水胺硫磷分子印迹固相微萃取涂层的制备及在果蔬水胺硫磷农药检测中的应用
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摘要
以聚乙二醇为功能单体,水胺硫磷为模板分子,采用溶胶-凝胶技术,制备水胺硫磷分子印迹固相微萃取涂层,并建立顶空固相微萃取与气相色谱(HS-SPME/GC)联用检测果蔬中水胺硫磷残留量的方法。结果表明,制备的印迹涂层对水胺硫磷具有较高的选择性,且萃取能力大大高于非印迹涂层及常用商用涂层。在最优条件下,建立的检测方法在10～10 000μg/kg范围内线性相关系数为0.999 6,检出限为5.6μg/kg,5次重复实验所得相对标准偏差为2.29%。应用该检测方法测定黄瓜、蕃茄、苹果、梨和大白菜等5种果蔬基质中水胺硫磷含量时,均未有水胺硫磷检出,在5种基质中加标回收率均在89.4%～106.6%之间。
An isocarbophos molecularly imprinted solid-phase microextraction(MISPME)coating was prepared by sol-gel technology with polyethylene glycol as a monomer and isocarbophos as a template,and a headspace solid phase microextraction method coupled with gas chromatography(HSSPME/GC)for the determination of isocarbophos in fruits and vegetables was established.Results showed that the imprinted coating had very good selectivity to isocarbophos,and its extraction capability was better than the non-imprinted fiber and commercial fibers.At the optimum conditions,the proposed method was linear in the range of 10-10 000μg/kg with a coefficient of 0.999 6.The limit of detection was 5.6μg/kg.The relative standard deviation of 5 replicates was 2.29%.The method was used for the determination of isocarbophos in 5 kinds of real samples including cucumber,tomato,apple,pear and cabbage.The results indicated that no residue of isocarbophos was detected in these samples.Satisfactory recoveries of 89.4%-106.6% were obtained in these matrices,indicating the accuracy of the method.
An isocarbophos molecularly imprinted solid-phase microextraction(MISPME)coating was prepared by sol-gel technology with polyethylene glycol as a monomer and isocarbophos as a template,and a headspace solid phase microextraction method coupled with gas chromatography(HSSPME/GC)for the determination of isocarbophos in fruits and vegetables was established.Results showed that the imprinted coating had very good selectivity to isocarbophos,and its extraction capability was better than the non-imprinted fiber and commercial fibers.At the optimum conditions,the proposed method was linear in the range of 10-10 000μg/kg with a coefficient of 0.999 6.The limit of detection was 5.6μg/kg.The relative standard deviation of 5 replicates was 2.29%.The method was used for the determination of isocarbophos in 5 kinds of real samples including cucumber,tomato,apple,pear and cabbage.The results indicated that no residue of isocarbophos was detected in these samples.Satisfactory recoveries of 89.4%-106.6% were obtained in these matrices,indicating the accuracy of the method.
引文
[1]胡媛,刘文民,周艳明,等.固相微萃取-气相色谱法测定红葡萄酒中残留的有机磷农药[J].色谱,2006,24(3):290-293.
[2]ABDULRA'UF L B,HAMMED W A,TAN G H.SPME fibers for the analysis of pesticide residues in fruits and vegetables:a review[J].Critical reviews in analytical chemistry,2012,42(2):152-161.
[3]李曌,张雪娜,李秀娟.基于溶胶-凝胶技术的乐果分子印迹固相微萃取涂层的评价及应用[J].食品安全质量检测学报,2015,6(12):4719-4725.
[4]ZHANG H,YAO R,WANG N,et al.Soluble molecularly imprinted polymer-based potentiometric sensor for determination of bisphenol AF[J].Analytical chemistry,2018,90(1):657-662.
[5]FENG S,WEI X,ZHONG L,et al.A novel molecularly imprinted photoelectrochemical sensor based on g-C3N4-AuNPs for the highly sensitive and selective detection of triclosan[J].E-lectroanalysis,2018,30(2):320-327.
[6]WACKERLIG J,SCHIRHAGL R.Applications of molecularly imprinted polymer nanoparticles and their advances toward industrial use:a review[J].Analytical chemistry,2016,88(1):250-261.
[7]ZHAO Q L,ZHOU J,ZHANG L S,et al.Coatings of molecularly imprinted polymers based on polyhedral oligomeric silsesquioxane for open tubular capillary electrochromatography[J].Talanta,2016,152:277-282.
[8]KONG Y,ZHAO W,YAO S P,et al.Molecularly imprinted polypyrrole prepared by electrodeposition for the selective recognition of tryptophan enantiomers[J].Journal of applied polymer science,2010,115(4):1952-1957.
[9]SUN G,LIU Y,AHAT H,et al.“Two-dimensional”molecularly imprinted solid-phase extraction coupled with crystallization and high performance liquid chromatography for fast semipreparative purification of tannins from pomegranate husk extract[J].Journal of chromatography A,2017,1505(7):35-42.
[10]WANG G N,YANG K,LIU H Z,et al.Molecularly imprinted polymer-based solid phase extraction combined high performance liquid chromatography for determination of fluoroquinolones in milk[J].Analytical methods,2016,8(27):5511-5518.
[11]ATLABACHEW M,TORTO N,CHANDRAVANSHI B S,et al.A(-)-norephedrine-based molecularly imprinted polymer for the solid-phase extraction of psychoactive phenylpropylamino alkaloids from Khat(Catha edulis Vahl.Endl.)chewing leaves[J].Biomed chromatogr,2016,30(7):1007-1015.
[12]祖广权,赵琪,谭策,等.分子印迹固相萃取-超高效液相色谱串联质谱法测定猪肉中磺胺二甲氧嗪[J].分析测试学报,2017,36(3):292-296.
[13]李蓉,储大可,高永清,等.复合分子印迹固相萃取-HPLC-MS/MS法测定植物源性食品中多种农药残留[J].分析测试学报,2015,34(8):907-912.
[14]LAI C,WANG M M,ZENG G M,et al.Synthesis of surface molecular imprinted TiO2/graphene photocatalyst and its highly efficient photocatalytic degradation of target pollutant under visible light irradiation[J].Applied surface science,2016,390:368-376.
[15]RESMINI M.Molecularly imprinted polymers as biomimetic catalysts[J].Analytical and bioanalytical chemistry,2012,402(10):3021-3026.
[16]KOSTER E H M,CRESCENZI C,HOEDT W D,et al.Fibers coated with molecularly imprinted polymers for solid-phase microextraction[J].Analytical chemistry,2001,73(13):3140-3145.
[17]MULLETT W M,MARTIN P,PAWLISZYN J.In-tube molecularly imprinted polymer solid-phase microextraction for the selective determination of propranolol[J].Analytical chemistry,2001,73(11):2383-2389.
[18]WANG Y L,GAO Y L,WANG P P,et al.Sol-gel molecularly imprinted polymer for selective solid phase microextraction of organophosphorous pesticides[J].Talanta,2013,115(17):920-927.
[19]LI J W,WANG Y L,YAN S,et al.Molecularly imprinted calixarene fiber for solid-phase microextraction of four organophosphorous pesticides in fruits[J].Food chemistry,2016,192:260-267.
[20]中华人民共和国国家卫生和计划生育委员会,中华人民共和国农业部国家食品药品监督管理总局.GB 2763-2016,食品安全国家标准:食品中农药最大残留限量[S].北京:中国标准出版社,2017.
[21]HE J,LV R,ZHAN H,et al.Preparation and evaluation of molecularly imprinted solid-phase micro-extraction fibers for selective extraction of phthalates in an aqueous sample[J].Analytica chimica acta,2010,674(1):53-58.
[22]KHORRAMI A R,NAROUENEZHAD E.Synthesis of molecularly imprinted monolithic fibers for solid-phase microextraction of acetaldehyde from head-space of beverages stored in PET bottles[J].Talanta,2011,86(1):58-63.
[23]MOEIN M M,JAVANBAKHT M,KARIMI M,et al.Molecularly imprinted sol-gel nanofibers based solid phase microextraction coupled on-line with high performance liquid chromatography for selective determination of acesulfame[J].Talanta,2015,134:340-347.
[24]TERZOPOULOU Z,PAPAGEORGIOU M,KYZAS G Z,et al.Preparation of molecularly imprinted solid-phase microextraction fiber for the selective removal and extraction of the antiviral drug abacavir in environmental and biological matrices[J].Analytica chimica acta,2016,913:63-75.
[25]SOUZA I D,MELO L P,JARDIMI C S F,et al.Selective molecularly imprinted polymer combined with restricted access material for in-tube SPME/UHPLC-MS/MS of parabens in breast milk samples[J].Analytica chimica acta,2016,932:49-59.
[26]HU X,CAI Q,FAN Y,et al.Molecularly imprinted polymer coated solid-phase microextraction fibers for determination of Sudan I-IV dyes in hot chili powder and poultry feed samples[J].Journal of chromatography A,2012,1219(1):39-46.
[2]ABDULRA'UF L B,HAMMED W A,TAN G H.SPME fibers for the analysis of pesticide residues in fruits and vegetables:a review[J].Critical reviews in analytical chemistry,2012,42(2):152-161.
[3]李曌,张雪娜,李秀娟.基于溶胶-凝胶技术的乐果分子印迹固相微萃取涂层的评价及应用[J].食品安全质量检测学报,2015,6(12):4719-4725.
[4]ZHANG H,YAO R,WANG N,et al.Soluble molecularly imprinted polymer-based potentiometric sensor for determination of bisphenol AF[J].Analytical chemistry,2018,90(1):657-662.
[5]FENG S,WEI X,ZHONG L,et al.A novel molecularly imprinted photoelectrochemical sensor based on g-C3N4-AuNPs for the highly sensitive and selective detection of triclosan[J].E-lectroanalysis,2018,30(2):320-327.
[6]WACKERLIG J,SCHIRHAGL R.Applications of molecularly imprinted polymer nanoparticles and their advances toward industrial use:a review[J].Analytical chemistry,2016,88(1):250-261.
[7]ZHAO Q L,ZHOU J,ZHANG L S,et al.Coatings of molecularly imprinted polymers based on polyhedral oligomeric silsesquioxane for open tubular capillary electrochromatography[J].Talanta,2016,152:277-282.
[8]KONG Y,ZHAO W,YAO S P,et al.Molecularly imprinted polypyrrole prepared by electrodeposition for the selective recognition of tryptophan enantiomers[J].Journal of applied polymer science,2010,115(4):1952-1957.
[9]SUN G,LIU Y,AHAT H,et al.“Two-dimensional”molecularly imprinted solid-phase extraction coupled with crystallization and high performance liquid chromatography for fast semipreparative purification of tannins from pomegranate husk extract[J].Journal of chromatography A,2017,1505(7):35-42.
[10]WANG G N,YANG K,LIU H Z,et al.Molecularly imprinted polymer-based solid phase extraction combined high performance liquid chromatography for determination of fluoroquinolones in milk[J].Analytical methods,2016,8(27):5511-5518.
[11]ATLABACHEW M,TORTO N,CHANDRAVANSHI B S,et al.A(-)-norephedrine-based molecularly imprinted polymer for the solid-phase extraction of psychoactive phenylpropylamino alkaloids from Khat(Catha edulis Vahl.Endl.)chewing leaves[J].Biomed chromatogr,2016,30(7):1007-1015.
[12]祖广权,赵琪,谭策,等.分子印迹固相萃取-超高效液相色谱串联质谱法测定猪肉中磺胺二甲氧嗪[J].分析测试学报,2017,36(3):292-296.
[13]李蓉,储大可,高永清,等.复合分子印迹固相萃取-HPLC-MS/MS法测定植物源性食品中多种农药残留[J].分析测试学报,2015,34(8):907-912.
[14]LAI C,WANG M M,ZENG G M,et al.Synthesis of surface molecular imprinted TiO2/graphene photocatalyst and its highly efficient photocatalytic degradation of target pollutant under visible light irradiation[J].Applied surface science,2016,390:368-376.
[15]RESMINI M.Molecularly imprinted polymers as biomimetic catalysts[J].Analytical and bioanalytical chemistry,2012,402(10):3021-3026.
[16]KOSTER E H M,CRESCENZI C,HOEDT W D,et al.Fibers coated with molecularly imprinted polymers for solid-phase microextraction[J].Analytical chemistry,2001,73(13):3140-3145.
[17]MULLETT W M,MARTIN P,PAWLISZYN J.In-tube molecularly imprinted polymer solid-phase microextraction for the selective determination of propranolol[J].Analytical chemistry,2001,73(11):2383-2389.
[18]WANG Y L,GAO Y L,WANG P P,et al.Sol-gel molecularly imprinted polymer for selective solid phase microextraction of organophosphorous pesticides[J].Talanta,2013,115(17):920-927.
[19]LI J W,WANG Y L,YAN S,et al.Molecularly imprinted calixarene fiber for solid-phase microextraction of four organophosphorous pesticides in fruits[J].Food chemistry,2016,192:260-267.
[20]中华人民共和国国家卫生和计划生育委员会,中华人民共和国农业部国家食品药品监督管理总局.GB 2763-2016,食品安全国家标准:食品中农药最大残留限量[S].北京:中国标准出版社,2017.
[21]HE J,LV R,ZHAN H,et al.Preparation and evaluation of molecularly imprinted solid-phase micro-extraction fibers for selective extraction of phthalates in an aqueous sample[J].Analytica chimica acta,2010,674(1):53-58.
[22]KHORRAMI A R,NAROUENEZHAD E.Synthesis of molecularly imprinted monolithic fibers for solid-phase microextraction of acetaldehyde from head-space of beverages stored in PET bottles[J].Talanta,2011,86(1):58-63.
[23]MOEIN M M,JAVANBAKHT M,KARIMI M,et al.Molecularly imprinted sol-gel nanofibers based solid phase microextraction coupled on-line with high performance liquid chromatography for selective determination of acesulfame[J].Talanta,2015,134:340-347.
[24]TERZOPOULOU Z,PAPAGEORGIOU M,KYZAS G Z,et al.Preparation of molecularly imprinted solid-phase microextraction fiber for the selective removal and extraction of the antiviral drug abacavir in environmental and biological matrices[J].Analytica chimica acta,2016,913:63-75.
[25]SOUZA I D,MELO L P,JARDIMI C S F,et al.Selective molecularly imprinted polymer combined with restricted access material for in-tube SPME/UHPLC-MS/MS of parabens in breast milk samples[J].Analytica chimica acta,2016,932:49-59.
[26]HU X,CAI Q,FAN Y,et al.Molecularly imprinted polymer coated solid-phase microextraction fibers for determination of Sudan I-IV dyes in hot chili powder and poultry feed samples[J].Journal of chromatography A,2012,1219(1):39-46.