CN110760039A - 一种检测中药材中菊酯类农残的样品前处理方法 - Google Patents
一种检测中药材中菊酯类农残的样品前处理方法 Download PDFInfo
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Abstract
本发明公开了一种检测中药材中菊酯类农残的样品前处理方法,其特征在于:按每1mL中药材提取液添加20mg~50mg菊酯类农残的磁性分子印迹聚合物的比例,在中药材提取液中添加菊酯类农残的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,然后用乙腈超声洗脱6~8h,再用0.45μm滤膜过滤后,滤液用于菊酯类农残分析检测;本发明方法效果好,选择性强,干扰少,操作简单,有利于降低成本,提高工作效率。
Description
技术领域
本发明涉及一种检测中药材中菊酯类农残的样品前处理方法,属于中药材中农残检测样品前处理领域。
背景技术
中药作为传统药物,在中国有着上千年的使用历史。随着中药产品的影响力越来越大,中药材更是受到国际高度关注。其中,农药残留是影响中药材质量安全的主要因素,同时也是严重制约我国中药产品走向国际市场的重要原因,直接影响了中药在国际市场上的竞争力。
菊酯类农药是一种毒性较低、杀虫活性较高的拟除虫菊酯类杀虫剂。其作用在于改变昆虫神经膜的通透性,使中毒昆虫过度兴奋、麻痹而死亡;是一种世界各地广泛使用的杀虫剂。但其具有蓄积毒性,即长期低剂量接触该药物会引起慢性疾病,对人类具有中等神经毒性、免疫系统毒性、心血管毒性和遗传毒性,甚至具有致突变性、致癌性和致畸性。
由于中药材的种类繁多,且中药材中的基质较为复杂,通常在检测其农药残留前需采用一些前处理方式,如索氏提取、超声提取、超临界萃取、固相萃取(SPE)、固相微萃取(SPME)等。但这些方法常常有操作繁琐、费时、效率低等缺点。
分子印迹技术( Molecular Imprinting Technique, MIT) 指的是制备某种对目标物质( 模板分子) 具备高度选择性的物质,进而达到物质分离的目的。这种技术充分利用抗体-抗原特异性结合的原理,制备有特定尺寸、形状、序列的功能性基团聚合物,能够特异性识别模板分子,进而达到分离与选择的目的。而磁性分子印迹技术则是在此技术上引入具有磁性颗粒,使得分离更加快速,方便。
发明内容
本发明的目的在于克服现有技术的不足,提供一种检测中药材中菊酯类农残的样品前处理方法;这种方法操作简单、快速、选择性强,能用于中药材中各类残留农药提取分离;本发明方法是按每1mL中药材提取液添加20mg~50mg菊酯类农残的磁性分子印迹聚合物的比例,在中药材提取液中添加菊酯类农残的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,用水冲洗分离出磁性分子聚合物,然后用乙腈超声洗脱6~8h,再用0.45μm滤膜过滤后,滤液用于菊酯类农残分析检测(采用常规方法进行检测,例如HPLC)。
其中所述菊酯类农残的磁性分子印迹聚合物的制备方法如下
(1)Fe3O4的制备
将FeCl3·6H2O溶液和FeCl2·4H2O溶液混合,在氮气、60℃~70℃下搅拌20~50min后,按每100mL混合液滴加15mL~20mL氨水的比例,在混合液中添加氨水,继续反应30min
~60min,溶液中出现黑色沉淀即生成了Fe3O4;其中FeCl3·6H2O与FeCl2·4H2O的质量比为2:1~3:1,FeCl3·6H2O溶液浓度为50~60g/L;反应液自然冷却后,用外加磁场分离获得Fe3O4颗粒,Fe3O4颗粒用水清洗至pH=7;
(2)将清洗后的Fe3O4颗粒超声分散到质量浓度75%~85%的乙醇溶液中,Fe3O4颗粒在乙醇溶液中的浓度为10g/L~15g/L,然后按每100mL分散液添加氨水6mL~8mL、硅酸四乙酯0.5mL~1mL的比例在分散液中加入氨水和硅酸四乙酯,氮气、40℃条件下搅拌反应10h~20h,反应结束后,在外加磁场作用下进行分离,固体用纯水洗5~6次,然后在50℃~60℃下真空干燥,制得Fe3O4@SiO2颗粒;
(3)将模板分子与功能单体按摩尔比1:4~1:8的比例分散在二甲基亚砜中,然后在温度0~24℃下反应5~12h,制得预聚合物;
(4)在预聚合物中加入Fe3O4@SiO2二甲基亚砜分散液、交联剂、引发剂,其中Fe3O4@SiO2颗粒与模板分子的质量比为1:20~1:30,交联剂与模板分子的摩尔比为20:1~30:1,引发剂与模板分子的摩尔比为1:1~1:3;在50℃~70℃、氮气保护下搅拌反应18~27h,反应结束后,固体用甲醇-乙酸混合液洗涤至洗液中检测不到模板分子,洗涤后固体在40~60℃下真空干燥,制得菊酯类农残的磁性分子印迹聚合物。
所述中药材提取液是取研磨后的10mg~20mg中药材用40mL~60mL乙腈超声提取4h~6h后制得。
所述模板分子为氟氯氰菊酯、氰戊菊酯、溴氰菊酯或联苯菊酯。
所述功能单体为丙烯酰胺或甲基丙烯酸。
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。
所述引发剂为偶氮二异丁腈。
所述甲醇-乙酸的混合溶液中甲醇与乙酸体积比为8:2~9:1
与现有技术相比,本发明有以下优点:
(1)本发明不需要繁琐的净化过程,简化了样品前处理的步骤,减少了目标物质的损失;
(2)磁性分子印迹聚合物上有与模板分子结构完全匹配的空穴,使得聚合物表现出特异性吸附,可实现从复杂基质中分离、富集和纯化拟除虫菊酯类农残;
(3)磁性分子印迹聚合物采用沉淀聚合法制备磁性纳米微球,制备方法简单,所得颗粒粒径均匀,磁响应强,在分离时不需要额外的离心或过滤,分离效率大大提高;
(4)磁性分子印迹聚合物的合成方法简单,原料廉价易得,重复性好。比起传统样品前处理方法,本发明不需要繁琐的净化过程,简化了样品前处理的步骤,减少了目标物质的损失。因此本发明可以在食品安全,环境检测等方面有良好的经济效益和应用前景,可以良好的代替传统方法。
附图说明
图1为Fe3O4和磁性分子印迹聚合物的振动样品磁强计图(VSM)
图2为Fe3O4和磁性分子印迹聚合物的透射电子显微镜图(TEM),其中A图为Fe3O4颗粒的外貌特征;B图为磁性分子印迹聚合物颗粒的外貌特征;
图3为本发明制备的磁性分子印迹聚合物和磁性分子非印迹聚合物对溴氰菊酯的吸附动力学曲线;
图4为发明制备的磁性分子印迹聚合物和磁性分子非印迹聚合物对溴氰菊酯的等温吸附曲线。
具体实施方式
下面通过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:本中药材中菊酯类农残的简易样品前处理方法如下:
1、菊酯类农残的磁性分子印迹聚合物的制备
(1)将FeCl3·6H2O溶液和FeCl2·4H2O溶液混合,在氮气、60℃下搅拌40min后,按每100mL混合液滴加15mL氨水的比例,在混合液中添加氨水,继续反应30min,溶液中出现黑色沉淀即生成了Fe3O4;其中FeCl3·6H2O与FeCl2·4H2O的质量比为2:1,FeCl3·6H2O溶液浓度为50g/L;反应液自然冷却后,用外加磁场分离获得Fe3O4颗粒,Fe3O4颗粒用水清洗至pH=7;
(2)将清洗后的Fe3O4颗粒超声分散到质量浓度75%的乙醇溶液中,Fe3O4颗粒在乙醇溶液中的浓度为10g/L,然后按每100mL分散液添加氨水6mL、硅酸四乙酯0.5mL的比例在分散液中加入氨水和硅酸四乙酯,氮气、40℃条件下搅拌反应10h,反应结束后,在外加磁场作用下进行分离,固体用纯水洗6次,然后在50℃下真空干燥,制得Fe3O4@SiO2颗粒;(3)将氟氯氰菊酯与甲基丙烯酸按摩尔比1:4的比例分散在二甲基亚砜中,氟氯氰菊酯在二甲基亚砜的浓度为0.5g/L,然后在温度0℃下反应12h,制得预聚合物;
(4)在预聚合物中加入Fe3O4@SiO2二甲基亚砜分散液、乙二醇二甲基丙烯酸酯、偶氮二异丁腈,其中Fe3O4@SiO2二甲基亚砜分散液按每100mL 体积浓度90%的二甲基亚砜中分散100mg Fe3O4@SiO2颗粒制得,Fe3O4@SiO2颗粒与氟氯氰菊酯的质量比为1:20,乙二醇二甲基丙烯酸酯与氟氯氰菊酯的摩尔比为20:1,偶氮二丁腈与氟氯氰菊酯的摩尔比为1:1在50℃、氮气保护下搅拌反应27h,反应结束后,固体用甲醇-乙酸混合液(体积比9:1)洗涤至洗液中检测不到氟氯氰菊酯,洗涤后固体在40℃下真空干燥,制得氟氯氰菊酯的磁性分子印迹聚合物;磁性非印迹分子聚合物的制备过程除了不加氟氯氰菊酯以外,其余步骤相同。
本实例制得的菊酯类磁性分子印迹聚合物的结构表征如下:
(1)振动样品磁强计图(VSM)
结果见图1,由图1可见:由于对Fe3O4的修饰和聚合物的包裹,使得磁性聚合物的磁性较Fe3O4明显减弱;表明磁性分子印迹聚合物制备成功。
(2)透射电子显微镜图(TEM)
结果见图2,由图2(a)可以观察到Fe3O4粒子均匀,且有较好的分散性,而图2(b)的粒子外层有明显的包裹物,粒径增大。
2、样品前处理
按每1mL中药材提取液添加20mg氟氯氰菊酯的磁性分子印迹聚合物的比例,在金银花提取液(取研磨后的10mg金银花用40mL乙腈超声提取4h后制得)中添加氟氯氰菊酯的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,用水冲洗分离出磁性分子聚合物,然后用8mL乙腈超声洗脱6h,再用0.45μm滤膜过滤后,滤液采用加标的方式,用HPLC检测样品中氟氯氰菊酯的含量,表1为金银花中氟氯氰菊酯的加标回收率检测结果;
表1
。
实施例2:中药材中菊酯类农残的简易样品前处理方法如下:
1、菊酯类农残的磁性分子印迹聚合物的制备
(1)将FeCl3·6H2O溶液和FeCl2·4H2O溶液混合,在氮气、65℃下搅拌50min后,按每100mL混合液滴加18mL氨水的比例,在混合液中添加氨水,继续反应40min,溶液中出现黑色沉淀即生成了Fe3O4;其中FeCl3·6H2O与FeCl2·4H2O的质量比为2.5:1,FeCl3·6H2O溶液浓度为55g/L;反应液自然冷却后,用外加磁场分离获得Fe3O4颗粒,Fe3O4颗粒用水清洗至pH=7;
(2)将清洗后的Fe3O4颗粒超声分散到质量浓度80%的乙醇溶液中,Fe3O4颗粒在乙醇溶液中的浓度为12g/L,然后按每100mL分散液添加氨水7mL、硅酸四乙酯0.8mL的比例在分散液中加入氨水和硅酸四乙酯,氮气、40℃条件下搅拌反应15h,反应结束后,在外加磁场作用下进行分离,固体用纯水洗6次,然后在55℃下真空干燥,制得Fe3O4@SiO2颗粒;(3)将联苯菊酯与甲基丙烯酸按摩尔比1:8的比例分散在二甲基亚砜中,联苯菊酯在二甲基亚砜的浓度为1.5g/L,然后在温度20℃下反应6h,制得预聚合物;
(4)在预聚合物中加入Fe3O4@SiO2二甲基亚砜分散液、三羟甲基丙烷三甲基丙烯酸酯、偶氮二异丁腈,其中Fe3O4@SiO2二甲基亚砜分散液按每100mL 体积浓度90%的二甲基亚砜中分散100mg Fe3O4@SiO2颗粒制得,Fe3O4@SiO2颗粒与联苯菊酯的质量比为1:30,三羟甲基丙烷三甲基丙烯酸酯与联苯菊酯的摩尔比为,30:1,偶氮二丁腈与联苯菊酯的摩尔比为1:3在70℃、氮气保护下搅拌反应18h,反应结束后,固体用甲醇-乙酸混合液(体积比6:1)洗涤至洗液中检测不到联苯菊酯,洗涤后固体在60℃下真空干燥,制得联苯菊酯的磁性分子印迹聚合物;
2、样品前处理
按每1mL中药材提取液添加45mg联苯菊酯的磁性分子印迹聚合物的比例,在金银花提取液(取研磨后的15mg金银花用60mL乙腈超声提取5h后制得)中添加联苯菊酯的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,用水冲洗分离出磁性分子聚合物,然后用8mL乙腈超声洗脱8h,再用0.45μm滤膜过滤后,用HPLC检测样品中联苯菊酯的含量,表2为金银花中联苯菊酯加标回收率检测结果。
表2
。
实施例3:本中药材中菊酯类农残的简易样品前处理方法如下:
1、菊酯类农残的磁性分子印迹聚合物的制备
(1)将FeCl3·6H2O溶液和FeCl2·4H2O溶液混合,在氮气、70℃下搅拌25min后,按每100mL混合液滴加20mL氨水的比例,在混合液中添加氨水,继续反应50min,溶液中出现黑色沉淀即生成了Fe3O4;其中FeCl3·6H2O与FeCl2·4H2O的质量比为3:1,FeCl3·6H2O溶液浓度为60g/L;反应液自然冷却后,用外加磁场分离获得Fe3O4颗粒,Fe3O4颗粒用水清洗至pH=7;
(2)将清洗后的Fe3O4颗粒超声分散到质量浓度85%的乙醇溶液中,Fe3O4颗粒在乙醇溶液中的浓度为15g/L,然后按每100mL分散液添加氨水8mL、硅酸四乙酯1mL的比例在分散液中加入氨水和硅酸四乙酯,氮气、40℃条件下搅拌反应18h,反应结束后,在外加磁场作用下进行分离,固体用纯水洗5次,然后在60℃下真空干燥,制得Fe3O4@SiO2颗粒;
(3)将溴氰菊酯与丙烯酰胺按摩尔比1:6的比例分散在二甲基亚砜中,溴氰菊酯在二甲基亚砜的浓度为1g/L,然后在温度10℃下反应8h,制得预聚合物;
(4)在预聚合物中加入Fe3O4@SiO2二甲基亚砜分散液、乙二醇二甲基丙烯酸酯、偶氮二异丁腈,其中Fe3O4@SiO2二甲基亚砜分散液按每100mL 体积浓度85%的二甲基亚砜中分散140mg Fe3O4@SiO2颗粒制得,Fe3O4@SiO2颗粒与溴氰菊酯的质量比为1:25,乙二醇二甲基丙烯酸酯与溴氰菊酯的摩尔比为25:1,偶氮二丁腈与溴氰菊酯的摩尔比为1:2,在60℃、氮气保护下搅拌反应25h,反应结束后,固体用甲醇-乙酸混合液(体积比4:1)洗涤至洗液中检测不到溴氰菊酯,洗涤后固体在55℃下真空干燥,制得溴氰菊酯的磁性分子印迹聚合物。
磁性非印迹分子聚合物的制备过程除了不加溴氰菊酯以外,其余步骤相同。
利用吸附动力试验和等温吸附试验来评价磁性分子聚合物的吸附性能,通过图3的吸附动力学曲线可以看到聚合过程中加入了模板分子的聚合物(MMIPs)的吸附量始终大于未加入模板分子的聚合物(MNIPs),且在平衡时达到了最大差异;通过图4的等温吸附试验可以看到随着初始浓度的增大,MMIPs和MNIPs的吸附差异越来越大,直至平衡;从图3、图4可以看出MMIPs较MNIPs的吸附性能有了很大的提高。
2、样品前处理
按每1mL中药材提取液添加30mg溴氰菊酯的磁性分子印迹聚合物的比例,在金银花提取液(取研磨后的20mg金银花用50mL乙腈超声提取6h后制得)中添加溴氰菊酯的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,用水冲洗分离出磁性分子聚合物,然后用8mL乙腈超声洗脱7h,再用0.45μm滤膜过滤后,用于溴氰菊酯农残分析检测,表3为金银花中溴氰菊酯加标回收率检测结果;
表3
Claims (8)
1.一种检测中药材中菊酯类农残的样品前处理方法,其特征在于:按每1mL中药材提取液添加20mg~50mg菊酯类农残的磁性分子印迹聚合物的比例,在中药材提取液中添加菊酯类农残的磁性分子印迹聚合物,充分震荡后,在外加磁场作用下分离出磁性分子聚合物,用水冲洗分离出磁性分子聚合物,然后用乙腈超声洗脱6~8h,再用0.45μm滤膜过滤后,滤液用于菊酯类农残分析检测。
2.根据权利要求1所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于,菊酯类农残的磁性分子印迹聚合物的制备方法如下:
(1)将FeCl3·6H2O溶液和FeCl2·4H2O溶液混合,在氮气、60℃~70℃下搅拌20~50min后,按每100mL混合液滴加15mL~20mL氨水的比例,在混合液中添加氨水,继续反应30min~60min,溶液中出现黑色沉淀即生成了Fe3O4;其中FeCl3·6H2O与FeCl2·4H2O的质量比为2:1~3:1,FeCl3·6H2O溶液浓度为50~60g/L;反应液自然冷却后,用外加磁场分离获得Fe3O4颗粒,Fe3O4颗粒用水清洗至pH=7;
(2)将清洗后的Fe3O4颗粒超声分散到质量浓度75%~85%的乙醇溶液中,Fe3O4颗粒在乙醇溶液中的浓度为10g/L~15g/L,然后按每100mL分散液添加氨水6mL~8mL、硅酸四乙酯0.5mL~1mL的比例在分散液中加入氨水和硅酸四乙酯,氮气、40℃条件下搅拌反应10h~20h,反应结束后,在外加磁场作用下进行分离,固体用纯水洗5~6次,然后在50℃~60℃下真空干燥,制得Fe3O4@SiO2颗粒;
(3)将模板分子与功能单体按摩尔比1:4~1:8的比例分散在二甲基亚砜中,然后在温度0~24℃下反应5~12h,制得预聚合物;
(4)在预聚合物中加入Fe3O4@SiO2二甲基亚砜分散液、交联剂、引发剂,其中Fe3O4@SiO2颗粒与模板分子的质量比为1:20~1:30,交联剂与模板分子的摩尔比为20:1~30:1,引发剂与模板分子的摩尔比为1:1~1:3;在50℃~70℃、氮气保护下搅拌反应18~27h,反应结束后,固体用甲醇-乙酸混合液洗涤至洗液中检测不到模板分子,洗涤后固体在40~60℃下真空干燥,制得菊酯类农残的磁性分子印迹聚合物。
3.根据权利要求1所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于:中药材提取液是取研磨后的10mg~20mg中药材用40mL~60mL乙腈超声提取4h~6h后制得。
4.根据权利要求2所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于:模板分子为氟氯氰菊酯、氰戊菊酯、溴氰菊酯或联苯菊酯。
5.根据权利要求2所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于:功能单体为丙烯酰胺或甲基丙烯酸。
6.根据权利要求2所述的检测中药材中菊酯类农残的样品前处理方法,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。
7.根据权利要求2所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于:引发剂为偶氮二异丁腈。
8.根据权利要求2所述的检测中药材中菊酯类农残的样品前处理方法,其特征在于:甲醇-乙酸的混合溶液中甲醇与乙酸体积比为8:2~9:1。
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