High performance aniline vapor detection based on multi-branched fluorescent triphenylamine-benzothiadiazole derivatives: branch effect and aggregation control of the sensing performance
High performance aniline vapor detection based on multi-branched fluorescent triphenylamine-benzothiadiazole derivatives: branch effect and aggregation control of the sensing performance
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DOI：
10.1039/c2jm30933e
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发表时间：
2012-05
影响因子：
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通讯作者：
Liqi Shi;Chao He;D. Zhu;Qingguo He;Yang Li;Yan Chen;Yuxi Sun;Yanyan Fu;D. Wen;H. Cao-
中科院分区：
文献类型：
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作者：
Liqi Shi;Chao He;D. Zhu;Qingguo He;Yang Li;Yan Chen;Yuxi Sun;Yanyan Fu;D. Wen;H. Cao-
设计并合成了一系列苯并噻二唑-吡啶支链三苯胺衍生物TPA1BP、TPA2BP和TPA3BP，通过光诱导电子转移（PET）检测苯胺蒸汽，具有优异的灵敏度、选择性和重复性。合适的能级保证了三种感应材料对苯胺的高选择性。然而，在石英衬底上，三种材料在薄膜状态下的聚集随着分支的增加而增加，这严重影响了传感性能，导致荧光效率降低，接触面积减少，蒸汽穿透性差。取向ZnO纳米棒阵列由于具有高的表面体积比和三维结构，可以消除聚集现象，提高传感性能。因此，可以观察到TPAnBP的感知性能随着分支数的增加而增加的协同效应；在300 ppm苯胺蒸气中暴露时间不超过5 s时，薄膜的荧光强度分别为TPA1BP、TPA2BP和TPA3BP，猝灭率分别为34%、45%和54%。此外，所有三种传感材料的荧光几乎100%被新鲜空气冲洗20秒，并可以立即重复使用。根据拟合图，预测TPA1BP的检出限为1 ppm， TPA2BP为100 ppb， TPA3BP为1 ppb，表明分子分支具有显著的协同效应。
A series of benzothiadiazole-pyridine branched triphenylamine derivatives TPA1BP, TPA2BP and TPA3BP have been designed and synthesized to sense aniline vapor with distinguished sensitivity, selectivity and repeatability via photoinduced electron transfer (PET). Suitable energy levels ensure the high selectivity to aniline for all three sensory materials. However, the aggregations of the three materials in the film state on a quartz substrate increase along with the branches, which highly deteriorate the sensing performance for less efficient fluorescence, lower contact area and inferior vapor penetration. The oriented ZnO nanorod array is introduced as the substrate to eliminate the aggregation and enhance the sensing performance, because of its high surface-to-volume ratio and 3D structure. Therefore, the cooperative effect that the sensing performance of TPAnBP increases with the number of branches could be observed; fluorescence intensities of the films on the nano-substrate are 34%, 45% and 54% quenched for TPA1BP, TPA2BP and TPA3BP, respectively, after exposure to 300 ppm aniline vapor for less than 5 s. Moreover, the fluorescences of all three sensory materials are almost 100% recovered by eluting with fresh air for 20 s and could be reused immediately. The detection limits are predicted to be 1 ppm for TPA1BP, 100 ppb for TPA2BP and 1 ppb for TPA3BP according to the fitted plot, demonstrating a significant cooperative effect of the molecular branches.