radical Trapping
In Situ and Real-Time Visualization of Mechanochemical Damage in Double-Network Hydrogels by Prefluorescent Probe via Oxygen-Relayed Radical Trapping
复制标题
利用预荧光探针通过氧中继自由基捕获对双网络水凝胶中的机械化学损伤进行原位实时可视化
DOI：
10.1021/jacs.2c13764
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发表时间：
2023
影响因子：
15
通讯作者：
Gong Jian Ping
中科院分区：
文献类型：
--
作者：
Zheng Yong;Jiang Julong;Jin Mingoo;Miura Daiyo;Lu Fei Xue;Kubota Koji;Nakajima Tasuku;Maeda Satoshi;Ito Hajime;Gong Jian Ping
机械化学损伤的可视化，特别是对于分子尺度的损伤（例如，聚合物材料中的键断裂），具有重要的工业和学术意义。在这里，我们报告了一种新的战略，在原位和实时可视化的水凝胶中的机械化学损伤，通过利用预荧光探针通过氧中继自由基捕获。双网络（DN）水凝胶，产生大量的机械自由基的脆性第一网络在大变形的均裂键断裂被用作模型材料。理论计算表明，第一网络的损伤产生的机械自由基进行氧中继自由基转移过程，可以检测到的预荧光探针通过自由基-自由基偶联反应。这种氧中继自由基捕获过程的prefluorescent探针表现出显着增强的发射，这使得实时传感和可视化的机械化学损伤DN水凝胶从不同的化学结构的脆性网络。据作者所知，这项工作是第一份利用氧作为自由基中继分子来可视化聚合物材料中机械自由基损伤的报告。此外，这种基于探针后加载的新方法很简单，不会在材料中引入任何化学结构变化，优于大多数以前需要将机械载体化学掺入聚合物网络的方法。
Visualization of mechanochemical damages, especially for those in the molecular-scale (e.g., bond scission in polymeric materials), is of great industrial and academic significance. Herein, we report a novel strategy for in situ and real-time visualization of mechanochemical damages in hydrogels by utilizing prefluorescent probes via oxygen-relayed free-radical trapping. Double-network (DN) hydrogels that generate numerous mechanoradicals by homolytic bond scission of the brittle first network at large deformation are used as model materials. Theoretical calculation suggests that mechanoradicals generated by the damage of the first network undergo an oxygen-relayed radical-transfer process which can be detected by the prefluorescent probe through the radical–radical coupling reaction. Such an oxygen-relayed radical-trapping process of the prefluorescent probe exhibits a dramatically enhanced emission, which enables the real-time sensing and visualization of mechanochemical damages in DN hydrogels made from brittle networks of varied chemical structures. To the best of authors’ knowledge, this work is the first report utilizing oxygen as a radical-relaying molecule for visualizing mechanoradical damages in polymer materials. Moreover, this new method based on the probe post-loading is simple and does not introduce any chemical structural changes in the materials, outperforming most previous methods that require chemical incorporation of mechanophores into polymer networks.