衍生瓜环固相微萃取搅拌棒-高效液相色谱测定食品中残留雌激素
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摘要
建立了基于单羟基取代七元瓜环的固相微萃取搅拌棒(SBSE)-液体解析(LD)-高效液相色谱(HPLC)-紫外吸收检测器(UV)同时测定动物源性食品(猪肉,鸡肉)中残留的3种雌激素(双酚A(BPA)、雌二醇(E2)和己烯雌酚(DES))的测定方法。以单羟基七元瓜环(Q7-OH)和羟基聚二甲基硅氧烷(PDMS-OH)为固定相,采用溶胶-凝胶法制备了PDMS/Q7-OH涂层的固相微萃取小棒。萃取小棒表面粗糙、多孔、制备重复精度好(RSD≤8.4%)、使用寿命长。萃取机理的考察实验结果表明,小棒萃取效率的提高源于七元瓜环对分析物具有较好的分子识别能力。在优化的实验条件下,建立的PDMS/Q7-OH SBSE-LD-HPLC-UV分析方法对3种雌激素的检出限为0.05～0.56μg/L,富集倍数19～25倍,线性范围在0.2～5000μg/L之间,RSD为3.9%～7.5%(n=5,C=100μg/L),3个浓度水平的平均回收率(n=3)在72.7%～109.2%范围内。本方法简单、灵敏、选择性好,可用于动物源性食品(猪肉,鸡肉)中残留雌激素的检测。
A method of stir bar sorptive extraction (SBSE) based on monohydroxyl cucurbit7 uril (Q7-OH)-liquid desorption (LD)-high performance liquid chromatography (HPLC)-ultraviolet detection was developed for measurement of three residual estrogens (bisphenol A,estradiol and diethylstillbestrol) from animalderived foods (pork and chicken samples). The hydroxyl polydimethylsiloxane (PDMS-OH)/Q7-OH-coated stir bar was conducted by the sol-gel technique with the synthesized Q7-OH as a selective stationary phase. The innovative SBSE exhibited a rough and porous surface structure,a good preparation reproducibility (RSD≤8.4%) and a long lifespan. Extraction mechanism indicated that the increase of extraction efficiency was attributed to the excellent molecular recognition of Q7 towards analytes. Under the optimal experimental conditions,the limits of detection of the developed PDMS/Q7-OH SBSE-LD-HPLC-UV method were 0.05-0.56 μg/L for the target estrogens with enrichment factors of 19-25 folds,the dynamic linear range was0.2-5000 μg/L,and the RSDs were in the range of 3. 9%-7. 5% (n = 5,C = 100 μg/L). The mean recoveries (n = 3) at three different concentration levels were 72. 7%-109. 2%. The developed method was simple,sensitive,and selective,and was successfully applied to the analysis of estrogens in animal-derived foods (pork and chicken samples).
A method of stir bar sorptive extraction (SBSE) based on monohydroxyl cucurbit7 uril (Q7-OH)-liquid desorption (LD)-high performance liquid chromatography (HPLC)-ultraviolet detection was developed for measurement of three residual estrogens (bisphenol A,estradiol and diethylstillbestrol) from animalderived foods (pork and chicken samples). The hydroxyl polydimethylsiloxane (PDMS-OH)/Q7-OH-coated stir bar was conducted by the sol-gel technique with the synthesized Q7-OH as a selective stationary phase. The innovative SBSE exhibited a rough and porous surface structure,a good preparation reproducibility (RSD≤8.4%) and a long lifespan. Extraction mechanism indicated that the increase of extraction efficiency was attributed to the excellent molecular recognition of Q7 towards analytes. Under the optimal experimental conditions,the limits of detection of the developed PDMS/Q7-OH SBSE-LD-HPLC-UV method were 0.05-0.56 μg/L for the target estrogens with enrichment factors of 19-25 folds,the dynamic linear range was0.2-5000 μg/L,and the RSDs were in the range of 3. 9%-7. 5% (n = 5,C = 100 μg/L). The mean recoveries (n = 3) at three different concentration levels were 72. 7%-109. 2%. The developed method was simple,sensitive,and selective,and was successfully applied to the analysis of estrogens in animal-derived foods (pork and chicken samples).
引文
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26 Vinciguerra B,Cao L P,Cannon J R,Zavalij P Y,Fenselau C,Isaacs L.J.Am.Chem.Soc.,2012,134(31):13133-13140
27 Dong N,He J,Li T,Peralta A,Avei M R,Ma M F,Kaifer A E.J.Org.Chem.,2018,83(10):5467-5473
28 Sarafraz A,Amiri A,Rounaghi G,Eshtiagh-Hosseini H.Anal.Chim.Acta,2012,720:134-141
29 Liu Y,Kang S Z.Sci.China Ser.B,2001,44(3):260-267
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31 Yan W,Li Y,Zhao L X,Lin J M.J.Chromatogr.A,2009,1216(44):7539-7545
32 Hu C,He M,Chen B B,Hu B.J.Agr.Food Chem.,2012,60(42):10494-10500
2 Giese R W.J.Chromatogr.A,2003,1000(1):401-412
3 Pacakova V,Loukotkova L,Bosakova Z,Stulik K.J.Sep.Sci.,2009,32(5-6):867-882
4 LIN Xiao-Li,LI Ning,HUO Feng,DONG Yan-Feng,PENG Wei.Journal of Instrumental Analysis,2016,35(3):322-326林小莉,李宁,霍峰,董艳峰,彭玮.分析测试学报,2016,35(3):322-326
5 Soliman M,Pedersen J,Suffet I H.J.Chromatogr.A,2004,1029(1-2):223-237
6 Bravo J C,Garcinuno R M,Fernandez P,Durand J S.Anal.Bioanal.Chem.,2007,388(5-6):1039-1045
7 LIAO Tao,WU Xiao-Cui,WANG Shao-Hua,XIE Song-Guang,XIONG Guang-Quan,GENG Sheng-Rong,LI Xin,ZU 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
8 LI Yu,LIU Jian-Lin,ZHANG Chen,WANG Xia-Jiao.Chinese J.Anal.Chem.,2012,40(1):107-112李鱼,刘建林,张琛,王夏娇,分析化学,2012,40(1):107-112
9 Chang C C,Huang S D.Anal.Chim.Acta,2010,662(1):39-43
10 Hu Y L,Wang Y Y,Chen X G,Hu Y F,Li G K.Talanta,2010,80(5):2099-2105
11 Liu M H,Li M J,Qiu B,Chen G N.Anal.Chim.Acta,2010,663(1):33-38
12 Huang X J,Yuan D X,Huang B L.Talanta,2008,75(1):172-177
13 David F,Sandra P.J.Chromatogr.A,2007,1152(1-2):54-69
14 Nogueira J M F.Tr AC-Trend.Anal.Chem.,2015,71:214-223
15 Nogueira J M F.Anal.Chim.Acta,2012,757:1-10
16 Camino-Sánchez F J,Rodríguez-Gómez R,Zafra-Gómez A,Santos-Fandila A,Vílchez J L.Talanta,2014,130:388-399
17 Almeida C,Nogueira J M F.J.Pharm.Biomed.Anal.,2006,41(4):1303-1311
18 Huang X J,Lin J B,Yuan D X,Hu R Z.J.Chromatogr.A,2009,1216(16):3508-3511
19 Hu Y L,Zheng Y J,Zhu F,Li G K.J.Chromatogr.A,2007,1148(1):16-22
20 Lee J W,Samal S,Selvapalam N,Kim H J,Kim K.Acc.Chem.Res.,2003,36(8):621-630
21 Ong W,Kaifer A E.Organometallics,2003,22(21):4181-4183
22 CHEN Shi-Yan,CUI Xiao-Wei,WANG Chuan-Zeng,NI Xin-Long,MA Pei-Hua,ZHANG Jian-Xin.Chem.J.Chinese Universities,2015,36(10):1919-1923陈仕焰,崔晓伟,王传增,倪新龙,马培华,张建新.高等学校化学学报,2015,36(10):1919-1923
23 Rahul V P,Jayshree K K,Shridhar P G.J.Inc.Phe.Mac.Chem.,2010,66:371-380
24 Isaacs L.Chem.Commun.,2009,6:619-629
25 Dong N,Li T,Luo Y J,Shao L,Tao Z,Zhu C.J.Chromatogr.A,2016,1470:9-18
26 Vinciguerra B,Cao L P,Cannon J R,Zavalij P Y,Fenselau C,Isaacs L.J.Am.Chem.Soc.,2012,134(31):13133-13140
27 Dong N,He J,Li T,Peralta A,Avei M R,Ma M F,Kaifer A E.J.Org.Chem.,2018,83(10):5467-5473
28 Sarafraz A,Amiri A,Rounaghi G,Eshtiagh-Hosseini H.Anal.Chim.Acta,2012,720:134-141
29 Liu Y,Kang S Z.Sci.China Ser.B,2001,44(3):260-267
30 Fabes B D,Uhlmann D R.J.Am.Ceram.Soc,1990,73(4):978-988
31 Yan W,Li Y,Zhao L X,Lin J M.J.Chromatogr.A,2009,1216(44):7539-7545
32 Hu C,He M,Chen B B,Hu B.J.Agr.Food Chem.,2012,60(42):10494-10500