基于分子印迹富集及HPLC-ICP-MS检测海产品中三丁基锡的研究
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摘要
本文以甲基丙烯酸为功能单体,三丁基锡为模板分子,二甲基丙烯酸乙二醇酯为交联剂,乙腈为致孔剂,采用分子印迹技术并联合高效液相色谱电感耦合等离子质谱(HPLC-ICP-MS)成功地制备了能特异性识别TBT的MIPs。所合成的MIPS经过选择识别、吸附动力学及再生性能等检测,对三丁基锡具有良好的吸附能力和高选择识别能力。并以分子印迹聚合物作为固相萃取吸附剂分离富集TBT,联合高效液相色谱-电感耦合等离子质谱(HPLC-ICP-MS)检测海水及海产品中的三丁基锡。结果表明,用传统分子印迹聚合物作为吸附剂富集分离,在海水、贻贝和大黄鱼样品中检测限(LOD)分别为0.06μg/L、4.0 ng/g和5.0 ng/g,加标回收率分别是61.5%~84.5%、76.2%~93.9%和74.2%~93.3%,线性范围分别是0.1μg/L~30μg/L、5 ng/g~50 ng/g和5 ng/g~500 ng/g。为海产品中有机锡等有机金属的检测提供方法。
With methacrylate as functional monomer,tributyltin(TBT) as template molecule,ethylene glycol dimethyl ester as crosslinking agent,and acetonitrile as porogen,a molecularly imprinted polymer(MIP) with specific recognition towards TBT was successfully prepared using molecular imprinting technology combined with high performance liquid chromatography-inductively coupled plasma-mass spectrometry(HPLC-ICP-MS).Experiments on selective recognition,adsorption kinetics,and regeneration performance showed that the synthesized MIPS had a good adsorption capacity and high selective recognition ability for TBT.Additionally,MIPs were used as solid phase extraction sorbents to separate and enrich TBT,and the TBT in seawater and seafood was detected using HPLC-ICP-MS.The results indicated that,compared with traditional MIPs as an adsorbent for enrichment and separation,the limits of detection(LODs) for seawater,mussels,and large yellow croaker samples were 0.06 μg/L,4.0 ng/g,and 5.0 ng/g,respectively,the recoveries were 61.5%~84.5%,76.2%~93.9%,and 74.2%~93.3%,respectively,and the linear ranges were 0.1 μg/L~30 μg/L,5 ng/g~50 ng/g,and 5 ng/g~500 ng/g,respectively.This study provides a method for the detection of organic tin and other organometallic compounds in seafood.
With methacrylate as functional monomer,tributyltin(TBT) as template molecule,ethylene glycol dimethyl ester as crosslinking agent,and acetonitrile as porogen,a molecularly imprinted polymer(MIP) with specific recognition towards TBT was successfully prepared using molecular imprinting technology combined with high performance liquid chromatography-inductively coupled plasma-mass spectrometry(HPLC-ICP-MS).Experiments on selective recognition,adsorption kinetics,and regeneration performance showed that the synthesized MIPS had a good adsorption capacity and high selective recognition ability for TBT.Additionally,MIPs were used as solid phase extraction sorbents to separate and enrich TBT,and the TBT in seawater and seafood was detected using HPLC-ICP-MS.The results indicated that,compared with traditional MIPs as an adsorbent for enrichment and separation,the limits of detection(LODs) for seawater,mussels,and large yellow croaker samples were 0.06 μg/L,4.0 ng/g,and 5.0 ng/g,respectively,the recoveries were 61.5%~84.5%,76.2%~93.9%,and 74.2%~93.3%,respectively,and the linear ranges were 0.1 μg/L~30 μg/L,5 ng/g~50 ng/g,and 5 ng/g~500 ng/g,respectively.This study provides a method for the detection of organic tin and other organometallic compounds in seafood.
引文
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[22]Zhang Y,Liu R J,Hu Y L,et al.Microwave heating in preparation of magnetic molecularly imprinted polymer beads for trace triazines analysis in complicated samples[J].Anal Chem.,2009,81(3):967
[23]Luo X B,Zhan Y C,Huang Y N,et al.Removal of water-soluble acid dyes from water environment using a novel magnetic molecularly imprinted polymer[J].J Hazard Mater,2011,187(1-3):274-282
[24]Liu L L,Wang J T,Chung K N,et al.Distribution and accumulation of organotin species in seawater,sediments and organisms collected from a Taiwan mariculture area[J].Mar Pollut Bull,2011,63(5-12):535-540
[25]周红,朱明,等.功能化四氧化三铁的合成和表征及其对钙离子的吸附[J].武汉工程大学学报,2013,35(4):14-20ZHOU Hong,ZHU Ming,et al.Synthesis and adsorption of calcium ions of functionalized core-shell Fe3O4 nanoparticles[J].J.Wuhan Inst.Tech.,2013,35(4):14-20
[26]Li Y,Li X,Chu J,et al.Synthesis of core-shell magnetic molecular imprinted by the surface RAFT polymerization for the fast and selective removal of endocrine disrupting chemicals from aqueous solutions[J].Environ.Pollut.,2010,158(6):2317-2323
[27]Wang S B,Ng C W,Wang W T,et al.A comparative study on the adsorption of acid and reactive dyes on multiwall carbon nanotubes in single and binary dye systems[J].J.Chem.Eng.Data,2012,57(5):1563-1569
[2]Ye L,Mosbach K.Molecularfy imprinted microspheres as antibody binding mimics[J].React.Funeut.,Polym.,2001,48(12):149-157
[3]Zhang M L,Me J p,Zhou Q,et al.Online solid-phase extraction of ceramides from yeast with ceramideШimprinted monolith[J].J.Chromatogra.A,2003,222(14):173-183
[4]Ebarvia B S,Binag C A,Sevilla F.Biomimetic piezoelectric quartz sensor for caffeine based on molecularly imprinted polymer[J].Anal Bioanal Chem.,2004,378(5):1331-337
[5]Wuiff G.Enzyme-like catalysis by molecularly imprinted polymers[J].Chem.Rev.,2002,102(l):1-27
[6]Turiel E,Martin2Esteban A,Femandez P,et al.Molecular recognition in a propazine-imprinted polymer and its application to the determination of triazines in environmental samples[J].Anal.Chem.,2001,73(51):33-41
[7]Lars LAndersson.Molecular imprinting for drμg bioanalysis a review on the application of imprinted polymers to solid-phase extraction and binding assay[J].Journal of Chromatography B,2000,739(1):63-73
[8]Christine Widstrand,redrik Larsson,Maurizio Fiori,et al.Evaluation of MISPE for the multi-residue extraction of B-agonists from calves urine[J].Journal of Chromatography B,2004,804:85-91
[9]Viktor Koch kodan,Wilfried weigel,Mathias Ulbricht.Molecularly imprinted composite membranes for selective binding of desmetryn from aqueous solutions[J].Desalination,2002,149:323-328
[10]范立民.三丁基锡(TBT)对奥利亚罗非鱼精巢细胞凋亡影响的研究[D].南京:南京农业大学,2010FAN Li-min.Study on spermary cells apoptosis induced by tbtcl in Oreochromis aureus[D].Nanjing:Nanjing Agricultural University,2010
[11]Ema M,Haraz ono A,Miyawaki E,et al.Effect of the day of administration on the developmental toxicity of tributyltin chloride in rats[J].Arch.Environ.C ontam.Toxicol.,1997,33(1):90-96
[12]Y amabe Y,Hoshino A,Imura N,et al.Enhancement of androgen dependent transcription and cell proliferation by tributyltin and triphenyltin in human prostate cancer cells[J].Toxicol.Appl.Pharmacol.,2000,169(2):177-184
[13]柳英霞,李娟,鄢爱平,等.食品中有机锡化合物分析方法研究进展[J].食品科学,2010,31(19):435-442LIU Ying-xia,LI Juan,YAN Ai-ping,et al.Research progress in analytical methods of organotin in food[J].Food Science,2010,31(19):435-442
[14]Sellergren B.Direct drug determination by selective sample enrichment on an imprinted polymer[J].Ana.Chem.,1994,66:1578-1582
[15]侯信,张哲国,高博,等.制备单分散聚丙烯酰胺微球的方法:中国,200510015571[P]2006-03-29HOU Xin,ZHANG Zhe-guo,GAO Bo,et al.Method for preparing monodisperse polyacrylamide sphere:China,200510015571[P]2006-03-29
[16]贺小进,谭天伟,戚以政,等.球形壳聚糖树脂制备方法及吸附性能研究[J].离子交换与吸附,2000,16:47-53HE Xiao-jin,TAN Tian-wei,QI Yi-zheng,et al.Study on synthesis and adsorption properties to metal of chitosan chelated resins[J].Ion Exchange and Adsorption,2000,16:47-53
[17]雷晓康.ICP-MS及其联用技术用于海产品和水样中锡形态分析的研究[D].南昌:南昌大学理学院化学系,2012LEI Xiao-kang.Study on the speciation analysis of organotin in seafood and water samples by ICP-MS and its hyphenated techniques[D].Nanchang:Department of Chemistry,Faculty of Science,Nanchang University,2012
[18]朱珊珊.基于分子印迹技术对海产品及海水中痕量有机锡的检测方法研究[D].宁波:宁波大学,2013ZHU Shan-shan.Determination method research based on molecular imprinting technolgy in seawater and seafood for trace organotin compounds[D].Ningbo:Ningbo University,2013
[19]Mercedes Gallego-Gallegos,María Liva,Riansares Mu?oz Olivas,et al.Focused ultrasound and molecularly imprinted polymers:A new approach to organotin analysis in environmental samples[J].Chromatography A,2006,1114(1):82-88
[20]Julia Saloni,Pawel Lipkowski,Samuel S R Dasary,et al.Theoretical study of molecular interactions of TNT,acrylic acid,and ethylene glycol dimethacrylate-elements of molecularly imprinted polymer modeling process[J].Polymer,2011,52(4):1206-1216
[21]Shan-shan Zhu,Fu-tao Hu,Ting Yang,et al.Synthesis and characterization of a molecularly imprinted polymer for the determination of trace tributyltin in seawater and seafood by liquid chromatography-tandem mass spectroscopy[J].J.Chromatogr.B,2013,921(6):21-26
[22]Zhang Y,Liu R J,Hu Y L,et al.Microwave heating in preparation of magnetic molecularly imprinted polymer beads for trace triazines analysis in complicated samples[J].Anal Chem.,2009,81(3):967
[23]Luo X B,Zhan Y C,Huang Y N,et al.Removal of water-soluble acid dyes from water environment using a novel magnetic molecularly imprinted polymer[J].J Hazard Mater,2011,187(1-3):274-282
[24]Liu L L,Wang J T,Chung K N,et al.Distribution and accumulation of organotin species in seawater,sediments and organisms collected from a Taiwan mariculture area[J].Mar Pollut Bull,2011,63(5-12):535-540
[25]周红,朱明,等.功能化四氧化三铁的合成和表征及其对钙离子的吸附[J].武汉工程大学学报,2013,35(4):14-20ZHOU Hong,ZHU Ming,et al.Synthesis and adsorption of calcium ions of functionalized core-shell Fe3O4 nanoparticles[J].J.Wuhan Inst.Tech.,2013,35(4):14-20
[26]Li Y,Li X,Chu J,et al.Synthesis of core-shell magnetic molecular imprinted by the surface RAFT polymerization for the fast and selective removal of endocrine disrupting chemicals from aqueous solutions[J].Environ.Pollut.,2010,158(6):2317-2323
[27]Wang S B,Ng C W,Wang W T,et al.A comparative study on the adsorption of acid and reactive dyes on multiwall carbon nanotubes in single and binary dye systems[J].J.Chem.Eng.Data,2012,57(5):1563-1569