TLC-SERS高通量筛查中成药与保健食品中添加的降糖化学物质
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摘要
目的:建立层色谱-表面增强拉曼光谱(TLC-SERS)方法现场快速筛查标示降糖作用的中成药与保健食品中非法掺杂的化学物质,并验证其可靠性。方法:待测样品TLC分离、在斑点表面增强后,采集拉曼光谱信息,利用药品快检支撑系统,与对照品增强后拉曼光谱库信息进行相似度评价、特征峰匹配,筛查斑点表面增强拉曼光谱与对照品增强后拉曼光谱库的相似顺序,相似度高于80%的拟定为疑似阳性样品,采用HPLC-MS离子谱和/或一级、二级质谱库进行比对确证。结果:12种常见添加降糖化学物质,4种使用水胶(AgNO_3+柠檬酸钠)、8种采用DMF胶(有机胶,AgNO_3+PVP),表面增强拉曼光谱信号满意,可以作为标准入库。TLC-SERS筛查发现,2种模拟中成药、4种模拟保健食品中疑似添加了降糖化学物质,经HPLC-MS保留时间、母离子与碎片离子质荷比对比确证,筛查结果与确证结果一致。结论:本方法适用于现场快速高通量筛查中成药、保健食品中非法掺杂的化学物质,TLC-SERS方法可靠。
Objective:To establish a rapid on-site screening method for illegal additives in hypoglycemic Chinese patent medicines or health foods and validate the feasibility of TLC-SERS method. Methods:Samples were separated by TLC and the surface enhanced Raman spectra were collected. Using rapid drug testing system,the spectra were compared with the enhanced Raman spectra of the reference substances by similarity evaluation and characteristic peak matching. When the similarity was higher than 80%,the sample was labeled as a suspected positive sample. Then the result was confirmed by HPLC-MS ion spectroscopy and/or primary and secondary mass spectrometry libraries. Results:Among 12 hypoglycemic chemicals,4 used water glue(fabricated by silver nitrate and sodium citrate)and 8 used DMF glue(fabricated by silver nitrate and polyvidone),and the spectral signals were satisfactory and could be used as standard spectra. TLC-SERS screening showed that two simulated Chinese patent medicines and four simulated health foods were suspected for addition of hypoglycemic chemicals.The results were confirmed by HPLC-MS retention time,parent ion and fragment ion mass-to-charge ratio.Conclusion:The method is suitable for on-site rapid high-throughput screening of the chemical substances which are illegally doped in Chinese patent medicine and health food,and the TLC-SERS method is reliable.
Objective:To establish a rapid on-site screening method for illegal additives in hypoglycemic Chinese patent medicines or health foods and validate the feasibility of TLC-SERS method. Methods:Samples were separated by TLC and the surface enhanced Raman spectra were collected. Using rapid drug testing system,the spectra were compared with the enhanced Raman spectra of the reference substances by similarity evaluation and characteristic peak matching. When the similarity was higher than 80%,the sample was labeled as a suspected positive sample. Then the result was confirmed by HPLC-MS ion spectroscopy and/or primary and secondary mass spectrometry libraries. Results:Among 12 hypoglycemic chemicals,4 used water glue(fabricated by silver nitrate and sodium citrate)and 8 used DMF glue(fabricated by silver nitrate and polyvidone),and the spectral signals were satisfactory and could be used as standard spectra. TLC-SERS screening showed that two simulated Chinese patent medicines and four simulated health foods were suspected for addition of hypoglycemic chemicals.The results were confirmed by HPLC-MS retention time,parent ion and fragment ion mass-to-charge ratio.Conclusion:The method is suitable for on-site rapid high-throughput screening of the chemical substances which are illegally doped in Chinese patent medicine and health food,and the TLC-SERS method is reliable.
引文
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[12]朱青霞,曹永兵,曹颖瑛,等.TLC-SERS法快速检测降压类中药中非法添加的四种化学成分[J].光谱学与光谱分析,2014,34(4):990ZHU QX,CAO YB,CAO YY,et al.Rapid detection of four antipertensive chemicals adulterated in traditional Chinese medicine for hypertension using TLC-SERS[J].Spectrosc Spect Anal,2014,34(4):990
[13]FANG F,QI Y,LU F,et al.Highly sensitive on-site detection of drugs adulterated in botanical dietary supplements using thin layer chromatography combined with dynamic surface enhanced Raman spectroscopy[J].Talanta,2016,146(1):351
[14]秦剑红.TLC-SERS联用法检测降糖中成药中添加的格列类药品[J].药学实践杂志,2014,32(03):206QIN JH.Detection of glinides adulterated in traditional Chinese medicine for diabetes by TLC-SERS[J].J Pharm Pract,2014,32(3):206
[15]陈娟,孙楠楠,邵亚兰,等.TLC-SERS法快速检测复方杜仲胶囊中非法添加化学药物的研究[J].激光与光电子学进展,2015,52(7):289CHEN J,SUN NN,SHAO YL,et al.Rapid detection of antipertensive chemicals adulterated in compound eucommia ulmoides capsule using TLC-SERS[J].Laser Optoelect Progr,2015,52(7):289
[16]de LUCA E,REDAELLI M,ZAFFINO C,et al.A SERS and HPLCstudy of traditional dyes from native Chinese plants[J].Vibrat Spectrosc,2018,95(1):62
[17]HOU R,TONG M,GAO W,et al.Investigation of degradation and penetration behaviors of dimethoate on and in spinach leaves using in situ SERS and LC-MS[J].Food Chem,2017,237(3):305
[2]董晶晶,郝翔.激光拉曼光谱法测定中药三七花中非法添加的化学降压药[J].中国药师,2017,20(2):391DONG JJ,HAO X.Identification of hypotensive drugs illegally added to flower buds of Panax Notoginseng by laser Raman spectraosocpy[J].China Pharm,2017,20(2):391
[3]甘盛,韩婷,李志成,等.减肥中成药中非法添加酚酞的拉曼光谱快速检测[J],中国实验方剂学杂志.2014,20(21):63GAN S,HAN T,LI ZC,et al.Rapid detection of adulterated phenolphthalein to Chinese pattern diet drugs by Raman spectroscopy[J].Chin J Exper Tradit Med Form,2014,20(21):63
[4]甘勇强,纪南,田萍,等.拉曼光谱快速检测减肥保健品中非法添加酚酞的研究[J].中国药师,2014,36(10):1675GAN YQ,JI N,TIAN P,et al.A Fast determination method for phenolphthalein illegally added into diet health products by Raman spectroscopy[J].China Pharm,2014,36(10):1675
[5]刘元瑞,葛海生,赵康虎,等.薄层原位表面增强拉曼光谱法检测中成药和保健品中添加的西地那非[J].药物分析杂志,2014,34(7):1241LIU RY,GE HS,ZHAO KH,et al.In-situ fast determination method for illegally added into traditional chinese medicine and diet health products by TLC-SERS[J].Chin J Pharm Anal,2014,34(7),1241
[6]李革,李菁.化妆品中非法添加甲硝唑的拉曼光谱快速筛查研究[J].中国药事,2016,30(4):303LI G,LI J.Rapid screening of metronidazole illegally added to cosmetics by Raman spectroscopy[J],Chin Pharm Aff,2016,30(4):303
[7]陈梦云.TLC-SERS法同时检测中成药中十余种掺伪化药的研究[D].广州:广东药科大学,2016CHEN MY.Rapid Detection of More Than 10 Chemicals Added in Traditional Chinese Medicine by TLC-SERS[D].Guangzhou:Gaungdong Pharmaceutical University,2016
[8]陈梦云,李晓,王磊,等.清热类中成药中非法添加化药的TLC-SERS研究[J],光散射学报,2015,27(4):326CHEN MY,LI X,WANG L,et al.Rapid detection of the chemicals added in traditional Chinese medicine for heat-clearing drugs by TLC-SERS[J].J Light Scatt,2015,27(4):326
[9]李丹,汪冰,李晓,等.表面增强拉曼光谱法快速鉴别非法染色的关黄柏药材[J].药学研究,2015,5(4):202LI D,WANG B,LI X,et al.Identification of dyeing adulteration in Amur Cork-tree Bark by surface enhanced Raman spectroscopy[J].J Pharm Res,2015,5(4),202
[10]李皓,朱青霞,柴逸峰,等.TLC-SERS法快速检测止咳平喘类中成药中4种添加化学成分[J].药物分析杂志,2014,34(4),693.LI H,ZHU QX,CHAI YF,et al.Rapid screening of the four chemical components illegally added in antitussive antiasthmatic drugs by TLC-SERS method[J].Chin J Pharm Anal,2014,34(4):693
[11]吴棉棉,武媚然,张彬彬,等.降压中成药中违禁添加化学成分的TLC-SERS法快速筛查[J].中国医药工业杂志,2017,48(1):82WU MM,WU MR,ZHANG BB,et al.Rapid screening of the chemical components illegally added in anti-hypertensive Chinese patent medicine by TLC-SERS method[J].Chin J Pharm,2017,48(1):82
[12]朱青霞,曹永兵,曹颖瑛,等.TLC-SERS法快速检测降压类中药中非法添加的四种化学成分[J].光谱学与光谱分析,2014,34(4):990ZHU QX,CAO YB,CAO YY,et al.Rapid detection of four antipertensive chemicals adulterated in traditional Chinese medicine for hypertension using TLC-SERS[J].Spectrosc Spect Anal,2014,34(4):990
[13]FANG F,QI Y,LU F,et al.Highly sensitive on-site detection of drugs adulterated in botanical dietary supplements using thin layer chromatography combined with dynamic surface enhanced Raman spectroscopy[J].Talanta,2016,146(1):351
[14]秦剑红.TLC-SERS联用法检测降糖中成药中添加的格列类药品[J].药学实践杂志,2014,32(03):206QIN JH.Detection of glinides adulterated in traditional Chinese medicine for diabetes by TLC-SERS[J].J Pharm Pract,2014,32(3):206
[15]陈娟,孙楠楠,邵亚兰,等.TLC-SERS法快速检测复方杜仲胶囊中非法添加化学药物的研究[J].激光与光电子学进展,2015,52(7):289CHEN J,SUN NN,SHAO YL,et al.Rapid detection of antipertensive chemicals adulterated in compound eucommia ulmoides capsule using TLC-SERS[J].Laser Optoelect Progr,2015,52(7):289
[16]de LUCA E,REDAELLI M,ZAFFINO C,et al.A SERS and HPLCstudy of traditional dyes from native Chinese plants[J].Vibrat Spectrosc,2018,95(1):62
[17]HOU R,TONG M,GAO W,et al.Investigation of degradation and penetration behaviors of dimethoate on and in spinach leaves using in situ SERS and LC-MS[J].Food Chem,2017,237(3):305