衍生化-磁固相萃取高效液相色谱荧光检测内分泌干扰物
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摘要
食品与环境中的极微量内分泌干扰物即可严重干扰人体的内分泌功能,对人类健康构成巨大威胁。本研究通过荧光衍生化和磁固相萃取(MDSPE)样品前处理技术,建立了高效液相色谱荧光检测(HPLC-FLD)三氯生(TCS)、β-雌二醇(E2)、壬基酚(NP)和4-辛基酚(OP)的分析方法。以2'-甲酰氯罗丹明(RHB-Cl)为柱前衍生试剂,考察并优化了衍生化和MDSPE实验条件。结果表明,最优的衍生化条件为在室温(20℃)、p H 9.5的Na_2CO_3-NaHCO_3缓冲液条件下,衍生反应5 min得到衍生产物。磁性氧化石墨烯作为MDSPE吸附剂,用量15 mg,萃取时间15 min,洗脱剂为甲醇-乙酸(9∶1,V/V)、洗脱时间3 min,能够实现4种内分泌干扰物衍生物的富集与净化。在优化的色谱条件下,12 min内实现了4种衍生物的分离。荧光激发和发射波长分别为554和570 nm,方法检出限为1.1～1.9 ng/L,定量限为4.0～7.5 ng/L,线性、精密度和回收率良好。与已报道的方法相比,本方法具有简便、快速、灵敏度高等优势,可用于牛奶、牙膏、生活废水中TCS、E2、NP和OP的测定,为食品和饮用水安全监督提供了一种新方法。
A new high performance liquid chromatography-fluorescence detection( HPLC-FLD) method was developed by fluorescence derivatization and magnetic dispersive solid phase extraction( MDSPE) technology for the determination of triclosan( TCS),β-estradiol( E2),nonylphenol( NP),and 4-octylphenol( OP).With 2'-carbonyl chloride rosamine( RHB-Cl) as precolumn derivatization reagent,the derivatization and MDSPE conditions were investigated. The results showed that the maximum derivatives were obtained after derivatizationin for 5 min in Na2 CO3-NaHCO3 buffer solution at pH 9.5 at room temperature( 20℃). Under the optimized conditions including using magnetic graphene oxide as MDSPE adsorbent( 15 mg),extraction for 5 min,methanol/acetic acid( 9∶ 1,V/V) as elution agent,and elution for 3 min,four endocrine disruptor compound derivatives were enriched and purified. Under optimized chromatographic conditions,the four derivatives were separated within 12 min. The fluorescence excitation and emission wavelengths were set at 554 nm and 570 nm,respectively,achieving highest detection sensitivity for four endocrine disruptor compounds derivatives. The limits of detection( LODs) were in the range of 1.1-1.9 ng/L,and the limits of quantification( LOQs) were in the range of 4.0-7.5 ng/L. This method had good linearity,precision and recovery results,and also showed obvious advantages such as simplicity,rapidity and high sensitivity comparing to the reported methods. It was a convenient and validated method for the routine analysis of endocrine disruptor compounds in milk,toothpaste and waste water,and could provide a new method for food,drinking and water safety supervision.
A new high performance liquid chromatography-fluorescence detection( HPLC-FLD) method was developed by fluorescence derivatization and magnetic dispersive solid phase extraction( MDSPE) technology for the determination of triclosan( TCS),β-estradiol( E2),nonylphenol( NP),and 4-octylphenol( OP).With 2'-carbonyl chloride rosamine( RHB-Cl) as precolumn derivatization reagent,the derivatization and MDSPE conditions were investigated. The results showed that the maximum derivatives were obtained after derivatizationin for 5 min in Na2 CO3-NaHCO3 buffer solution at pH 9.5 at room temperature( 20℃). Under the optimized conditions including using magnetic graphene oxide as MDSPE adsorbent( 15 mg),extraction for 5 min,methanol/acetic acid( 9∶ 1,V/V) as elution agent,and elution for 3 min,four endocrine disruptor compound derivatives were enriched and purified. Under optimized chromatographic conditions,the four derivatives were separated within 12 min. The fluorescence excitation and emission wavelengths were set at 554 nm and 570 nm,respectively,achieving highest detection sensitivity for four endocrine disruptor compounds derivatives. The limits of detection( LODs) were in the range of 1.1-1.9 ng/L,and the limits of quantification( LOQs) were in the range of 4.0-7.5 ng/L. This method had good linearity,precision and recovery results,and also showed obvious advantages such as simplicity,rapidity and high sensitivity comparing to the reported methods. It was a convenient and validated method for the routine analysis of endocrine disruptor compounds in milk,toothpaste and waste water,and could provide a new method for food,drinking and water safety supervision.
引文
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20 Hao Y,Gao R X,Shi L,Liu D C,Tang Y H,Guo Z J. J. Chromatogr. A,2015,1396:7-16
21 JING Tao,DAI Ying,MA Xiao-Juan,HUANG Bai-Biao. Chinese Optics,2016,9(1):1-15荆涛,戴瑛,马晓娟,黄柏标.中国光学,2016,9(1):1-15
2 Dotan P,Yeshayahu M,Odeh W,Gordon-Kirsch N,Groisman L,Al-Khateeb N,Rabbo A A,Tal A,Arnon S.J. Environ Manage.,2017,204(1):355-364
3 ZHANG Pin,ZHANG Jing,CHEN Jie-Jun,DUAN He-Jun,SHAO Bing. Chinese J. Anal. Chem.,2014,42(12):1811-1817张品,张晶,陈洁君,段鹤君,邵兵.分析化学,2014,42(12):1811-1817
4 Nehring I,Grajewska A,Falkowska L,Staniszewska M,Saniewska D. J. Environ Pollut.,2017,231(1):1005-1012
5 LIAO Tao,WU Xiao-Cui,WANG Shao-Hua,XIE Song-Guang,XIONG Guang-Quan,GENG Sheng-Rong,LI Xin,JU Xiao-Yan,HU Xiao-Bo. Chinese J. Anal. Chem.,2013,41(3):422-426廖涛,吴晓翠,王少华,谢松光,熊光权,耿胜荣,李新,鉏晓艳,胡筱波.分析化学,2013,41(3):422-426
6 NIU Yu-Min,ZHANG Jing,ZHANG Shu-Jun,SHAO Bing. Chinese J. Anal. Chem.,2012,40(4):534-538牛宇敏,张晶,张书军,邵兵.分析化学,2012,40(4):534-538
7 SUNXiu-Wu,ZHAGN Yuan-Biao,LIN Hui,LIN Hong-Mei,KUANG Wei-Ming,HUANG Hai-Ning,JI Wei-Dong.Chinese J. Anal. Sci.,2013,29(2):149-153孙秀武,张元标,林辉,林红梅,邝伟明,黄海宁,暨卫东.分析科学学报,2013,29(2):149-153
8 LIU Jun,TANG Cai-Ming,XIONG Song-Song,FAN Yu-Juan,ZHENG Ke,PENG Xian-Zhi. Chinese J. Anal. Chem.,2017,45(3):434-440刘珺,唐才明,熊松松,凡玉娟,郑可,彭先芝.分析化学,2017,45(3):434-440
9 YAN Wei,LIN Jin-Ming.Chinese J. Anal. Chem.,2010,38(4):598-606严炜,林金明.分析化学,2010,38(4):598-606
10 Alabi A,Caballero-Casero N,Rubio S. J. Chromatogr. A,2014,1336:23-33
11 Martínez N A,Pereira S V,Bertolino F A,Schneider R J,Messina J A,Raba J. Anal. Chim. Acta,2012,723:27-32
12 ZHAO Xian-En,LYU Tao,WEI Na,ZHU Shu-Yun,YOU Jin-Mao. Chinese J. Anal. Chem.,2014,42(11):1629-1633赵先恩,吕涛,魏娜,朱树芸,尤进茂.分析化学,2014,42(11):1629-1633
13 Qi B L,Liu P,Wang Q Y,Cai W J,Yuan B F,Feng Y Q. TrA C-Trend. Anal. Chem.,2014,59:121-132
14 He Y R,Zhao X E,Wang R J,Wei N,Sun J,Dang J,Chen G,Liu Z Q,Zhu S Y,You J M. J. Agric. Food Chem.,2016,64(43):8225-8234
15 HUANG Wei,DING Jun,FENG Yu-Qi. Chinese J. Anal. Chem.,2012,40(6):830-834黄维,丁俊,冯钰锜.分析化学,2012,40(6):830-834
16 Zheng L F,Zhao X E,Ji W H,Wang X,Tao Y D,Sun Jing,Xu Y Q,Wang X,Zhu S Y,You J M. J. Chromatogr. A,2018,1532:30-39
17 Ren H,Kulkarni D D,Kodiyath R,Choi I,Tsukruk V V. ACS Appl. Mater. Interfaces,2014,6(4):2459-2470
18 HAN Weng,YANG Yun-Xu,XU Tai-Lin,SHENG Rui-Long,LI Bin-Lian,ZHU Hai-Bo. J. Imag. Sci. Photochem.,2015,33(02):144-153韩文,杨运旭,许太林,盛瑞隆,李斌莲,朱海波.影像科学与光化学,2015,33(02):144-153
19 Zou Y M,Zhang Z,Shao X L,Chen Y,Wu X Y,Yang L Q,Zhu J J,Zhang D M. J. Water Sci Technol.,2014,69(5):1028-1035
20 Hao Y,Gao R X,Shi L,Liu D C,Tang Y H,Guo Z J. J. Chromatogr. A,2015,1396:7-16
21 JING Tao,DAI Ying,MA Xiao-Juan,HUANG Bai-Biao. Chinese Optics,2016,9(1):1-15荆涛,戴瑛,马晓娟,黄柏标.中国光学,2016,9(1):1-15