CN108623834A - 分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法 - Google Patents
分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法 Download PDFInfo
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Abstract
本发明公开了一种分子印迹‑分散固相萃取检测农产品中三嗪类除草剂痕量残留的方法。该方法以三嗪类化合物为模板分子，在致孔剂中加入模板分子、功能单体、交联剂和引发剂，通过沉淀聚合法制备了分子印迹纳米微球；将分子印迹纳米微球经活化后，作为分散固相萃取的吸附材料，与UPLC‑MS/MS联用，用于检测复杂的农产品基质中多种三嗪类除草剂；本发明制备的分子印迹纳米微球对模板分子及其结构类似物具有良好选择性吸附能力，且颗粒粒径分布均匀，提高了检测重现性；并克服了传统固相萃取柱的流速不易控制，重现性差的缺陷，可满足各种基质中痕量三嗪类农残的检测要求。
Description
技术领域
本发明涉及功能高分子材料合成和分离工程领域，具体涉及一种分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法。
背景技术
样品前处理过程所用吸附剂要求能对目标分析物进行选择性吸附，类似于天然抗体对受体，酶对底物的识别。蛋白质在极端温度、pH以及有机溶剂中极易变性，因此生物识别过程对环境要求十分苛刻。为了克服以上的局限性，近年来人工合成受体分子印迹技术受到了人们的广泛关注。分子印迹技术所合成的分子印迹聚合物在三维空间和吸附位点上与模板互补，对于模板分子及其结构类似物都有一定的选择性吸附作用。近年来在分离工程领域得到了人们的广泛关注。
适宜的样品前处理是分析结果的准确性和精确度的保证。目前，大豆等农作物中三嗪类除草残留的前处理主要是以传统固相萃取为主。对于烟叶、大豆的提取液的粘稠度较大，且其中存在许多颗粒物质，使用常规的固相萃取装置对样品进行前处理的流速不易控制，柱压大，一些杂质易通过物理作用停留在柱子中，前处理效率低；分散固相萃取过程吸附剂均匀分散在液体介质中，吸附过程可控，可针对性的吸附待测化合物，达到样品高效萃取和净化的目的。
三嗪类除草剂是目前应用最广的除草剂之一。环境和农产品中的三嗪类除草剂残留可能导致多种癌症、先天缺陷和生殖肿瘤以及影响正常激素功能和胚胎发育，严重危害人体健康。许多国家都对三嗪类除草剂在环境和农作物中的最大残留限量制定了严格的标准。我国自2017年6月18开始实施GB 2763-2016标准，规定糙米的西草净限量为0.05μg/g，玉米的莠去津、氰草津、嗪草酮农残限量均为0.05μg/g，玉米的特丁津、西玛津限量分别为0.1和0.02μg/g。因此，开发一种简单、快速、低检测限的三嗪类除草剂分析方法具有重要意义。
发明内容
本发明所要解决的问题是针对传统分子印迹聚合物制备过程复杂、颗粒不均匀，吸附时间长的缺陷，提供一种分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，该方法可简单快速制备粒径小、高度均匀的分子印迹纳米微球，所制备的分子印迹纳米微球对模板分子及其结构类似物具有良好的选择性吸附能力和较高的印迹因子；进一步将这种分子印迹纳米微球作为吸附剂，开发了一种分散固相萃取前处理方法，有效地克服了传统固相萃取流速不易控制，净化效率低的缺陷，可实现农产品中多种三嗪类除草剂痕量残留分析。
本发明的上述目的通过以下技术方案予以实现：
（1）分子印迹纳米微球制备：以三嗪类化合物为模板分子，在致孔剂中加入模板分子和功能单体，超声混合溶解，在-10℃～25℃下密封自组装得到模板-单体复合物；然后加入交联剂和引发剂，通入N2除氧，在振荡条件下50～70℃水浴热引发，发生沉淀聚合反应；反应结束后，高速离心分离得到聚合物颗粒，利用索氏提取器以甲醇-乙酸混合溶液洗脱聚合物颗粒中的模板分子，至提取器中溶液不能检测到模板分子为止；然后用甲醇、丙酮依次清洗聚合物颗粒除去聚合物中非特异性杂质，离心、干燥得到分子印迹纳米微球，其中模板分子和功能单体的摩尔比为1:3～6；
（2）样品的提取：将农产品待测部分样品粉碎，过40～50目筛后置于40～80℃下恒温真空干燥6～12h；称取干燥后样品0.5～1.5g置于离心管中，加入10～15mL乙腈，超声提取30～60min后过滤，滤液旋转蒸干后加入2～5mL上样溶剂复溶，即得到待测样品提取液；
（3）分散固相萃取：依次采用甲醇、乙腈和上样溶剂冲洗活化分子印迹纳米微球；然后将待测样品提取液和活化后的分子印迹纳米微球放入底部装有筛板的固相萃取空柱中混合均匀，静置30~60min后通过负压抽干溶液；再加入淋洗液淋洗分子印迹纳米微球，静置后负压抽干弃去淋洗液；最后分次加入甲醇-乙酸混合溶液洗脱，合并收集洗脱液，旋转蒸干后用乙腈溶解，供UPLC-MS/MS检测。
所述功能单体为甲基丙烯酸、丙烯酸或三氟甲基丙烯酸。
所述交联剂为乙二醇二甲基丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯，功能单体和交联剂的摩尔比为1:3-5；
所述引发剂为偶氮二异丁腈，添加量为功能单体和交联剂总质量的2-5%。
所述致孔剂为乙腈、水、甲醇或二氯甲烷，用量为30-70mL。
所述高速离心转速为6000～15000rpm。
所述聚合过程中的振荡是在转速50～150rpm下进行，聚合反应时间为12h-48h。
所述步骤（1）和步骤（3）中所用甲醇-乙酸混合溶液是甲醇和乙酸按体积比9:1～99:1的比例混合制得。
所述步骤（3）混合是通过超声或涡旋振荡使分子印迹纳米微球悬浮在样品提取液中。
所述步骤（3）中活化后的分子印迹纳米微球的质量mg与待测样品提取液的体积mL比为10: 0.5～5。
所述上样溶剂为二氯甲烷、乙腈、甲苯或丙酮。
所述淋洗液为二氯甲烷、正己烷、甲苯或丙酮。
与现有技术相比，本发明具有如下有益效果：
本发明利用沉淀聚合法制备了分子印迹纳米微球，通过改变反应条件实现了纳米级均匀微球的制备；与现有的分子印迹技术相比，得到的分子印迹纳米微球颗粒径小，结构完整、粒径分布高度均匀，提高了实验的重现性，有利于进一步的应用；同时，将得到的分子印迹纳米微球作为吸附剂，结合分散固相萃取技术，克服了传统固相萃取流速不易控制，柱压高，分离效率低的缺陷，可用于分离和富集农产品中的多种三嗪类除草剂痕量残留。通过这种分子印迹基质分散固相萃取的样品前处理方式，基质效应显著降低，提高了分析复杂基质中的痕量农残的准确度与精密度。
附图说明
图1是西草净分子印迹纳米微球的扫描电镜图；
图2是西草净分子印迹纳米微球的静态吸附曲线，其中SINs是西草净印迹纳米微球，NINs是非分子印迹纳米微球；
图3是分子印迹分散固相萃取前后基质效应影响，其中a图为未经过分散固相萃取，b图为经过分散固相萃取。
具体实施方式
以下结合实施例对本发明作进一步详细说明，但本发明保护范围不局限于所述内容。
实施例1：本分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，具体内容如下：
向100mL硼硅酸玻璃瓶中加入50.66mg西草净、0.081mL甲基丙烯酸、40mL乙腈，超声3min，放入4℃冰箱中，静置12h密封自组装得到模板-单体复合物；再向其中加入30mg偶氮二异丁腈、0.597mL乙二醇二甲基丙烯酸酯，通入高纯N2 15min，然后在60℃水浴、转速60rpm下热引发发生沉淀聚合反应48h；反应结束后，10000rpm离心分离得到聚合物颗粒，然后用索式提取装置，以甲醇-乙酸混合溶液（9:1，v/v）为洗脱液洗涤聚合物颗粒中的模板分子，每8小时更换一次洗脱液，洗脱16小时至提取器中溶液不能检测到模板分子为止；洗脱结束后用甲醇、丙酮依次清洗聚合物颗粒三次，以6000rpm高速离心10min收集聚合物颗粒，最后在50℃真空条件下干燥得到西草净印迹纳米微球。
作为对照，非分子印迹纳米微球（non-molecular imprinted nanospheres，NINs）的制备除了不加入模板分子外，所有步骤同上。西草净印迹纳米微球的场发射扫描电镜如图1；图2是西草净印迹纳米微球和非分子印迹纳米微球的吸附曲线，表明这种西草净纳米微球有良好的特异性吸附能力和较高的吸附容量。
将得到的西草净印迹纳米微球作为吸附剂，通过分散固相萃取应用于烟叶中西草净、扑草净、特丁津、莠去津残留的检测。具体过程为分为两个步骤：
1、样品提取：向烟叶控制样（不含农残）中加标，加标浓度为0.05、0.25和0.5μg/g。将加标烟叶用粉碎机打碎，过40目筛后置于50℃下恒温真空干10h；将干燥后样品1g置于25mL离心管中，加入10mL乙腈，超声提取40min后过滤，滤液干燥加入2mL二氯甲烷复溶，即得到加标烟叶提取液；
2、将空心萃取柱下方用筛板压实，向其中加入20mg西草净印迹纳米微球，形成分散固相萃取柱；依次加入甲醇、乙腈和二氯甲烷5mL对分散固相萃取柱进行活化，抽干溶液；向活化后的萃取柱中加入2mL加标烟叶提取液，涡旋混匀，静置1h后抽去溶液；再向萃取柱加入2mL二氯甲烷淋洗吸附材料，静置2min后抽去溶液；最后向萃取柱加入10mL甲醇-乙酸混合液（9:1，v/v）溶液（分两次加入）洗脱，将洗脱液抽入25mL茄形瓶中；旋转蒸干后用1mL乙腈溶液复溶，上UPLC-MS/MS检测。可以发现，经过这种分散固相萃取后烟叶带来的杂峰显著减少，证明这种分子印迹分散固相萃取技术可以有效消除分析方法的基质效应（经过分散固相萃取和未经过分散固相萃取的烟叶控制样品的离子流如图3所示），且对4种三嗪类除草剂的回收率在84.03%-119.05% (n=5) 之间，满足定量检测要求；这种以西草净印迹纳米微球为吸附材料的分散固相萃取结合UPLC-MS/MS检测方法对烟叶中4种三嗪类除草剂农残的定量限（LOQ）为10-20ng/mL，实现了对烟叶中多种三嗪类农残的痕量检测，结果见表1。
表1 标准曲线与检测限、定量限（n=5）
。
实施例2：本分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，具体内容如下：
（1）向100mL硼硅酸玻璃瓶中加入63.33mg西草净、0.127mL丙烯酸、50mL甲醇，超声3min，放入-5℃冰箱中，静置12h密封自组装得到模板-单体复合物；再向其中加入35mg偶氮二异丁腈、0.746mL三羟甲基丙烷三甲基丙烯酸酯，通入高纯N2 15min，然后在50℃水浴、转速100rpm下热引发发生沉淀聚合反应20h；反应结束后，10000rpm离心分离得到聚合物颗粒，然后用索式提取装置，以甲醇-乙酸混合溶液（20:1，v/v）为洗脱液洗涤聚合物颗粒中的模板分子，每8小时更换一次洗脱液，洗脱至提取器中溶液不能检测到模板分子为止；洗脱结束后用甲醇、丙酮依次清洗聚合物颗粒三次，以6000rpm高速离心10min收集聚合物颗粒，最后在50℃真空条件下干燥得到西草净印迹纳米微球。
将得到的西草净印迹纳米微球作为吸附剂，通过分散固相萃取应用于市售烟叶中西草净、氰草津、特丁津、莠去津残留的检测。具体过程为分为两个步骤：1、样品提取：将在市场购买的烟叶用粉碎机打碎，过50目筛后置于65℃下恒温真空干10h；将干燥后样品0.5g置于离心管中，加入12mL乙腈，超声提取50min后过滤，滤液干燥加入3mL丙酮复溶，即得到烟叶提取液；2、将空心萃取柱下方用筛板压实，向其中加入20mg西草净印迹纳米微球，形成分散固相萃取柱；依次加入甲醇、乙腈和丙酮5mL对分散固相萃取柱进行活化，抽干溶液；向活化后的萃取柱中加入2mL烟叶提取液，涡旋混匀，静置40min后负压抽去溶液；再向萃取柱加入5mL正己烷淋洗吸附材料，静置2min后负压抽去溶液；最后向萃取柱加入10mL甲醇-乙酸混合液（20:1，v/v）溶液（分两次加入）洗脱，将洗脱液抽入25mL茄形瓶中；旋转蒸干后用1mL乙腈溶液复溶，上UPLC-MS/MS检测。
采用西草净印迹纳米微球和C18为吸附材料所制备的分散固相萃取柱检测样品中4种目标三嗪类除草剂，结果如表2所示：
表2 市售烟草中4种农残目标分析物的检测结果
。
实施例3：本分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，具体内容如下：
向100mL硼硅酸玻璃瓶中加入53.92mg莠去津、0.101mL三氟甲基丙烯酸、50mL二氯甲烷，超声5min，放入10℃冰箱中静置12h密封自组装得到模板-单体复合物；再向其中加入30mg偶氮二异丁腈、0.746mL乙二醇二甲基丙烯酸酯，通入高纯N2 15min，然后在70℃水浴、转速120rpm下热引发发生沉淀聚合反应15h，反应结束后，12000pm离心分离得到聚合物颗粒；然后用索式提取装置，以甲醇/乙酸（50:1，v/v）为洗脱液洗涤聚合物颗粒；每8小时更换一次洗脱液，洗脱结束后至用HPLC从上清液中不能检测到莠去津；洗脱结束后用甲醇、丙酮依次清洗聚合物颗粒三次，以10000rpm高速离心10min收集聚合物颗粒，最后在50℃真空条件下干燥得到莠去津印迹纳米微球。作为对照，非分子印迹纳米微球的制备除了不加入模板分子外，所有步骤同上。
将得到的莠去津印迹纳米微球作为吸附剂，通过分散固相萃取的应用于糙米中莠去津、西玛通、氰草津、莠去通、特丁津、扑灭通的检测。具体过程为分为两个步骤：1、样品提取：向糙米控制样（不含农残）中加标，加标浓度为0.05、0.25和0.5μg/g；将加标糙米用粉碎机打碎，过45目筛后置于75℃下恒温真空干6h；将干燥后样品1.5g置于离心管中，加入15mL乙腈，超声提取60min后过滤，滤液干燥加入4mL二氯甲烷复溶，即得到加标糙米提取液。2、将空心萃取柱下方用筛板压实，向其中加入50mg莠去津印迹纳米微球，形成分散固相萃取柱；依次加入甲醇、乙腈和二氯甲烷5mL对分散固相萃取柱进行活化，抽干溶液；向活化后的萃取柱中加入5mL加标烟叶提取液，涡旋混匀，静置50min后负压抽去溶液；再向萃取柱加入5mL丙酮淋洗吸附材料，静置2min后负压抽去溶液；最后向萃取柱加入15mL甲醇-乙酸混合液（50:1，v/v）溶液（分两次加入）洗脱，将洗脱液抽入25mL茄形瓶中；旋转蒸干后用5mL乙腈溶液复溶，上UPLC-MS/MS检测。计算得到这种分析方法对6种三嗪类除草剂的回收率在81.2%-126.3% (n=5) 之间，满足定量检测要求；这种以莠去津印迹纳米微球为吸附剂的分散固相萃取结合UPLC-MS/MS检测方法对糙米中6种三嗪类除草剂农残的定量限（LOQ）为10-20ng/mL，低于国标中规定的最大残留限量50μg/g，实现了对糙米中多种三嗪类农残的痕量检测，结果见表3。
表3 标准曲线与检测限、定量限（n=5）
。
Claims (11)
1.一种分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于，操作步骤如下：
（1）分子印迹纳米微球制备：以三嗪类化合物为模板分子，在致孔剂中加入模板分子和功能单体，超声混合溶解，在-10℃～25℃下密封自组装得到模板-单体复合物；然后加入交联剂和引发剂，通入N2除氧，在振荡条件下50～70℃水浴热引发，发生沉淀聚合反应；反应结束后，高速离心分离得到聚合物颗粒，利用索氏提取器以甲醇-乙酸混合溶液洗脱聚合物颗粒中的模板分子，至提取器中溶液不能检测到模板分子为止；然后用甲醇、丙酮依次清洗聚合物颗粒除去聚合物中非特异性杂质，离心、干燥得到分子印迹纳米微球，其中模板分子和功能单体的摩尔比为1:3～6；
（2）样品的提取：将农产品待测部分样品粉碎，过40～50目筛后置于40～80℃下恒温真空干燥6～12h；称取干燥后样品0.5～1.5g置于离心管中，加入10～15mL乙腈，超声提取30～60min后过滤，滤液旋转蒸干后加入2～5mL上样溶剂复溶，即得到待测样品提取液；
（3）分散固相萃取：依次采用甲醇、乙腈和上样溶剂冲洗活化分子印迹纳米微球；然后将待测样品提取液和活化后的分子印迹纳米微球混合均匀，静置30~60min后通过负压抽干溶液；再加入淋洗液淋洗分子印迹纳米微球，静置后负压抽干弃去淋洗液；最后分次加入甲醇-乙酸混合溶液洗脱，合并收集洗脱液，旋转蒸干后用乙腈溶解，供UPLC-MS/MS检测。
2.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：功能单体为甲基丙烯酸、丙烯酸或三氟甲基丙烯酸。
3.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：交联剂为乙二醇二甲基丙烯酸酯或三羟甲基丙烷三甲基丙烯酸酯，功能单体和交联剂的摩尔比为1:3-5；引发剂为偶氮二异丁腈，添加量为功能单体和交联剂总质量的2-5%。
4.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：致孔剂为乙腈、水、甲醇或二氯甲烷。
5.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：高速离心转速为6000～15000rpm。
6.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：聚合过程中的振荡是在转速50～150rpm下进行，聚合反应时间为12h-48h。
7.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：步骤（1）和步骤（3）中所用甲醇-乙酸混合溶液是甲醇和乙酸按体积比9:1～99:1的比例混合制得。
8.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：步骤（3）混合是通过超声或涡旋振荡使分子印迹纳米微球悬浮在样品提取液中。
9.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：步骤（3）中活化后的分子印迹纳米微球的质量mg与待测样品提取液的体积mL比为10: 0.5～5。
10.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：上样溶剂为二氯甲烷、乙腈、甲苯或丙酮。
11.根据权利要求1所述的分子印迹-分散固相萃取检测农产品中三嗪类除草剂残留的方法，其特征在于：淋洗液为二氯甲烷、正己烷、甲苯或丙酮。
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| CN112461960B (zh) * | 2020-11-16 | 2022-06-14 | 湖南省生态环境监测中心 | 同时测定水质中多种杂环农药、降解物和中间体的方法 |
| CN112979858A (zh) * | 2021-03-02 | 2021-06-18 | 南京财经大学 | 一种三嗪类双模版分子印迹聚合物及其制备方法和应用 |
| CN112979858B (zh) * | 2021-03-02 | 2022-05-17 | 南京财经大学 | 一种三嗪类双模版分子印迹聚合物及其制备方法和应用 |
| CN115382514A (zh) * | 2022-08-08 | 2022-11-25 | 宁波大学 | 一种选择性去除水环境中三嗪类除草剂污染的分子印迹MOFs材料制备方法及应用 |
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