CAS Key Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Polymer Science and Engineering, Anhui Key Laboratory of Optoelectronic Science and Technology, University of Science and Technology of China , Hefei, Anhui 230026, China.
ACS Appl Mater Interfaces. 2015 Jan 14;7(1):241-9. doi: 10.1021/am505950c. Epub 2014 Dec 18.
In this paper, we report a facile strategy to fabricate fluorescent porous thin film on the surface of U-bent poly(methyl methacrylate) optical fiber (U-bent POF) in situ via "click" polymerization for vapor phase sensing of explosives. Upon irradiation of evanescent UV light transmitting within the fiber under ambient condition, a porous film (POSS-thiol cross-linking film, PTCF) is synthesized on the side surface of the fiber by a thiol-ene "click" reaction of vinyl-functionalized polyhedral oligomeric silsesquioxanes (POSS-V8) and alkane dithiols. When vinyl-functionalized porphyrin, containing four allyl substituents at the periphery, is added into precursors for the polymerization, fluorescence porphyrin can be covalently bonded into the cross-linked network of PTCF. This "fastened" way reduces the aggregation-induced fluorescence self-quenching of porphyrin and enhances the physicochemical stability of the porous film on the surface of U-bent POF. Fluorescent signals of the PTCF/U-bent POF probe made by this method exhibit high fluorescence quenching toward trace TNT and DNT vapor and the highest fluorescence quenching efficiency is observed for 1, 6-hexanedimercaptan-based film. In addition, because of the presence of POSS-V8 with multi cross-linkable groups, PTCF exhibits well-organized pore network and stable dye dispersion, which not only causes fast and sensitive fluorescence quenching against vapors of nitroaromatic compounds, but also provides a repeatability of the probing performance.
在本文中，我们报告了一种简便的策略，通过“点击”聚合在 U 型聚甲基丙烯酸甲酯（PMMA）光纤（U 型光纤）的表面原位制造荧光多孔薄膜，用于爆炸物的气相传感。在环境条件下通过光纤内传输的消逝紫外光照射下，纤维的侧面通过乙烯基官能化的多面体低聚倍半硅氧烷（POSS-V8）和烷烃二硫醇的硫醇-烯“点击”反应合成多孔膜（POSS-硫醇交联膜，PTCF）。当将含有四个烯丙基取代基的外围的荧光卟啉加入到聚合的前体中时，荧光卟啉可以共价键合到 PTCF 的交联网络中。这种“固定”方式减少了卟啉的聚集诱导荧光自猝灭，并提高了 U 型光纤表面多孔膜的物理化学稳定性。通过这种方法制成的 PTCF/U 型光纤探针的荧光信号对痕量 TNT 和 DNT 蒸气表现出高荧光猝灭，并且在用 1,6-己二硫醇为基础的薄膜观察到最高的荧光猝灭效率。此外，由于存在具有多个可交联基团的 POSS-V8，PTCF 表现出组织良好的孔网络和稳定的染料分散性，这不仅导致对硝基芳烃化合物蒸气的快速和灵敏荧光猝灭，而且还提供了探测性能的可重复性。
