Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, P. R. China.
National Supercomputer Research Center of Advanced Materials, Advanced Materials Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250014, P. R. China.
Anal Chem. 2021 Feb 2;93(4):2367-2376. doi: 10.1021/acs.analchem.0c04226. Epub 2021 Jan 6.
Flexible optical sensors are widely studied and applied in many fields. However, developing highly stable and washable wearable sensors in optics is still facing significant challenges. Here, we demonstrate an AIEgen-organosilica framework (TPEPMO) hybrid nanostructure-based flexible optical sensor, which is prepared by a two-step co-condensation and electrospinning superassembly process. Organosilica precursors with aggregation-induced emission (AIE) features are covalently linked into periodic mesoporous organosilica (PMO) frameworks with high fluorescent efficiency due to the restriction of intramolecular motion. The three-dimensional space of ordered porous materials provides abundant reaction sites, allowing rapid and sensitive monitoring of analytes. TPEPMOs exhibit good properties as acidic pH fluorescent sensors with a p of 4.3. A flexible film is obtained by dispersing TPEPMO nanospheres in a poly(lactic--glycolic acid) (PLGA) and polyacrylonitrile (PAN) hybrid fibrous matrix (TPEPMO-CFs) using the electrospinning superassembly technique and is successfully served as an efficient fluorescent probe for the naked eye detection of ammonia gas and HCl vapor by emission changes. The fluorescence of TPEPMO-CFs can be reversed in the presence of volatile acidic/alkaline gas for more than five cycles, exhibiting excellent recyclability. In addition, TPEPMO-CF sensors show excellent washability and long-term photostability (fluorescence was maintained above 94% after washing 10 times). These stimuli-responsive AIEgen-organosilica frameworks featuring diversified forms and superstability for wearable and washable solid-state fluorescence exhibit great potential for smart gas sensors, wearable devices, and solid-state lighting applications.
柔性光学传感器在许多领域得到了广泛的研究和应用。然而，在光学领域开发高度稳定和可清洗的可穿戴传感器仍然面临着重大挑战。在这里，我们展示了一种基于聚集诱导发射（AIE）有机硅纳米框架（TPEPMO）杂化纳米结构的柔性光学传感器，该传感器是通过两步共缩聚和静电纺丝超组装工艺制备的。具有聚集诱导发射（AIE）特性的有机硅前体由于分子内运动的限制，通过共价键连接到具有高荧光效率的周期性介孔有机硅（PMO）框架中。有序多孔材料的三维空间为快速和敏感地监测分析物提供了丰富的反应位点。TPEPMO 表现出良好的性质，可作为酸性 pH 荧光传感器，p 值为 4.3。通过将 TPEPMO 纳米球分散在聚（乳酸-乙交酯）（PLGA）和聚丙烯腈（PAN）杂化纤维基质中（TPEPMO-CFs），采用静电纺丝超组装技术获得了柔性薄膜，并成功用作氨气和 HCl 蒸气的肉眼检测的高效荧光探针，通过发射变化进行检测。在挥发性酸性/碱性气体存在下，TPEPMO-CFs 的荧光可以反复反转超过五个循环，表现出优异的可循环性。此外，TPEPMO-CF 传感器表现出优异的可清洗性和长期光稳定性（洗涤 10 次后荧光保持在 94%以上）。这些具有多样化形态和超稳定性的刺激响应 AIE 有机硅纳米框架适用于可穿戴和可清洗的固态荧光，在智能气体传感器、可穿戴设备和固态照明应用方面具有巨大的潜力。
