CN108159734A - 一种氨基化多壁碳纳米管固相萃取柱及其制备方法 - Google Patents
一种氨基化多壁碳纳米管固相萃取柱及其制备方法 Download PDFInfo
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Abstract
本发明涉及了一种氨基化多壁碳纳米管固相萃取柱及其制备方法。本发明的氨基化多壁碳纳米管固相萃取柱采用氨基化多壁碳纳米管为固相萃取柱的填充材料，该氨基化多壁碳纳米管由多壁碳纳米管依次经羧基化、氨基化化学修饰所得。本发明主要适用于水果、蔬菜、茶叶等食用农产品中农药残留测定时对样品的净化。本发明中的固相萃取柱具有净化效果好，目标物回收率高，价格低廉，氨基化修饰过程简单，易于批量生产的特点。
Description
技术领域
本发明属于化学分析测试技术领域，具体涉及一种氨基化多壁碳纳米管固相萃取柱及其制备方法。
背景技术
固相萃取技术是近年来应用较为广泛一种样品前处理技术，该技术基于液-固相色谱理论，利用固相选择性吸附和选着性洗脱的液相色谱法原理对样品进行富集、分离和净化，达到对样品和基质干扰物之间的分离。通过固相萃取技术可在分析过程中有效去除基质干扰物的影响，保证检测的准确度和灵敏度。该技术广泛的应用在医药、食品和环境检验检测领域。
多壁碳纳米管是碳六元环构成的类石墨平面卷曲而成的纳米级中空管，具有良好的化学稳定性、热稳定性和高比表面积，是一种优秀的吸附材料。其作为一种新型材料，近年来在固相萃取中逐渐开始得到应用。目前在利用多壁碳纳米管为吸附剂进行固相萃取的应用过程中由于其结构单一，对极性化合物吸附能力较差，不能全面且有效吸附基质干扰物，限制了其净化效果。氨基化多壁碳纳米管在多壁碳纳米管原来的基础上增加氨基，可对有机酸、极性色素和脂肪酸等极性基质干扰物进行有效的吸附，可有效提升对样品的净化效果。
发明内容
针对现有技术存在的问题，本发明的目的在于设计提供一种氨基化多壁碳纳米管固相萃取柱及其制备方法的技术方案。
所述的一种氨基化多壁碳纳米管固相萃取柱，其特征在于采用氨基化多壁碳纳米管为固相萃取柱的填充材料，该氨基化多壁碳纳米管由多壁碳纳米管依次经羧基化、氨基化化学修饰所得，化学修饰按以下步骤进行：
（1）羧基化：将多壁碳纳米管置于体积比为浓硫酸：浓硝酸=3:1的混合液中，在60-70℃下回流4-6小时，冷却至室温，加入去离子水洗涤至中性，过0.45µm 滤膜过滤后真空干燥；
（2）氨基化：将羧基化后的多壁碳纳米管、乙二胺和二环己基碳二亚胺混合后在110-120 ℃下加热回流24-36小时，反应完成后用无水乙醇洗涤，过0.45 µm 滤膜过滤后60℃真空干燥，完全去除水分，得氨基化多壁碳纳米管。
所述的一种氨基化多壁碳纳米管固相萃取柱，其特征在于所述的氨基化多壁碳纳米管的外径为8-15 nm，长度为50µm；固相萃取柱空管材质为高纯度聚丙烯，容积为6 mL；筛板材质为高纯度聚乙烯；装填量为200 mg±5 mg，装填为0.7 cm。
所述的氨基化多壁碳纳米管固相萃取柱的制备方法，其特征在于包括以下步骤：
（1）将下筛板置于固相萃取柱空管底部；
（2）放入200 mg的氨基化多壁碳纳米管填料，轻敲固相萃取柱侧壁，使填料分布均匀；
（3）将上筛板放入固相萃取柱中，下压上筛板，压紧填料，使填装高度在0.7 cm。
所述的氨基化多壁碳纳米管固相萃取柱在食用农产品中农药残留量检测中的应用。
与现有技术相比，本发明具有以下有益效果：
（1）本发明所提供的氨基化多壁碳纳米管固相萃取柱对样品净化效果显著。较传统固相萃取柱或多壁碳纳米管为基质的固相萃取柱，该固相萃取柱吸附容量更大，可对有机酸、极性色素和脂肪酸等极性基质干扰物进行有效的吸附，有效提升对样品的净化效果；
（2）本发明氨基化多壁碳纳米管固相萃取柱制备方法易于操作；
（3）氨基化多壁碳纳米管固相萃取柱成本低，适用范围广，实验结果的准确度和精确度均能达到较高的水平，易于批量生产和使用。
具体实施方式
以下结合实施例来进一步说明本发明。
实施例1：氨基化多壁碳纳米管固相萃取柱的制备方法
1）取材
取多壁碳纳米管、固相萃取柱空管和筛板。其中多壁碳纳米管的外径为8-15 nm，长度为50µm；固相萃取柱空管材质为高纯度聚丙烯，容积为6 mL；筛板材质为高纯度聚乙烯。
2）多壁碳纳米管氨基化
a羧基化：将多壁碳纳米管置于体积比为浓硫酸：浓硝酸=3:1的混合液中，在70 ℃下回流4小时，或在60 ℃下回流6小时，冷却至室温，加入去离子水洗涤至中性，过0.45µm 滤膜过滤后真空干燥；
b氨基化：将羧基化后的多壁碳纳米管、乙二胺和二环己基碳二亚胺混合后在120 ℃下加热回流24小时，或在110 ℃下加热回流36小时，反应完成后用无水乙醇洗涤，过0.45 µm滤膜过滤后60℃真空干燥，完全去除水分，得氨基化多壁碳纳米管。
3）装柱
a将下筛板置于固相萃取柱空管底部；
b放入200 mg的氨基化多壁碳纳米管填料，轻敲固相萃取柱侧壁，使填料分布均匀；
c将上筛板放入固相萃取柱中，下压上筛板，压紧填料，使填装高度在0.7 cm。
实施例2：黄瓜中检测农药残留
称取八份20g经粉碎搅拌均匀的黄瓜样品于离心管中，其中六份加入浓度为10µg/mL的α-六六六标准品溶液50µL，两份不添加作为对照，混匀静置1小时后，分别加入40.0 mL乙腈，用均质器在15000 r/min匀浆提取1 min, 加入5 g 氯化钠，再匀浆提取1min，将离心管放入离心机，在3000 r/min离心5min，取上清液20.0 mL，浓缩至约2 mL，待净化。
分别在实施例1制得的氨基化多壁碳纳米管固相萃取柱中加入约1cm高的无水硫酸钠，加样前先用4 mL乙腈-甲苯溶液（3+1，v/v）预洗柱，当液面到达硫酸钠顶部时，将待净化样品转移至净化柱上，再每次用2 mL乙腈-甲苯溶液（3：1）三次洗涤样液瓶，并将洗涤液转移入柱中。用约25mL乙腈-甲苯溶液（3：1）洗涤固相萃取柱，收集所有流出液于旋转蒸发瓶中。在40ºC水浴中旋转浓缩至近干，用正己烷复溶并定容至5.0 mL，过0.45µm滤膜后进行GC-MS分析。
检测结果显示两份对照样品中未检出α-六六六，其余六份加标样品中检出α-六六六加标回收率在92.5%-105.1%之间，相对标准偏差为4.6%。
实施例3：茶叶中检测农药残留
称取八份2 g经粉碎混匀的市售龙井茶样品于离心管中，其中六份加入浓度为1µg/mL的毒死蜱标准品溶液100µL，两份不添加作为对照，混匀静置1小时。分别加入15 mL乙腈，用均质器在15000 r/min匀浆提取1 min, 在3000 r/min离心5min，取上清液于旋转蒸发瓶中。样品残渣分别再用15 mL乙腈重复提取一次，离心后合并提取液，浓缩至约2 mL，待净化。
分别在实施例1制得的氨基化多壁碳纳米管固相萃取柱中加入约1cm高的无水硫酸钠，加样前先用4 mL乙腈-甲苯溶液（3+1）预洗柱，当液面到达硫酸钠顶部时，将待净化样品转移至净化柱上，再每次用2 mL乙腈-甲苯溶液（3+1）三次洗涤样液瓶，并将洗涤液转移入柱中。用约25mL乙腈-甲苯溶液（3+1）洗涤固相萃取柱，收集所有流出液于旋转蒸发瓶中。在40ºC水浴中旋转浓缩至近干，用正己烷复溶并定容至2.0 mL，过0.45µm滤膜后进行GC-MS分析。
检测结果显示两份对照样品中未检出毒死蜱，其余六份加标样品中检出毒死蜱加标回收率在90.9%-102.1%之间，相对标准偏差为5.3%。
Claims (4)
1.一种氨基化多壁碳纳米管固相萃取柱，其特征在于采用氨基化多壁碳纳米管为固相萃取柱的填充材料，该氨基化多壁碳纳米管由多壁碳纳米管依次经羧基化、氨基化化学修饰所得，化学修饰按以下步骤进行：
（1）羧基化：将多壁碳纳米管置于体积比为浓硫酸：浓硝酸=3:1的混合液中，在60-70℃下回流4-6小时，冷却至室温，加入去离子水洗涤至中性，过0.45µm 滤膜过滤后真空干燥；
（2）氨基化：将羧基化后的多壁碳纳米管、乙二胺和二环己基碳二亚胺混合后在110-120 ℃下加热回流24-36小时，反应完成后用无水乙醇洗涤，过0.45 µm 滤膜过滤后60℃真空干燥，完全去除水分，得氨基化多壁碳纳米管。
2.如权利要求1所述的一种氨基化多壁碳纳米管固相萃取柱，其特征在于所述的氨基化多壁碳纳米管的外径为8-15 nm，长度为50µm；固相萃取柱空管材质为高纯度聚丙烯，容积为6 mL；筛板材质为高纯度聚乙烯；装填量为200 mg±5 mg，装填为0.7 cm。
3.如权利要求1或2所述的氨基化多壁碳纳米管固相萃取柱的制备方法，其特征在于包括以下步骤：
（1）将下筛板置于固相萃取柱空管底部；
（2）放入200 mg的氨基化多壁碳纳米管填料，轻敲固相萃取柱侧壁，使填料分布均匀；
（3）将上筛板放入固相萃取柱中，下压上筛板，压紧填料，使填装高度在0.7 cm。
4.如权利要求1或2所述的氨基化多壁碳纳米管固相萃取柱在食用农产品中农药残留量检测中的应用。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745306A (zh) * | 2018-06-27 | 2018-11-06 | 东华理工大学 | 一种环氧氯丙烷交联壳聚糖/氨基化碳纳米管复合气凝胶的制备方法 |
| CN108889275A (zh) * | 2018-08-01 | 2018-11-27 | 东华理工大学 | 一种功能化单壁碳纳米角的制备方法及应用 |
| CN109622011A (zh) * | 2018-12-06 | 2019-04-16 | 浙江工业大学 | 一种氨基化多壁碳纳米管负载钌催化剂及其制备与应用 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811024A (zh) * | 2010-04-02 | 2010-08-25 | 同济大学 | 一种富集铅离子用的固相萃取剂的制备及应用方法 |
| CN102527334A (zh) * | 2011-12-31 | 2012-07-04 | 汕头大学 | 功能化多壁碳纳米管基质的固相萃取柱及其制备方法 |
| CN103041773A (zh) * | 2012-12-04 | 2013-04-17 | 天津大学 | 一种磁性碳纳米管复合材料及其制备方法和应用 |
| CN105776183A (zh) * | 2016-05-16 | 2016-07-20 | 安徽工业大学 | 一种二茂铁基碳纳米管复合材料的制备方法及其应用 |
| CN106277172A (zh) * | 2016-10-14 | 2017-01-04 | 华北电力大学 | 一种利用石墨烯片与碳纳米管三维复合物吸附水中重金属的方法 |
| US20170184554A1 (en) * | 2016-01-07 | 2017-06-29 | Alireza Ghiasvand | Vacuum-assisted in-needle capplicary adsorption trap with multiwalled polyaniline/carbon nanotube nanocomposite sorbent |
| CN107486149A (zh) * | 2017-08-15 | 2017-12-19 | 太原理工大学 | 碳纳米管薄膜及其制备方法与应用 |
-
2018
- 2018-01-12 CN CN201810031376.7A patent/CN108159734A/zh active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811024A (zh) * | 2010-04-02 | 2010-08-25 | 同济大学 | 一种富集铅离子用的固相萃取剂的制备及应用方法 |
| CN102527334A (zh) * | 2011-12-31 | 2012-07-04 | 汕头大学 | 功能化多壁碳纳米管基质的固相萃取柱及其制备方法 |
| CN103041773A (zh) * | 2012-12-04 | 2013-04-17 | 天津大学 | 一种磁性碳纳米管复合材料及其制备方法和应用 |
| US20170184554A1 (en) * | 2016-01-07 | 2017-06-29 | Alireza Ghiasvand | Vacuum-assisted in-needle capplicary adsorption trap with multiwalled polyaniline/carbon nanotube nanocomposite sorbent |
| CN105776183A (zh) * | 2016-05-16 | 2016-07-20 | 安徽工业大学 | 一种二茂铁基碳纳米管复合材料的制备方法及其应用 |
| CN106277172A (zh) * | 2016-10-14 | 2017-01-04 | 华北电力大学 | 一种利用石墨烯片与碳纳米管三维复合物吸附水中重金属的方法 |
| CN107486149A (zh) * | 2017-08-15 | 2017-12-19 | 太原理工大学 | 碳纳米管薄膜及其制备方法与应用 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745306A (zh) * | 2018-06-27 | 2018-11-06 | 东华理工大学 | 一种环氧氯丙烷交联壳聚糖/氨基化碳纳米管复合气凝胶的制备方法 |
| CN108889275A (zh) * | 2018-08-01 | 2018-11-27 | 东华理工大学 | 一种功能化单壁碳纳米角的制备方法及应用 |
| CN108889275B (zh) * | 2018-08-01 | 2021-11-09 | 东华理工大学 | 一种功能化单壁碳纳米角的制备方法及应用 |
| CN109647001A (zh) * | 2018-11-30 | 2019-04-19 | 中国刑事警察学院 | 一种呋喃丹碳纳米管表面分子印迹固相萃取柱 |
| CN109622011A (zh) * | 2018-12-06 | 2019-04-16 | 浙江工业大学 | 一种氨基化多壁碳纳米管负载钌催化剂及其制备与应用 |
| CN110243955A (zh) * | 2019-05-20 | 2019-09-17 | 兰韬 | 专用于去除茶叶和烟叶中干扰成分的QuEChERS净化管及应用方法 |
| CN110243955B (zh) * | 2019-05-20 | 2022-06-14 | 北京科德诺思技术有限公司 | 专用于去除茶叶和烟叶中干扰成分的QuEChERS净化管及应用方法 |
| CN112034079A (zh) * | 2020-09-29 | 2020-12-04 | 中国科学院上海营养与健康研究所 | 一种检测茶叶样品中黄曲霉毒素含量的新型方法 |
| CN112229938A (zh) * | 2020-11-13 | 2021-01-15 | 上海市农业科学院 | 一种全氟化合物检测用固相萃取柱及其制作方法和应用 |
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