CN109647001A - 一种呋喃丹碳纳米管表面分子印迹固相萃取柱 - Google Patents

一种呋喃丹碳纳米管表面分子印迹固相萃取柱 Download PDF

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CN109647001A
CN109647001A CN201811449771.3A CN201811449771A CN109647001A CN 109647001 A CN109647001 A CN 109647001A CN 201811449771 A CN201811449771 A CN 201811449771A CN 109647001 A CN109647001 A CN 109647001A
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张文骥
郑吉龙
姜兆林
许英健
李栋
王鹏
陈洋
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CHINA COLLEGE OF CRIMINAL POLICE
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Abstract

本发明公开了一种呋喃丹碳纳米管表面分子印迹固相萃取柱，从生物检材中选择性提取分离呋喃丹的碳纳米管表面分子印迹材料，可将该材料作为填充剂制备成固相萃取柱。所述的固相萃取柱的基质为呋喃丹碳纳米管表面分子印迹聚合物，呋喃丹碳纳米管表面分子印迹聚合物是通过在碳纳米管表面进行分子印迹聚合反应，并进行模板分子洗脱制得的,固相萃取柱空管容积为1‑5ml，填装高度为0.5‑2.0 cm，空管材质为聚丙烯。本发明提供的碳纳米管表面分子印迹固相萃取柱对目标物质具有高选择性、高柱容量（20μg/g）、良好回收率（80%‑102%）及制备成本低、材料易得，适于批量生产等特点，具有良好的应用前景。

Description

一种呋喃丹碳纳米管表面分子印迹固相萃取柱
技术领域
本发明属于碳纳米管表面分子印迹技术在中毒生物检材前处理中应用的技术领域，涉及一种呋喃丹碳纳米管表面分子印迹聚合物的制备及利用该纳米材料为固相萃取剂制备纳米管表面分子印迹固相萃取柱，用来分离、提取、纯化生物检材中的呋喃丹。
背景技术
呋喃丹是一种氨基甲酸酯类杀虫剂，纯品为白色结晶，主要用于需求量种子包衣处理。按中国农药毒性分级标准，呋喃丹高毒农药，不能用在蔬菜和果树上。近年来,我国已严禁其在蔬菜上使用,并限制施用范围,禁止注册含有呋喃丹样品的农药,但是由于农资市场的管理尚未完全规范,且呋喃丹具有杀虫效果好、见效快、使用方便等特点,还有相当一部分地区农民仍在温室大棚或田间继续大量使用，导致呋喃丹中毒事件时有发生。【杜秋红,赵国宇,李玉梅,贾锡云,王根林.呋喃丹特性及生物降解研究进展[J].北方园艺,2010(14):210-212.】
生物检材中的成分十分复杂，含有蛋白质、脂肪、糖类等多种性质千差万别甚至完全相反的物质。虽然通过不同极性的溶剂，采用不同的萃取方式，可以将毒物溶解于极性相似的溶剂中而洗脱出来，但有研究表明，即使采用非常苛刻的溶剂条件和洗脱方式，也无法将生物检材中的干扰物质同分析物单纯依靠分子极性加以分离【Richter B E, Jones B A,Ezzell J L, et al. Accelerated solvent extraction: a technique for samplepreparation[J]. Analytical Chemistry, 1996, 68(6): 1033-1039.】。目前，对于生物样品的处理技术，主要集中在固相萃取、液相萃取、超临界流体萃取、微波萃取等。其中，固相萃取由于操作简单，快速，成本低等优点，逐渐成为最有前景的技术手段。固相萃取的性能通常与其填料性能密切相关，早期的硅胶柱、C18键合相柱、AL2O3柱因选择性差、富集容量低限制了其发展【王洪允, 江骥, 胡蓓,等. 固相萃取技术进展及在生物药物分析中的应用[J]. 药物分析杂志, 2003(3):236-241.】。
分子印迹技术的引入为生物检材的处理提供了独特的方案。分子印迹技术起源于免疫学中用锁匙理论解释免疫体系的尝试，它利用分子印迹聚合物经洗脱后，能够留下与模板分子形状、大小及识别位点相匹配的空穴的特点，来分离、筛选、纯目标化化合物。与常规的分离介质相比，其突出的优势是对被分离物或分析物具有极高的选择性和亲和性；同时又具有制备方便、耐受性好、使用寿命长等长处。然而，目前广泛使用的分子印迹材料有效印迹位点的密度很低，对目标分子的结合容量小， 结合动力学慢。而纳米结构的分子印迹材料具有较高的比表面积， 印迹材料上大多结合位点位于或接近材料表面，具有对目标分子高亲和力，结合动力学快速等特点，是弥补传统分子印迹缺陷的极佳手段。
发明内容
为了克服上述现有技术的不足，本发明提供了一种以呋喃丹为模板的以碳纳米管表面分子印迹聚合物为新型吸附材料为固定相的呋喃丹纳米管表面分子印迹固相萃取柱，并从呋喃丹中毒生物检材中定向分离、富集、纯化呋喃丹的方法，由此可以获得高提取率的目标成分。本发明通过以下技术方案实现。
采用的技术方案：
一种呋喃丹碳纳米管表面分子印迹固相萃取柱，所述的固相萃取柱的基质为呋喃丹碳纳米管表面分子印迹聚合物，呋喃丹碳纳米管表面分子印迹聚合物是通过在碳纳米管表面进行分子印迹聚合反应及模板分子洗脱制得，固相萃取柱空管容积为1-5ml，填装高毒为0.5-2.0cm，空管材质为聚丙烯。
1. 呋喃丹碳纳米管表面分子印迹聚合物的制备：
（1） 羧基化碳纳米管的制备：将多壁碳纳米管加入浓HNO3溶液中，超声处理1h使其分散，再于 80℃在磁力搅拌下回流24h，之后采用0.22μm滤膜过滤分散液，将得到的颗粒用蒸馏水反复洗涤至中性，65℃真空干燥过夜，备用；
（2）酰氯化碳纳米管的制备：将步骤（1）制得的羧基化碳纳米管加入氯化亚砜与氯仿的混合溶液（体积比1:3）中，于60℃在磁力搅拌下回流24h，冷却后，将混合物利用无水四氢呋喃通过0.22μm滤膜分散，并用蒸馏水多次洗涤至中性，65℃真空干燥过夜，备用；
（3）乙烯基修饰碳纳米管的合成：将步骤（2）制得的碳纳米管与丙烯醇、4-DMAP及三乙胺混合，加入20ml无水THF，于50℃在磁力搅拌下回流24h，冷却后离心并收集产物，用无水THF洗涤数次后，真空干燥过夜，备用；
（4）将模板分子、功能单体加入溶剂中混合，振荡2h，得到预装配溶液，备用；将步骤（3）制得的乙烯基修饰磁性碳纳米管加入溶剂中超声分散， 然后加入上述预装配溶液、引发剂及交联剂，超声30min后通入高纯氮气除净体系中氧气，置于油浴中于60℃反应16h，冷却后收集产物，并用乙醇洗涤过量反应物，至检测不到模板分子，聚合物再用水洗涤数次，于60℃下干燥至恒重，得到碳纳米管表面分子印迹材料。
2. 呋喃丹碳纳米管表面分子印迹固相萃取柱的制备
（1）将一片多孔性聚乙烯筛板放入固相萃取柱空管底部，聚乙烯筛板孔径为5-20μm，厚度为0.1-0.5cm；
（2）将相当于固相萃取柱空管容积30%-70%的呋喃丹碳纳米管表面分子印迹聚合物干法填装入柱内；
（3）在填装的呋喃丹碳纳米管表面分子印迹聚合物上放入另一片多孔性聚乙烯筛板，聚乙烯筛板孔径为5-20μm，厚度为0.1-0.5cm，压紧填料使固相萃取柱的填装高度保持在0.5-2.0cm,制备得固相萃取柱。
3. 固相萃取柱分离提取纯化生物检材中的呋喃丹
在进行固相萃取之前，首先用5-20mL甲醇、乙腈或者相应的缓冲溶液活化碳纳米管表面分子印迹聚合物，然后在重力或者真空泵负压驱动下使得生物检材匀浆液流过柱子，采用适量体积清洗液基质的杂质，使用合适的洗脱液甲醇、乙腈等把分析物洗脱并收集到容器中，然后进行定性、定量分析。
与现有的固相萃取柱相比，本发明所提供的呋喃丹碳纳米管表面分子印迹固相萃取柱具有以下优点：
（1）选择性好，柱容量高，达到20μg/g;
（2）选择实验大鼠为研究目标，对所述的呋喃丹碳纳米管表面分子印迹固相萃取柱的各项性能指标进行反复测试。结果表明，大鼠心、肝、脾、肺、肾、脾、脑、肌肉、心血等对于呋喃丹的加标回收率均能达到80%-102%，且解析过程简单。
附图说明
图1为呋喃丹碳纳米管表面分子印迹聚合物合成及其用于固相萃取呋喃丹示意图；
图2为呋喃丹碳纳米管表面分子印迹固相萃取柱示意图。
图中为：固相萃取柱柱管1、上筛板2、下筛板3、呋喃丹碳纳米管表面分子印迹聚合物填料4；
图3为合成到的呋喃丹碳纳米管表面分子印迹聚合物扫描电镜图。
具体实施方式
以下通过实施例形式，对本发明的上述内容再作进一步的详细说明，但不应将此理解为本发明上述主题的范围仅限于以下实例，凡基于本发明上述内容所实现的技术均属于本发明的范围。
实施例1 呋喃丹碳纳米管表面分子印迹聚合物（固相萃取柱填料）的制备
将0.5g多壁碳纳米管加入100ml浓HNO3溶液中，超声处理1h，再于80℃在磁力搅拌下回流24h。之后采用0.22μm滤膜过滤分散液，将得到的颗粒用蒸馏水反复洗涤至中性，65℃真空干燥过夜，备用；将0.2g上述制得的羧基化碳纳米管加入5mL氯化亚砜与15ml氯仿的混合溶液中，于60℃在磁力搅拌下回流24h，冷却后，将混合物利用无水四氢呋喃通过0.22μm滤膜分散，并用蒸馏水多次洗涤至中性，65℃真空干燥过夜，备用；将0.15g上述制得的碳纳米管与0.87g丙烯醇、0.18g4-DMAP及4.5g三乙胺混合，加入20ml无水THF，于50℃在磁力搅拌下回流24h，冷却后离心并收集产物，用无水THF洗涤数次后，真空干燥过夜，备用；将0.2mmol呋喃丹、1.0 mmolMMA加入溶剂中混合，振荡2h，得到预装配溶液，备用；将0.08g上述制得的乙烯基修饰磁性碳纳米管加入溶剂中超声分散，然后加入上述预装配溶液、2 mmolTRIM及30mg AIBN，超声30min后通入高纯氮气除净体系中氧气，置于油浴中于60℃反应16h，冷却后收集产物，并用乙醇洗涤过量反应物，至检测不到模板分子，聚合物再用水洗涤数次，于60℃下干燥至恒重，得到呋喃丹碳纳米管表面分子印迹聚合物。
实施例2 呋喃丹碳纳米管表面分子印迹固相萃取柱的制备
1、空柱材料及规格
现有的固相萃取小柱空柱规格从1cm到5cm不等。空柱材料聚丙烯，小柱上下各有20μm孔径的聚乙烯筛板。上述空柱均可用于本发明，但下面的实施例中采用3cm规格。
2、固相萃取柱的填料
固相萃取柱的填料为呋喃丹碳纳米管表面分子印迹聚合物。
3、填装量和填装高度
用上述制备的呋喃丹碳纳米管表面分子印迹聚合物填装3cm固相萃取柱，如附图2，将一片多孔性聚乙烯下筛板3置于固相萃取柱管1底部，称取相当于固相萃取柱溶剂50%的呋喃丹碳纳米管表面分子印迹聚合物放入固相萃取柱管1中，并将多孔性聚乙烯上筛板2放在填料上部，压紧填料使填装高度保持在1.0 cm,得到呋喃丹碳纳米管表面分子印迹固相萃取柱。
实施例3 固相萃取分离纯化生物检材中的呋喃丹
将大鼠按照4LD50（44 mg/kg）进行灌胃染毒，待大鼠死亡后，取其肝脏1g，剪碎，加入2μg 西维因和2 mL水，15000 rpm匀浆3 min。将制得的呋喃丹碳纳米管表面分子印迹固相萃取柱用4ml甲醇完全浸润填料保持5min，然后以1滴/秒的速度放掉液体，处理后小柱处于活化状态；连接好真空泵，使样品以2 ml/min的速度流过萃取柱，抽滤除去溶剂成分，再用甲醇/乙酸（90:10）洗脱固相萃取柱，用高效液相色谱仪器进行定性、定量分析，得肝脏中呋喃丹含量为0.1-10 μg/g。

Claims (3)

1.一种呋喃丹碳纳米管表面分子印迹固相萃取柱，其特征在于:所述的固相萃取柱的基质为呋喃丹碳纳米管表面分子印迹聚合物，呋喃丹碳纳米管表面分子印迹聚合物是通过在碳纳米管表面进行分子印迹聚合反应，并进行模板分子洗脱制得的,固相萃取柱空管容积为1-5ml，填装高度为0.5-2.0cm，空管材质为聚丙烯。
2.如权利要求1所述的一种呋喃丹碳纳米管表面分子印迹固相萃取柱，其特征在于：固相萃取柱制备方法为：
将一片多孔性聚乙烯筛板放入固相萃取柱空管底部，聚乙烯筛板孔径为5-20μm，厚度为0.1-0.5cm;
将相当于固相萃取柱空管容积30%-70%的呋喃丹碳纳米管表面分子印迹聚合物干法填装入柱内;
在填装的呋喃丹碳纳米管表面分子印迹聚合物上放入另一片多孔性聚乙烯筛板，聚乙烯筛板孔径为5-20μm，厚度为0.1-0.5cm，压紧填料使固相萃取柱的填装高度保持在0.5-2.0cm,制备得固相萃取柱。
3.一种如权利要求1所述制备呋喃丹碳纳米管表面分子印迹固相萃取柱，其特征在于：表面分子印迹聚合物由工业多壁纳米碳管经过以下步骤制得：
（1） 羧基化碳纳米管的制备：将多壁碳纳米管加入浓HNO3溶液中,超声处理1h使其分散，再于 80℃在磁力搅拌下回流24h,之后采用0.22μm滤膜过滤分散液，将得到的颗粒用蒸馏水反复洗涤至中性，65℃真空干燥过夜，备用；
（2）酰氯化碳纳米管的制备：将步骤（1）制得的羧基化碳纳米管加入氯化亚砜与氯仿的混合溶液中，体积比1:3，于60℃在磁力搅拌下回流24h，冷却后，将混合物利用无水四氢呋喃通过0.22μm滤膜分散，并用蒸馏水多次洗涤至中性，65℃真空干燥过夜，备用；
（3）乙烯基修饰碳纳米管的合成：将步骤（2）制得的碳纳米管与丙烯醇、4-DMAP及三乙胺混合，加入20ml无水THF，于50℃在磁力搅拌下回流24h，冷却后离心并收集产物，用无水THF洗涤数次后，真空干燥过夜，备用;
（4）将模板分子、功能单体加入溶剂中混合，振荡2h，得到预装配溶液，备用；将步骤（3）制得的乙烯基修饰磁性碳纳米管加入溶剂中超声分散， 然后加入上述预装配溶液、引发剂及交联剂，超声30min后通入高纯氮气除净体系中氧气，置于油浴中于60℃反应16h，冷却后收集产物，并用乙醇洗涤过量反应物，至检测不到模板分子，聚合物再用水洗涤数次，于60℃下干燥至恒重，得到碳纳米管表面分子印迹材料。
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Application publication date: 20190419