顶空薄膜微萃取-表面增强拉曼光谱法快速检测枸杞子中的二氧化硫残留量
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摘要
目的:结合顶空薄膜微萃取技术具有的本底基质干扰小、萃取效率高的优点和表面增强拉曼光谱技术具有的检测快速、灵敏的特点,拟实现枸杞子中二氧化硫残(SO_2)留量的快速分析。方法:在1个10 mL密闭的顶空瓶中放置1.0 g粉碎的枸杞子样品并加稀硫酸酸化,将一片氧化锌(ZnO)薄膜放置在密闭的顶空并于55℃萃取10 min。顶空萃取结束后取出ZnO薄膜,于ZnO薄膜上加入10μL浓缩的金胶后,采用便携式拉曼光谱仪进行检测。结果:在654 cm~(-1)可以检测到SO_2清晰明显的拉曼光谱特征峰。实验研究了影响萃取效率的因素,包括萃取时间、萃取温度、相比等。在优化的条件下,该方法的线性范围为25～800mg·kg~(-1),检测下限为15 mg·kg~(-1)。顶空薄膜微萃取-表面增强拉曼光谱检测枸杞子中SO_2含量的实验结果与传统的碘滴定法所测得的结果不存在显著性差异,加标回收率在83.7%～107.3%范围内。结论:该方法可实现枸杞子中SO_2残留量的快速分析。
Objective:Combined the advantage of low background interference and high extraction efficiency for headspace thin-film microextraction sample preparation technique with the advantage of fast detection and high sensitivity for surface-enhanced Raman spectroscopy(SERS),an approach had been developed for the rapid detection of residual sulfur dioxide in Lycii fructus. Methods:1.0 g of crashed Lycii fructus was put in a 10 mL glass vessel and then was acidized by diluted sulphuric acid. A ZnO film was hung in the head space of the sealed glass vessel to extract SO_2 from the sample solution at 55 ℃ for 10 mins. After the extraction,the ZnO film was taken out and 10 μL of concentrated AuNPs was dropped onto its surface for SERS analysis. All SERS measurements were carried out by a portable Raman spectrometer. Results:A characteristic peak for SO_2 can be detected at 654 cm~(-1). Experimental parameters related to extraction efficiency including extraction time,extraction temperature and phase ratio were investigated and optimized. Under the optimized conditions,a good linearity was in the range of 25-800 mg·kg~(-1) and the detection limit was 15 mg·kg~(-1). There was no significant difference between the developed method and the traditional distillation and titration method for the determination of SO_2 in Lycii fructus,and the recoveries were in the range of 83.7%-107.3%. Conclusion:The developed method coupled with headspace thin-film microextraction and surface-enhanced Raman spectroscopy can be used for quick determination of residual sulfur dioxide in Lycii fructus.
Objective:Combined the advantage of low background interference and high extraction efficiency for headspace thin-film microextraction sample preparation technique with the advantage of fast detection and high sensitivity for surface-enhanced Raman spectroscopy(SERS),an approach had been developed for the rapid detection of residual sulfur dioxide in Lycii fructus. Methods:1.0 g of crashed Lycii fructus was put in a 10 mL glass vessel and then was acidized by diluted sulphuric acid. A ZnO film was hung in the head space of the sealed glass vessel to extract SO_2 from the sample solution at 55 ℃ for 10 mins. After the extraction,the ZnO film was taken out and 10 μL of concentrated AuNPs was dropped onto its surface for SERS analysis. All SERS measurements were carried out by a portable Raman spectrometer. Results:A characteristic peak for SO_2 can be detected at 654 cm~(-1). Experimental parameters related to extraction efficiency including extraction time,extraction temperature and phase ratio were investigated and optimized. Under the optimized conditions,a good linearity was in the range of 25-800 mg·kg~(-1) and the detection limit was 15 mg·kg~(-1). There was no significant difference between the developed method and the traditional distillation and titration method for the determination of SO_2 in Lycii fructus,and the recoveries were in the range of 83.7%-107.3%. Conclusion:The developed method coupled with headspace thin-film microextraction and surface-enhanced Raman spectroscopy can be used for quick determination of residual sulfur dioxide in Lycii fructus.
引文
[1]WANG S,SUH JH,ZHENG X,et al.Identification and quantification of potential anti-inflammatory hydroxycinnamic acid amides from wolfberry[J].J Agric Food Chem,2017,65(2):364
[2]ZHOU ZQ,FAN HX,HE RR,et al.Lycibarbarspermidines A-O,new dicaffeoylspermidine derivatives from wolfberry,with activities against Alzheimer’s disease and oxidation[J].J Agric Food Chem,2016,64(11):2223
[3]汪小知,李娟,赵伟军,等.高场非对称波形离子迁移谱(FAIMS)技术快速检测中药材中二氧化硫[J].药物分析杂志,2014,34(9):1611WANG XZ,LI J,ZHAO WJ,et al.Rapid detection of sulfur dioxide in Chinese herbal medicine by FAIMS[J].Chin J Pharm Anal,2014,34(9):1611
[4]王晓伟,刘景富,关红,等.三重串联四极杆电感耦合等离子体质谱法测定植源性中药材中总硫含量[J].光谱学与光谱分析,2016,36(2):527WANG XW,LIU JF,GUAN H,et al.Determination of total sulfur dioxide in Chinese herbal medicines via triple quadrupole inductively coupled plasma mass spectrometry[J].Spectrosc Spect Anal,2016,36(2):527
[5]施玉珍,陈志春,林贤福.枸杞子的共聚焦显微拉曼光谱鉴别[J].光谱实验室,2004,21(6):1211SHI YZ,CHEN ZC,LIN XF.Identification of Lycium Barbarum(Gouqizi)by confocal microprobe Raman spectroscopy[J].Chin JSpectrosc Lab,2004,21(6):1211
[6]张琳,曹晓云.拉曼光谱技术及其在药物分析中的应用[J].天津药学,2014,26(4):46ZHANG L,CAO XY.Raman spectroscopy and its application in pharmaceutical analysis[J].Tianjin Pharm,2014,26(4):46
[7]ANASTASOPOULOS JA,BEOBIDE AS,MANIKAS AC,et al.Quantitative surface-enhanced resonance Raman scattering analysis of methylene blue using silver colloid[J].J Raman Spectrosc,2017,48(12):1762
[8]ZHANG M,ZHANG XZ,QU BF,et al.Portable kit for highthroughput analysis of polycyclic aromatic hydrocarbons using surface enhanced Raman scattering after dispersive liquid-liquid microextraction[J].Talanta,2017,175:495
[9]ROMERO V,COSTAS-MORA I,LAVILLA I,et al.Headspace thin-film microextraction onto graphene membranes for specific detection of methyl(cyclopentadienyl)-tricarbonyl manganesein water samples by total reflection X-ray fluorescence[J].Spectrochim Acta Part B,2016,126:65
[10]AHMADI F,SPARHAM C,BOYACI E,et al.Time weighted average concentration monitoring based on thin film solid phase microextraction[J].Environ Sci Technol,2017,51(7):3929
[11]DENG Z,CHEN XX,WANG YR,et al.Headspace thin-film microextraction coupled with surface-enhanced Raman scattering as a facile Method for reproducible and specific detection of sulfur dioxide in wine[J].Anal Chem,2015,87(1):633
[12]RINTOUL L,CRAWFORD K,SHURVELL HF,et al.Surfaceenhanced Raman scattering of inorganic oxoanions[J].Vib Spectrosc,1997,15(2):171
[2]ZHOU ZQ,FAN HX,HE RR,et al.Lycibarbarspermidines A-O,new dicaffeoylspermidine derivatives from wolfberry,with activities against Alzheimer’s disease and oxidation[J].J Agric Food Chem,2016,64(11):2223
[3]汪小知,李娟,赵伟军,等.高场非对称波形离子迁移谱(FAIMS)技术快速检测中药材中二氧化硫[J].药物分析杂志,2014,34(9):1611WANG XZ,LI J,ZHAO WJ,et al.Rapid detection of sulfur dioxide in Chinese herbal medicine by FAIMS[J].Chin J Pharm Anal,2014,34(9):1611
[4]王晓伟,刘景富,关红,等.三重串联四极杆电感耦合等离子体质谱法测定植源性中药材中总硫含量[J].光谱学与光谱分析,2016,36(2):527WANG XW,LIU JF,GUAN H,et al.Determination of total sulfur dioxide in Chinese herbal medicines via triple quadrupole inductively coupled plasma mass spectrometry[J].Spectrosc Spect Anal,2016,36(2):527
[5]施玉珍,陈志春,林贤福.枸杞子的共聚焦显微拉曼光谱鉴别[J].光谱实验室,2004,21(6):1211SHI YZ,CHEN ZC,LIN XF.Identification of Lycium Barbarum(Gouqizi)by confocal microprobe Raman spectroscopy[J].Chin JSpectrosc Lab,2004,21(6):1211
[6]张琳,曹晓云.拉曼光谱技术及其在药物分析中的应用[J].天津药学,2014,26(4):46ZHANG L,CAO XY.Raman spectroscopy and its application in pharmaceutical analysis[J].Tianjin Pharm,2014,26(4):46
[7]ANASTASOPOULOS JA,BEOBIDE AS,MANIKAS AC,et al.Quantitative surface-enhanced resonance Raman scattering analysis of methylene blue using silver colloid[J].J Raman Spectrosc,2017,48(12):1762
[8]ZHANG M,ZHANG XZ,QU BF,et al.Portable kit for highthroughput analysis of polycyclic aromatic hydrocarbons using surface enhanced Raman scattering after dispersive liquid-liquid microextraction[J].Talanta,2017,175:495
[9]ROMERO V,COSTAS-MORA I,LAVILLA I,et al.Headspace thin-film microextraction onto graphene membranes for specific detection of methyl(cyclopentadienyl)-tricarbonyl manganesein water samples by total reflection X-ray fluorescence[J].Spectrochim Acta Part B,2016,126:65
[10]AHMADI F,SPARHAM C,BOYACI E,et al.Time weighted average concentration monitoring based on thin film solid phase microextraction[J].Environ Sci Technol,2017,51(7):3929
[11]DENG Z,CHEN XX,WANG YR,et al.Headspace thin-film microextraction coupled with surface-enhanced Raman scattering as a facile Method for reproducible and specific detection of sulfur dioxide in wine[J].Anal Chem,2015,87(1):633
[12]RINTOUL L,CRAWFORD K,SHURVELL HF,et al.Surfaceenhanced Raman scattering of inorganic oxoanions[J].Vib Spectrosc,1997,15(2):171