CN114733496A - 除虫脲分子印迹磁性微球的制备及其在固相萃取中的应用 - Google Patents
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Abstract
本发明公开了一种除虫脲分子印迹磁性微球的制备及其在固相萃取中的应用,以除虫脲为模板分子,利用表面印迹技术制备了磁性印迹聚合物,由于印迹的位点形成于表面,提高了聚合物的吸附效率。本发明除虫脲磁性印迹聚合物具有很好的磁性,其饱和磁化强度可达到41.7emu/g,可以在外加磁场下分离和分析复杂样品中的除虫脲。应用本发明制备的除虫脲磁性印迹聚合物分析含有类似结构杀虫剂的混合溶液,具有选择性高和操作简便的特点,回收率可达到87‑98%。
Description
技术领域
本发明涉及一种除虫脲分子印迹磁性微球的制备方法及其在固相萃取中的应用。
背景技术
作为一种苯甲酰脲类低毒性杀虫剂,除虫脲广泛应用于果树、棉花以及蔬菜的杀虫处理。但长期过度使用会造成对环境、食品的污染,从而对人类造成潜在的危害。且通过光降解除虫脲,得到的产物对氯苯、氯苯基脲等化合物可能会具有致癌性。传统的固相萃取法大都使用孔介材料作为吸附剂,在分离处理过程中会导致损失或产生共沉淀,从而使其应用受到限制。因此建立一种新型、高效的富集和分离除虫脲的方法尤为重要。
分子印迹聚合物具有特异性识别能力,可以从复杂的环境基质中选择性吸附模板分子,将其作为固相萃取柱的吸附剂,达到良好的吸附容量以及能够萃取靶向目标物质。
大多数传统方法制备的分子印迹聚合物存在着一些缺点,例如结合位点分布不均匀以及模板分子和功能单体完全嵌入到聚合物基质中导致目标分子不易与识别位点相结合等。为了克服这些缺陷,表面印迹技术得到了进一步发展。表面印迹法是在固相载体表面进行聚合反应,使聚合物的印迹位点暴露在表面的一种技术。利用四氧化三铁作为载体制备的磁性印迹聚合物,不仅具有高选择性和超顺磁性,且不需要将吸附剂填充入固相萃取柱,可直接加入样品溶液中进行吸附,操作简便,在分离分析和检测领域具有更广阔的应用前景。
发明内容
本发明针对上述现有技术所存在的不足,提供了一种除虫脲分子印迹磁性微球的制备方法及其在固相萃取中的应用。
本发明除虫脲分子印迹磁性微球的制备方法,包括如下步骤:
步骤1:磁性Fe3O4纳米微球的表面修饰
将1.0g Fe3O4纳米粒子分散在乙醇/水混合体系中,在上述分散液中加入硅烷,超声混合均匀,充氮密封,40~80℃恒温搅拌反应4~8h,得到的反应产物用乙醇洗涤,磁分离,真空干燥;
步骤1中所述的乙醇/水混合体系中乙醇和水的体积比为1:(1~8)。所述水为去离子水、蒸馏水或超纯水。
步骤1中所述的硅烷为四乙氧基硅烷、3-(甲基丙烯酰氯)丙基三甲氧基硅烷、苯胺甲基三乙氧基硅烷中的至少一种,用量为0.1~2mL。
步骤2:预聚合产物的合成
将0.31g除虫脲和功能单体加入到50mL溶剂中充分溶解,室温下反应1~5h,得到混合液a;
步骤2中所述的功能单体为亚甲基丁二酸、甲基丙烯酸羟乙酯、乙烯基苯甲酸、丙烯酰胺、甲基丙烯酸、4-乙烯基吡啶、2-乙烯基吡啶中的至少一种。除虫脲和功能单体的摩尔比为1:1~12。
步骤2中所述的溶剂为氯仿、乙醇、乙腈中的至少一种。
步骤3:分子印迹磁性微球的制备
将0.1g~2.0g步骤1获得的Fe3O4纳米微球加入到混合液a中,并加入交联剂和引发剂,超声分散,通氮,40~80℃加热反应;磁分离获得产物,用乙酸/甲醇混合溶液洗涤除去模板分子,直至洗脱液中检测不到模板分子为止,真空干燥至恒重,得到除虫脲分子印迹磁性微球。
步骤3中所述的交联剂为甲基丙烯酸乙二醇酯、三羟甲基丙烷三丙烯酸甲酯、N,N-亚甲基双丙烯酰胺、二乙烯基苯中的至少一种。除虫脲与交联剂的摩尔比为1:(12~24)。
步骤3中所述的引发剂为偶氮二异丁腈、偶氮二甲基异戊腈中的至少一种。引发剂的质量与混合液a的体积比例为1g:(0.4~2L)。
步骤3中所述的乙酸/甲醇混合溶液中乙酸和甲醇的体积比为1:5~15。
本发明制备的除虫脲分子印迹磁性微球的应用,是将所述除虫脲分子印迹磁性微球用于固相萃取中,以实现对除虫脲的有效分离。
本发明的有益效果是:
(1)本发明以除虫脲为模板分子,利用表面印迹技术制备了磁性印迹聚合物,由于印迹的位点形成于表面,提高了聚合物的吸附效率。
(2)本发明除虫脲磁性印迹聚合物具有很好的磁性,其饱和磁化强度可达到41.7emu/g,可以在外加磁场下分离和分析复杂样品中的除虫脲。
(3)应用本发明制备的除虫脲磁性印迹聚合物分析含有类似结构杀虫剂的混合溶液,具有选择性高和操作简便的特点,回收率可达到87-98%。
附图说明
图1是本发明实施例1制备的除虫脲分子印迹磁性微球的扫描电镜图;
图2是本发明实施例2制备的除虫脲分子印迹磁性微球的扫描电镜图;
图3是本发明实施例3制备的除虫脲分子印迹磁性微球的扫描电镜图;
图4是本发明实施例4制备的除虫脲分子印迹磁性微球的磁滞回归线;
图5是分子印迹磁性微球和非印迹磁性微球对苯甲酰脲类杀虫剂混合溶液的吸附结果;
图6a是加标橙汁样品直接进样的高效液相色谱图,图6b是加标橙汁样品经过分子印迹磁性材料富集分离后的高效液相色谱图。
具体实施方式
下面通过实施例对本发明进行详细描述。
实施例1:
本实施例中除虫脲分子印迹磁性微球的制备方法如下:
步骤1:磁性Fe3O4纳米微球的表面修饰
取1.0g Fe3O4纳米粒子超声分散于25mL乙醇和25mL去离子水混合溶液中,加入1mL3-(甲基丙烯酰氯)丙基三甲氧基硅烷,超声混合均匀。并向其通入氮气密封,然后将所制备的悬浮液加热到50℃,搅拌反应6h,自然冷却至室温。所得产物用磁分离收集,乙醇洗涤数次,置于真空干燥箱过夜,制得硅烷修饰的Fe3O4纳米粒子。
步骤2:预聚合产物的合成
将0.31g除虫脲和0.34g甲基丙烯酸充分溶解于50mL氯仿溶液中,室温下反应1h,得到混合液a;
步骤3:分子印迹磁性微球的制备
将0.5g步骤1获得的Fe3O4纳米微球加入到混合液a中,并加入3.96g甲基丙烯酸乙二醇酯和0.05g偶氮二异丁腈,超声10min,通N210min后密封,60℃反应24h;利用磁分离分离出除虫脲分子印迹磁性微球,最后用乙酸-甲醇溶液(1:5~15,v:v)洗涤除去模板分子,直至洗脱液中检测不到模板分子为止,真空干燥至恒重,得到除虫脲分子印迹磁性微球。
将上述方法得到的除虫脲分子印迹微球在扫描电镜下观察,结果如图1所示,发现得到分子印迹磁性微球类似于海绵的不规则结构。
实施例2:
本实施例中除虫脲分子印迹磁性微球的制备方法如下:
步骤1:磁性Fe3O4纳米微球的表面修饰
取1.0g Fe3O4纳米粒子超声分散于25mL乙醇和25mL去离子水混合溶液中,加入1mL3-(甲基丙烯酰氯)丙基三甲氧基硅烷,超声混合均匀。并向其通入氮气密封,然后将所制备的悬浮液加热到50℃,搅拌反应6h,自然冷却至室温。所得产物用磁分离收集,乙醇洗涤数次,置于真空干燥箱过夜,制得硅烷修饰的Fe3O4纳米粒子。
步骤2:预聚合产物的合成
将0.31g除虫脲和0.34g甲基丙烯酸充分溶解于50mL乙醇溶液中,室温下反应1h,得到混合液a;
步骤3:分子印迹磁性微球的制备
将0.5g步骤1获得的Fe3O4纳米微球加入到混合液a中,并加入3.96g甲基丙烯酸乙二醇酯和0.05g偶氮二异丁腈,超声10min,通N210min后密封,60℃反应24h;利用磁分离分离出除虫脲分子印迹磁性微球,最后用乙酸-甲醇溶液(1:5~15,v:v)洗涤除去模板分子,直至洗脱液中检测不到模板分子为止,真空干燥至恒重,得到除虫脲分子印迹磁性微球。
将上述方法得到的除虫脲分子印迹微球在扫描电镜下观察,结果如图2所示,发现得到分子印迹磁性微球为不均匀的球状,尺寸大小不一。
实施例3:
本实施例中除虫脲分子印迹磁性微球的制备方法如下:
步骤1:磁性Fe3O4纳米微球的表面修饰
取1.0g Fe3O4纳米粒子超声分散于25mL乙醇和25mL去离子水混合溶液中,加入1mL3-(甲基丙烯酰氯)丙基三甲氧基硅烷,超声混合均匀。并向其通入氮气密封,然后将所制备的悬浮液加热到50℃,搅拌反应6h,自然冷却至室温。所得产物用磁分离收集,乙醇洗涤数次,置于真空干燥箱过夜,制得硅烷修饰的Fe3O4纳米粒子。
步骤2:预聚合产物的合成
将0.31g除虫脲和0.34g甲基丙烯酸充分溶解于50mL乙腈溶液中,室温下反应1h,得到混合液a;
步骤3:分子印迹磁性微球的制备
将0.5g步骤1获得的Fe3O4纳米微球加入到混合液a中,并加入3.96g甲基丙烯酸乙二醇酯和0.05g偶氮二异丁腈,超声10min,通N210min后密封,60℃反应24h;利用磁分离分离出除虫脲分子印迹磁性微球,最后用乙酸-甲醇溶液(1:5~15,v:v)洗涤除去模板分子,直至洗脱液中检测不到模板分子为止,真空干燥至恒重,得到除虫脲分子印迹磁性微球。
将上述方法得到的除虫脲分子印迹微球在扫描电镜下观察,结果如图3所示,发现得到分子印迹磁性微球为规则的球状,尺寸大小均一,分散性较好。
实施例4:除虫脲分子印迹磁性微球磁性能的测定
本实施例中除虫脲分子印迹磁性微球的制备方法与实施例3相同。
本实施例中磁性能的具体评价方法如下:称取30mg分子印迹磁性微球装入1cm左右长的塑料小管中,在振动样品磁强计的检测下,分析得到的结果如图4所示,可知实施例4制备的除虫脲分子印迹磁性微球具有超顺磁性,饱和磁化强度为41.7emu/g。
实施例5:除虫脲分子印迹磁性微球选择性吸附实验
本实施例中除虫脲分子印迹磁性微球的制备方法与实施例3相同。
非印迹磁性微球的制备方法与实施例3不同之处在于除去步骤2中不加除虫脲外,其余步骤与除虫脲分子印迹磁性微球制备相同。
本实施例中选择性吸附特性评价的具体方法如下:选择两种苯甲酰脲类杀虫剂(即杀铃脲HFM、氟苯脲TBZ)与除虫脲DBZ作为竞争分子。称取20mg分子印迹磁性微球(或非印迹磁性微球)于5mL三种苯甲酰脲类杀虫剂的混合溶液中,室温振荡3h后,使用磁分离,取上清液过滤,采用高效液相色谱仪测定混合溶液中三种苯甲酰脲类杀虫剂浓度。
吸附结果如图5显示,合成的除虫脲分子印迹磁性微球在复杂的苯甲酰脲类杀虫剂混合溶液中,对除虫脲的吸附效果最好。
实施例6:除虫脲分子印迹磁性微球应用于磁性固相萃取中
本实施例中除虫脲分子印迹磁性微球的制备方法与实施例3相同。
本实施例中制备的除虫脲分子印迹磁性微球应用于磁性固相萃取中,具体方法如下:称取20mg除虫脲分子印迹磁性微球于锥形瓶中,加入5mL含有除虫脲的橙汁(10mg/L)待测液。室温振荡20min后,利用磁分离,加入乙腈超声淋洗,淋洗后的聚合物加入洗脱液进行超声洗脱。洗脱溶液经过滤后用于高效液相色谱检测分析。
图6a是加标样品直接进样的高效液相色谱图,图6b是加标橙汁样品经过分子印迹磁性材料富集分离后的高效液相色谱图。检测结果表明,分子印迹磁性微球对加标橙汁样品中的除虫脲进行富集,回收率为97.2%,相对标准偏差RSD为1.63%。
Claims (9)
1.一种除虫脲分子印迹磁性微球的制备方法,其特征在于包括如下步骤:
步骤1:磁性Fe3O4纳米微球的表面修饰
将1.0g Fe3O4纳米粒子分散在乙醇/水混合体系中,在上述分散液中加入硅烷,超声混合均匀,充氮密封,40~80℃恒温搅拌反应4~8h,得到的反应产物用乙醇洗涤,磁分离,真空干燥;
步骤2:预聚合产物的合成
将0.31g除虫脲和功能单体加入到50mL溶剂中充分溶解,室温下反应1~5h,得到混合液a;
步骤3:分子印迹磁性微球的制备
将0.1g~2.0g步骤1获得的Fe3O4纳米微球加入到混合液a中,并加入交联剂和引发剂,超声分散,通氮,40~80℃加热反应;磁分离获得产物,用乙酸/甲醇混合溶液洗涤除去模板分子,直至洗脱液中检测不到模板分子为止,真空干燥至恒重,得到除虫脲分子印迹磁性微球。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1中,所述乙醇/水混合体系中乙醇和水的体积比为1:(1~8)。
3.根据权利要求1所述的制备方法,其特征在于:
步骤1中,所述硅烷为四乙氧基硅烷、3-(甲基丙烯酰氯)丙基三甲氧基硅烷、苯胺甲基三乙氧基硅烷中的至少一种,用量为0.1~2mL。
4.根据权利要求1所述的制备方法,其特征在于:
步骤2中,所述功能单体为亚甲基丁二酸、甲基丙烯酸羟乙酯、乙烯基苯甲酸、丙烯酰胺、甲基丙烯酸、4-乙烯基吡啶、2-乙烯基吡啶中的至少一种;除虫脲和功能单体的摩尔比为1:1~12。
5.根据权利要求1所述的制备方法,其特征在于:
步骤2中,所述溶剂为氯仿、乙醇、乙腈中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于:
步骤3中,所述交联剂为甲基丙烯酸乙二醇酯、三羟甲基丙烷三丙烯酸甲酯、N,N-亚甲基双丙烯酰胺、二乙烯基苯中的至少一种;除虫脲与交联剂的摩尔比为1:(12~24)。
7.根据权利要求1所述的制备方法,其特征在于:
步骤3中,所述引发剂为偶氮二异丁腈、偶氮二甲基异戊腈中的至少一种;引发剂的质量与混合液a的体积比例为1g:(0.4~2L)。
8.根据权利要求1所述的制备方法,其特征在于:
步骤3中,所述乙酸/甲醇混合溶液中乙酸和甲醇的体积比为1:5~15。
9.根据权利要求1-8所述任一项制备方法获得的除虫脲分子印迹磁性微球的应用,其特征在于:所述除虫脲分子印迹磁性微球用于固相萃取中,以实现对除虫脲的有效分离。
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