交联模式提升基于寡聚对苯撑乙烯撑荧光力敏团力刺激响应发光水凝胶性能研究

doi:10.6023/A26050175

摘要/Abstract

力刺激响应发光（MRL）水凝胶能够将机械刺激转化为可识别的光学信号,在柔性传感、损伤监测等领域受到广泛关注.荧光力敏团与水凝胶基质的复合方式对水凝胶力刺激响应发光性能起决定作用.针对物理掺杂体系响应对比度不够高的问题,本研究设计合成了两种分别带有乙烯基-乙烯基和乙烯基-动态四重氢键基团端基的氰基寡聚对苯撑乙烯撑衍生物（cyano-OPV）,将其作为化学键合型荧光力敏团,分别构筑了化学交联和动态交联型力刺激响应发光水凝胶.结果证明,两种水凝胶均表现出较高的力刺激响应发光对比度,其中,动态交联型体系水凝胶（UPy-OPV-Vin-PGASMN）荧光CIE坐标从（0.39, 0.59）移至（0.33, 0.60）,表现出更明显的荧光变化,且在高交联密度下仍保持较好的延展性和恢复能力,实现力响应灵敏度与网络适应性的协同优化.

关键词: 力刺激响应发光, 水凝胶, 发光力敏团, 化学交联, 动态交联

Mechanoresponsive luminescent (MRL) hydrogels, which convert mechanical stimuli into detectable optical signals, have attracted significant attention in fields of flexible sensing and damage monitoring. The integration of mechanochromic mechanophores with the hydrogel matrix plays a decisive role in determining the mechano-responsive luminescent performance of the hydrogels. The response signals in physically doped systems often suffer from low contrast. To address the issue, herein two types of cyano-oligo(p-phenylene vinylene) (cyano-OPV) derivatives, Vin-OPV-Vin and UPy-OPV-Vin, were designed and synthesized as chemically bonded mechanophores. Vin-OPV-Vin contains two polymerizable vinyl groups and serves as a permanent covalent crosslinking point, while UPy-OPV-Vin contains one vinyl group and one ureidopyrimidinone unit, providing covalent anchoring and reversible quadruple hydrogen bonding. In solution, when aggregated, Vin-OPV-Vin readily formed ordered π-π stacked excimer, whereas the bulky UPy group and hydrogen-bonding interactions suppressed compact face-to-face stacking and produced more diverse aggregates. The hydrogel matrix was optimized through orthogonal experiments and prepared by in situ photopolymerization combined with repeated freeze-thaw treatment. By varying the functionality of the mechanophores, chemically crosslinked (Vin-OPV-Vin-PGASMM) and dynamically crosslinked (UPy-OPV-Vin-PGASMM) hydrogels were constructed, respectively. The former exhibited higher fracture stress and Young’s modulus due to permanent covalent crosslinking, while the latter showed better deformation recoveribility because the reversible quadruple hydrogen bonds dissipated energy and allowed chain rearrangement. Upon stretching, both types of hydrogels exhibited MRL properties, and UPy-OPV-Vin-PGASMM showed a higher color contrast, with the CIE coordinates varying from (0.39, 0.59) to (0.33, 0.60) under 0-250% tensile strain. Notably, the dynamically crosslinked system achieved synergistic optimization of mechanoresponsive sensitivity and network adaptability.

Key words: Mechanoresponsive luminescence, hydrogel, mechanochromic mechanophore, chemical crosslinking, dynamic crosslinking

引用此文

林浩楠, 李庚, 马佳兴, 朱珊珊, 李洁. 交联模式提升基于寡聚对苯撑乙烯撑荧光力敏团力刺激响应发光水凝胶性能研究[J]. 化学学报, doi: 10.6023/A26050175.

Lin Haonan, Li Geng, Ma Jiaxing, Zhu Shanshan, Li Jie. Enhancing Mechanoresponsive Luminescence of Hydrogels Based on Cyano-Oligo(p-phenylene vinylene) Mechanophores via Crosslinking Mode[J]. Acta Chimica Sinica, doi: 10.6023/A26050175.

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