莠去津磁性分子印迹材料的制备及在蔬菜检测中的应用
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摘要
目的建立基于流动注射系统磁性分子印迹技术联用气相色谱法快速测定蔬菜中莠去津的检测方法。方法磁性分子印迹材料以壳聚糖包裹的四氧化三铁(Fe_3O_4-CS)为载体,莠去津为模板分子,甲基丙烯酸为功能单体,二甲基丙烯酸乙二醇酯为交联剂制备所得。蔬菜样品经乙酸乙酯提取,自制磁性分子印迹固相萃取柱净化富集,用甲醇洗脱目标化合物随后进入气相色谱仪进行定量测定。结果通过静态吸附实验考察磁性分子印迹材料对莠去津的最大吸附容量为52.0 mg/g。在本实验条件下,莠去津在5～100μg/L范围内线性良好,相关系数(R~2)0.9976,样品加标时,方法回收率为81.5%～107.7%(n=6),检出限为0.6μg/kg。结论本方法净化效果较好,可以用于蔬菜样品中莠去津残留检测。
OBJECTIVE A method for rapid determination of atrazine in vegetables by gas chromatography based on magnetic molecular imprinting technology in flow injection system was established. METHODS Core-shell magnetic molecularly imprinted polymers were prepared using ferroferric oxide modified with chitosan as the carrier, atrazine as the template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The attraction of the imprinted polymers for atrazine was studied through static equilibrium binding. The atrazine in the sample were extracted with ethyl acetate and then cleaned-up with MIPs SPE cartridges.The target molecules were eluted by methanol and then quantitatively determined by gas chromatograph.RESULTS The maximum adsorption capacity was 52.0 mg/g. Under the optimal conditions, the linearity of the method obtained was 5-100 μg/L. The detection limits of atrazine was 0.6 μg/kg. The recoveries were between 81.5% and 107.7%(n=6).CONCLUSION The proposed method is successfully applied to determine atrazine in vegetables.
OBJECTIVE A method for rapid determination of atrazine in vegetables by gas chromatography based on magnetic molecular imprinting technology in flow injection system was established. METHODS Core-shell magnetic molecularly imprinted polymers were prepared using ferroferric oxide modified with chitosan as the carrier, atrazine as the template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The attraction of the imprinted polymers for atrazine was studied through static equilibrium binding. The atrazine in the sample were extracted with ethyl acetate and then cleaned-up with MIPs SPE cartridges.The target molecules were eluted by methanol and then quantitatively determined by gas chromatograph.RESULTS The maximum adsorption capacity was 52.0 mg/g. Under the optimal conditions, the linearity of the method obtained was 5-100 μg/L. The detection limits of atrazine was 0.6 μg/kg. The recoveries were between 81.5% and 107.7%(n=6).CONCLUSION The proposed method is successfully applied to determine atrazine in vegetables.
引文
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[11] 吴岩,赵伟,刘永,等.快速基质分散净化-超快速液相色谱-串联质谱法同时测定玉米中22种三嗪类除草剂残留[J].分析化学,2016,44(6):950-957.
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[14] 孙边成,邹威,文刚,等.液质联用法快速、同时测定水中的呋喃丹、莠去津、西维因和微囊藻毒素LR[J].中国卫生检验杂志,2015(9):1317-1319.
[15] DUCA R C,SALQUEBRE G,HARDY E,et al.Comparison of solid phase- and liquid/liquid-extraction for the purification of hair extract prior to multi-class pesticides analysis[J].J Chromatogr B,2014,955-956(5):98-107.
[16] 曹卫鑫,杨碧漪,祁菲菲,等.功能化聚丙烯腈纳米纤维膜同时高效萃取莠去津及其毒性代谢物[J].分析化学,2017,45(4):495-501.
[17] 贾春虹,朱晓丹,赵尔成,等.液相色谱质谱法测定玉米中莠去津和烟嘧磺隆的残留[J].江苏农业科学,2014,42(2):253-255.
[18] 刘伯洋,李利军,程昊,等.分子印迹固相萃取技术对六堡茶中表儿茶素的分离特性[J].食品科学,2017,38(2):164-169.
[19] WANG S,LIU L,FANG G,et al.Molecularly imprinted polymer for the determination of trace ractopamine in pork using SPE followed by HPLC with fluorescence detection[J].J Sep Sci,2015,32(9):1333-1339.
[20] ANENE A,HOSNI K,CHEVALIER Y,et al.Molecularly imprinted polymer for extraction of patulin in apple juice samples[J].Food Control,2016,70:90-95.
[21] 佟育奎,胡月,夏琴飞,等.新型磁性分子印迹聚合物的制备及其在氟喹诺酮类抗生素检测中的应用[J].色谱,2017,35(3):84-94.
[22] TANG Y,GAO J,LIU X,et al.Determination of ractopamine in pork using a magnetic molecularly imprinted polymer as adsorbent followed by HPLC[J].Food Chem,2016,201:72-79.
[23] HASHEMI M,NAZARI Z.Preparation of molecularly imprinted polymer based on the magnetic multiwalled carbon nanotubes for selective separation and spectrophotometric determination of melamine in milk samples[J].J Food Compos Anal,2018,69:98-106.
[24] SU L Q,GAO Y,QIN S L,et al.Determination of atrazine in vegetables with extraction by a magnetite - chitoan molecularly imprinted polymer and gas chromatography[J].Anal Lett,2016,49(14):2177-2192.
[25] YAN L,WANG J,LV P,et al.A facile synthesis of novel three-dimensional magnetic imprinted polymers for rapid extraction of bovine serum albumin in bovine calf serum[J].Analy Bioanaly Chem,2017,409(13):3453-3463.
[26] 中华人民共和国卫生部.食品中莠去津残留量的测定:GB/T 5009.132—2003 [S].北京:中国标准出版社,2004.
[27] 马婧玮,李萌,马欢.SPE净化-GC(NPD)测定土壤及玉米中莠去津残留量[J].分析试验室,2011,30(7):75-78.
[28] 苏趋,刘彬,洪军.加速溶剂萃取-高效液相色谱法测定土壤中11种三嗪类除草剂[J].环境化学,2017,36(3):628-634.
[29] 贾春虹,朱晓丹,赵尔成.液相色谱质谱法测定玉米中莠去津和烟嘧磺隆的残留[J].江苏农业科学,2014,42(2):253-255.
[30] 张贵江,臧晓欢,周欣.磁性石墨烯纳米粒子固相萃取与气相色谱-质谱相结合测定环境水样中的三嗪类除草剂[J].色谱,2013,31(11):1071-1075.
[31] 中国化学会.门海芬,张祖磊,张剑.核壳型磁性分子印迹聚合物的制备及色谱法测定玉米中的莠去津[C]// 中国化学会全国仪器分析及样品预处理学术研讨会.镇江:中国化学会,2011.
[2] SOUSA A S,DUAVI W C,CAVALCANTE R M,et al.Estimated levels of environmental contamination and health risk assessment for herbicides and insecticides in surface water of Ceará,Brazil[J].Bull Environ Contam Toxicol,2016,96(1):90-95.
[3] GUPTA V K,YOLA M L,EREN T,et al.Selective QCM sensor based on atrazine imprinted polymer:Its application to wastewater sample[J].Sensors Actuators B:Chem,2015,218:215-221.
[4] MORALES A A,ARIAS C,RAMIREZ R M.Removal of atrazine from water using an iron photo catalyst supported on activated carbon[J].Adsorption,2016,22(1):1-10.
[5] KABIR E R,RAHMAN M S,RAHMAN I.A review on endocrine disruptors and their possible impacts on human health[J].Environ Toxicol Pharmacol,2015,40(1):241-258.
[6] MANSKE M K,BELTZ L A,DHANWADA K R.Low-level atrazine exposure decreases cell proliferation in human fibroblasts[J].Arch Environ Contam Toxicol,2004,46(4):438-444.
[7] 主要贸易国家和地区食品中农兽药残留限量标准编委会.主要贸易国家和地区食品中农兽药残留限量标准(食品卷)[S].北京:中国标准出版社,2006.
[8] 郭和光,吴丹青,邵国健,等.顶空-固相微萃取-气相色谱法测定甘蔗中的莠去津[J].中国卫生检验杂志,2016(18):2614-2615.
[9] 杜利敏,王彦平,张瑞,等.大体积固相萃取GC-MS/MS测定水中莠去津的方法研究与应急检测应用[J].国际医药卫生导报,2016,22(16):2580-2584.
[10] 张翠华,张菊花,范小振.超声萃取高效液相色谱法检测土壤中烟嘧磺隆和莠去津的残留量[J].化学研究与应用,2018(1):114-118.
[11] 吴岩,赵伟,刘永,等.快速基质分散净化-超快速液相色谱-串联质谱法同时测定玉米中22种三嗪类除草剂残留[J].分析化学,2016,44(6):950-957.
[12] 杜鹏飞,金茂俊,石梦琪,等.分散固相萃取-气相色谱-质谱法同时测定玉米中乙草胺、莠去津和2,4-滴异辛酯[J].农药,2015,54(10):748-751.
[13] 白小军,吴燕,牛艳,等.玉米中乙草胺和莠去津残留量GC-MS/MS分析法的建立[J].江苏农业科学,2014,42(11):334-336.
[14] 孙边成,邹威,文刚,等.液质联用法快速、同时测定水中的呋喃丹、莠去津、西维因和微囊藻毒素LR[J].中国卫生检验杂志,2015(9):1317-1319.
[15] DUCA R C,SALQUEBRE G,HARDY E,et al.Comparison of solid phase- and liquid/liquid-extraction for the purification of hair extract prior to multi-class pesticides analysis[J].J Chromatogr B,2014,955-956(5):98-107.
[16] 曹卫鑫,杨碧漪,祁菲菲,等.功能化聚丙烯腈纳米纤维膜同时高效萃取莠去津及其毒性代谢物[J].分析化学,2017,45(4):495-501.
[17] 贾春虹,朱晓丹,赵尔成,等.液相色谱质谱法测定玉米中莠去津和烟嘧磺隆的残留[J].江苏农业科学,2014,42(2):253-255.
[18] 刘伯洋,李利军,程昊,等.分子印迹固相萃取技术对六堡茶中表儿茶素的分离特性[J].食品科学,2017,38(2):164-169.
[19] WANG S,LIU L,FANG G,et al.Molecularly imprinted polymer for the determination of trace ractopamine in pork using SPE followed by HPLC with fluorescence detection[J].J Sep Sci,2015,32(9):1333-1339.
[20] ANENE A,HOSNI K,CHEVALIER Y,et al.Molecularly imprinted polymer for extraction of patulin in apple juice samples[J].Food Control,2016,70:90-95.
[21] 佟育奎,胡月,夏琴飞,等.新型磁性分子印迹聚合物的制备及其在氟喹诺酮类抗生素检测中的应用[J].色谱,2017,35(3):84-94.
[22] TANG Y,GAO J,LIU X,et al.Determination of ractopamine in pork using a magnetic molecularly imprinted polymer as adsorbent followed by HPLC[J].Food Chem,2016,201:72-79.
[23] HASHEMI M,NAZARI Z.Preparation of molecularly imprinted polymer based on the magnetic multiwalled carbon nanotubes for selective separation and spectrophotometric determination of melamine in milk samples[J].J Food Compos Anal,2018,69:98-106.
[24] SU L Q,GAO Y,QIN S L,et al.Determination of atrazine in vegetables with extraction by a magnetite - chitoan molecularly imprinted polymer and gas chromatography[J].Anal Lett,2016,49(14):2177-2192.
[25] YAN L,WANG J,LV P,et al.A facile synthesis of novel three-dimensional magnetic imprinted polymers for rapid extraction of bovine serum albumin in bovine calf serum[J].Analy Bioanaly Chem,2017,409(13):3453-3463.
[26] 中华人民共和国卫生部.食品中莠去津残留量的测定:GB/T 5009.132—2003 [S].北京:中国标准出版社,2004.
[27] 马婧玮,李萌,马欢.SPE净化-GC(NPD)测定土壤及玉米中莠去津残留量[J].分析试验室,2011,30(7):75-78.
[28] 苏趋,刘彬,洪军.加速溶剂萃取-高效液相色谱法测定土壤中11种三嗪类除草剂[J].环境化学,2017,36(3):628-634.
[29] 贾春虹,朱晓丹,赵尔成.液相色谱质谱法测定玉米中莠去津和烟嘧磺隆的残留[J].江苏农业科学,2014,42(2):253-255.
[30] 张贵江,臧晓欢,周欣.磁性石墨烯纳米粒子固相萃取与气相色谱-质谱相结合测定环境水样中的三嗪类除草剂[J].色谱,2013,31(11):1071-1075.
[31] 中国化学会.门海芬,张祖磊,张剑.核壳型磁性分子印迹聚合物的制备及色谱法测定玉米中的莠去津[C]// 中国化学会全国仪器分析及样品预处理学术研讨会.镇江:中国化学会,2011.