The Synthesis of Phenothiazine Derivatives with Mechanofluorochromism Property and the Fluorescence Detection for 2, 4, 6-trinitrophenol
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摘要: 设计合成了2种具有明显聚集诱导发光(AIE)特性的吩噻嗪衍生物(SPA和SPN).荧光光谱研究表明, 这2种化合物在水溶液中能够特异性地识别2, 4, 6-三硝基苯酚(TNP), 其中SPA荧光检测TNP的猝灭率为89.1%, 猝灭常数Ksv为3.18×104 L/mol, 检出限为8.62×10-7 mol/L; SPN荧光检测TNP的猝灭率为90.4%, 猝灭常数Ksv为4.43×104 L/mol, 检出限为5.00×10-7 mol/L, 有望作为荧光探针特异性识别TNP.而且SPA分子具有可逆的力致荧光变色特性, 在紫外灯下发出蓝色荧光, 研磨后变为浅黄色, 有望被用于防伪材料或者可视化压力传感器领域.
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关键词:
- 吩噻嗪衍生物 /
- 聚集诱导发光 /
- 荧光检测 /
- 2, 4, 6-三硝基苯酚 /
- 力致荧光变色
Abstract: Two phenothiazine derivatives (SPA and SPN) with significant aggregation-induced emission (AIE) characteristics were designed and synthesized. Photoluminescence spectroscopy showed that these two compounds could specifically recognize TNP in aqueous media. The fiuorescence of SPA was quenched by 89.1% in the presence of TNP with a detection limit as low as 8.62×10-7 mol/L and a high Stern-Volmer quenching constant (Ksv) of 3.18×104 L/mol. The fluorescence of SPN was quenched by 90.4% after addition of TNP with a detection limit as low as 5.00×10-7 mol/L and a high Stern-Volmer quenching constant of 4.43×104 L/mol. It indicated that SPA and SPN were expected to work as fiuorescent probe to detection TNP with high sensitivity and selectivity. Moreover, SPA showed reversible mechanofluorochromic properties. It was observed that SPA emitted strong blue fluorescence under 365 nm UV light and the color changed light yellow after grinding. So it can promisingly be applied to the fields of visual pressure sensors or anti-counterfeiting materials. -
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图 2 SPA在不同φ(H2O)的H2O/THF溶液中的荧光光谱
注：插图为不同φ(H2O)下的荧光峰强度; SPA的浓度为10-5 mol/L.
Figure 2. The fluorescent spectra of SPA in H2O/THF mixture with different φ(H2O)
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图 3 SPN在不同φ(H2O)的H2O/THF溶液中的荧光光谱
注：插图为不同φ(H2O)下的荧光峰强度; SPA的浓度为10-5 mol/L.
Figure 3. The fluorescent spectra of SPN in H2O/THF mixture with different φ(H2O)
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图 4 SPA分子在水溶液中检测不同硝基芳香爆炸物的荧光光谱及荧光淬灭率
注：c(SPA)=1.0×10-4 mol/L.
Figure 4. The fluorescent spectra and the fluorescent quenching rate of SPA in the presence of different nitro explosives in aqueous media
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图 5 含不同浓度TNP的SPA溶液荧光光谱以及峰强度拟合曲线
Figure 5. The fluorescent spectra and the peak intensity fitting of SPA solution with the addition of different concentrations of TNP solutions
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图 6 SPN分子在水溶液中检测不同硝基芳香爆炸物的荧光光谱及荧光淬灭率
注：c(SPN)=1.0×10-4 mol/L.
Figure 6. The fluorescent spectra and the fluorescent quenching rate of SPN in the presence of different nitro explosives in aqueous media
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图 7 向XPA溶液中滴加不同浓度TNP溶液后的荧光强度变化及峰强度线性拟合
Figure 7. The fluorescent spectra and the peak intensity fitting of SPA solution with the addition of different concentrations of TNP solutions
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图 8 2次研磨和熏蒸后的SPA粉末的荧光光谱
Figure 8. The fluorescent spectra of SPA after 2 times of grinding and fumigating
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图 9 2次研磨和熏蒸后的SPA的XRD谱
Figure 9. The XRD patterns of SPA after 2 times of grinding and fumigating
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