一种可用于检测苦味酸的水溶性共轭聚合物荧光传感器的制备及应用

doi:10.7503/cjcu20170272

摘要/Abstract

摘要：

制备了一种高灵敏的水溶性荧光共轭聚合物(PPE-OBS), 将其用于苦味酸的荧光检测. 利用质谱、核磁共振波谱和红外光谱等方法对PPE-OBS进行了表征, 并对其检测苦味酸的条件进行了优化. 结果表明, 在硼酸-氢氧化钠缓冲溶液(pH=9.5)中作用20 min, 苦味酸对PPE-OBS荧光的猝灭效率最大. 在最优条件下, PPE-OBS检测苦味酸的线性范围为1.0~60 μmol/L(R²=0.999), 检出限为0.831 μmol/L(S/N=3). 将PPE-OBS制成荧光试纸用于检测环境样品中的苦味酸, 获得了较好的检测结果.

关键词: 水溶性荧光共轭聚合物, 苦味酸, 化学传感器, 荧光猝灭

Abstract:

A water soluble conjugated polymer{poly[2,5-bis(sodium 4-oxybutyrate)-1,4-phenylethyny-lene-alt-1,4-phenyleneethynylene], PPE-OBS}, was synthesized for the detection of picronitric acid(PA). PPE-OBS was characterized by means of mass spectrometry, NMR spectroscopy, infrared spectroscopy(IR), and so on. The experiment conditions and detection performance of PPE-OBS were systematically studied. The results show that the fluorescent quenching of PPE-OBS is the most efficient when the reaction time between PPE-OBS and PA is 20 min in the boric acid-sodium hydroxide buffer solution(pH=9.5). The results demonstrate that PPE-OBS as a sensor for PA has a good linear range from 1.0 to 60 μmol/L with the calculated limit of detection(LOD) to be 0.831 μmol/L. Meanwhile, PPE-OBS paper was applied to rapidly detecting PA in environmental water samples.

Key words: Water soluble fluorescence conjugated polymer, Nitrobenzene explosive, Chemical sensor, Fluorescence quenching

中图分类号:

O657

TrendMD:

刘吉林, 米红玉, 关明明, 郇延富, 费强, 张志权, 冯国栋. 一种可用于检测苦味酸的水溶性共轭聚合物荧光传感器的制备及应用. 高等学校化学学报, 2017, 38(12): 2163.

LIU Jilin, MI Hongyu, GUAN Mingming, HUAN Yanfu, FEI Qiang, ZHANG Zhiquan, FENG Guodong. Preparation and Application of Novel Fluorescence Chemical Sensor for Determining Trace Levels of Picronitric Acid Based on Water Soluble Conjugated Polymer. Chem. J. Chinese Universities, 2017, 38(12): 2163.

图/表 9

Scheme 1 Synthetic routes of PPE-OBSa. Dimethyl sulfoxide, potassium hydroxide, refluxing 24 h, argon, 25 ℃(yield 83%); b. ethanol, concentrated sulfuric acid, potassium iodate, iodine, tetrakis(triphenylphosphine)palladium, refluxing 48 h, argon, 60 ℃(yield 80%); c. chloroform, triethylamine, isopropylamine, 1,4-diacetylene benzene, water bath stirring 24 h, 50 ℃(yield 76%); d. tetrahydrofuran, methanol, NaOH, reflux for 24 h, 50 ℃(yield 88%).

Fig.1 Fluorescence emission spectrum of PPE-OBS(a), excitation spectra of PPE-OBS(b) and PPE-OBS+PA(c)(A) and images of the color changes of PPE-OBS(a, c) and PPE-OBS+PA(b, d) under a UV-lamp with visible light(a, b) and wavelength of 365 nm(c, d)(B)

Fig.2 Electron transfer mechanism of PPE-OBS with picric acid

Fig.3 Fluorescence intensity of PPE-OBS(0.05 mmol/L) assay system without(a) and with picric acid(0.1 mmol/L)(b) at different pH values(b)

Fig.4 Effects of different buffer solutions on the fluorescence intensity of PPE-OBSa. NaHCO3+Na2CO3; b. NH3+NH4Cl; c. H3BO3+NaOH; d. glycine+NaOH.

Fig.5 Fluorescence intensity of PPE-OBS(0.05 mmol/L) assay system with PA or several nitrobenzene compounds(0.1 mmol/L)(red bar) and the interference of coexisting several nitrobenzene compounds(0.1 mmol/L) on the determination of PA(black bar)a. Blank; b. PA; c. 3-MNT; d. 2-MNT; e. 4-MNT; f. 3-NA; g. 4-CNB; h. NB; i. 4-NBA.

Fig.6 Effect of reaction time on the fluorescence intensity of PPE-OBS with picric acid

Fig.7 Linear relationship between fluorescence quenching efficiency and concentration of picric acid

Fig.8 Determination of picric acid in tap water using PPE-OBS fluorescence test paper

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