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·1320· 精细化工 FINE CHEMICALS
图 8 加入不同浓度次氯酸钠后的探针 ZN1 的 HNMR 谱
图（溶剂为 d 6 -DMSO）
1
Fig. 8 HNMR spectra of the resulting solutions of ZN1
with different NaClO concentration (in d 6 -DMSO)
2.7 探针分子 ZN1 对次氯酸的识别机理研究
探针 ZN1 是一种激发态分子内质子转移（excited
state intramolecular proton transfer, ESIPT）荧光探
针；其存在 Enol 和 Keto 等多种能态
通过 ESIPT 形式发射 em =530 nm 处的橙色荧光（图
6、7）。但是在加入次氯酸钠后，由于次氯酸根的氧
化作用，破坏了探针原有的 ESIPT 过程，从而导致
 em =530 nm 处的荧光出现淬灭。
为了验证上述猜想，对加入次氯酸钠溶液的探
针 ZN1 溶液开展了质谱分析。高分辨质谱表明，反
应液中出现了的 m/Z=415.06812 的信号峰，而探针
ZN1 的质谱信号峰为 417.08373；这表明探针 ZN1
在次氯酸的作用被氧化，生成了失去 2 个氢原子的
产物 ZN2。此外，用微量注射器吸取一定量的次氯
酸钠溶液，并注射到含有探针 ZN1 的 d 6 -DMSO 溶
液中，摇晃混匀后进行核磁共振氢谱分析（图 8）。
探针分子的酚羟基氢原子信号峰在加入次氯酸钠后
逐渐消失（δ12.68），同时其席夫碱结构上氢原子
（==CH—）也受此影响，其信号峰逐渐向高场移动。
以上信息均表明，探针 ZN1 在次氯酸的作用下被氧
化生成脱氢产物 ZN2，并破坏了原有的 ESIPT 过程，
从而产生荧光信号的改变。
3 结论
通过较为简易的合成方法制备了一种基于次氯
酸的比率型荧光探针 ZN1。该探针可以快速灵敏、
选择性地识别次氯酸根离子，并且其荧光信号在
0~40 μmol/L 次氯酸浓度范围内呈现良好的线性关
系，其检测下限为 0.96 μmol/L。此外，还深入探
讨了该荧光探针的响应机理，同时将其成功应用
于实际水样中的次氯酸检测，并取得了满意的测试
结果。
第 36 卷
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