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基于固相萃取吸附剂在食品检测行业中应用研究

来源:食品安全质量检测学报 作者:范芳芳;魏宁果;邹力
发布于:2020-09-10 共9307字

  摘要:本文基于固相萃取吸附剂,综述了多种固相萃取小柱联用、分子印迹固相萃取、碳纳米管固相萃取和磁固相萃取等技术在食品分析前处理中的应用。研究表明,这些新型吸附剂相对于传统的固相萃取吸附剂具有分离速度快、效率高、环境友好、检出限低等优点。同时分别阐述了这4种萃取技术在食品检测领域的局限性。进一步指出开发高效快速分离目标物的吸附剂是固相萃取技术在食品检测行业的发展趋势。

  关键词:多种固相萃小柱联用; 分子印迹固相萃取; 碳纳米管固相萃取; 磁固相萃取; 食品分析; 发展趋势;

  Abstract:

  Based on solid phase extraction adsorbents, this paper reviewed the applications of various solid phase extraction small column combination, molecularly imprinted solid phase extraction, carbon nanotube solid phase extraction and magnetic solid phase extraction in food analysis pretreatment. The results showed that these new adsorbents had the advantages of high separation speed, high efficiency, environmental friendliness and low detection limit compared with traditional solid phase extraction adsorbents. At the same time, the limitations of these four extraction technologies in the field of food detection were expounded respectively. It is further pointed out that the development of adsorbents for efficient and rapid separation of target substances is the development trend of solid phase extraction technology in food detection industry.

  Keyword:several cartridges of solid-phase extraction; molecular imprinted solid-phase extraction; solid-phase extraction with packing of carbon nanotubes; magnetic solid-phase extraction; food analysis; the trend;

目录

  1引信………………………………………………………………………………1

  2固相萃取小柱填料的改进………………………………………………………………………………2

  3新型固相萃取填料的应用………………………………………………………………………………3

  3.1分子印迹固相萃取技术………………………………………………………………………………4

  3.2碳纳米管填料………………………………………………………………………………5

  3.3磁固相萃取技术………………………………………………………………………………6

  4结论与展望………………………………………………………………………………7

  文内图表………………………………………………………………………………8

  表1几种固相萃取吸附剂联用技术的应用………………………………………………………………………………8

  表2分子印迹固相萃取技术的应用………………………………………………………………………………8

  表3碳纳米管固相萃取技术的应用………………………………………………………………………………8

  表4 MSPE的应用………………………………………………………………………………8

  参考文献………………………………………………………………………………9

食品检验

  1 引言

  固相萃取技术(solid-phase extraction,SPE)是在液相色谱理论的基础上发展起来的一种分离、提取方法[1].该技术是利用固相萃取吸附剂与目标物吸附,样品基质和其他干扰物目标物分离,再利用有机溶剂或加热使目标物与吸附剂分离,并收集目标物,以达到样品基质中的目标物浓缩分离的目的[2].相对于液液分离法,该法具有试剂用量少、无乳化、效率高等优点,可采用烃类、有机氯以及有机磷类农药进行分离提纯[3].传统的固相萃取吸附剂,最初为键合硅胶C18,该填料疏水性较强,常用于萃取非极性、弱极性有机物,但由于性能单一,不太适用极性目标物质的分离[4],且食品样品基质繁杂多样,待测化合物的性质千差万别,传统的吸附剂已不能满足所有食品的分析要求[5].为解决这一问题,由改善吸附剂所形成新型SPE技术在食品检测行业得到迅猛发展。

  本文对近几年多种固相萃小柱联用、分子印迹固相萃取、碳纳米管固相萃取和磁固相萃取等4种技术在食品分析前处理中的应用进行了介绍和总结,分别阐述了这4种技术的优缺点,以期对以后的发展趋势做出展望。

  2 固相萃取小柱填料的改进

  由于食品样品前处理中的基质和干扰化合物多种多样,性质差别也较大,有时采用单一的固相萃取小柱难以有效去除样品基质和干扰物质[6],因此研究者将2个或多个不同填料的萃取小柱串联使用对样品进行前处理,具体应用见表1.

  几种固相萃取吸附剂联用技术主要应用于食品中抗生素类[8]以及农药残留类物质[9,10,11]的分离提取,具有除杂效果好,消除基质效应,有利于机子维稳等。该技术对目标物和杂质性质要求比较苛刻,在使用上具有一定的选择性,且经过几重固相萃取柱,有些目标物质会流失,导致回收率不高。随着研究的深入,多种固相萃取小柱联用技术的适用范围从茶叶[10]、谷物[9,11]等农产品扩大到动物源性食品[7,8]等复杂基质。

  该技术在食品检测行业中有着成熟的应用,采用C18柱、Ag和Na柱串联使用对乳粉基质进行除杂,该法对硝酸盐具有稳定良好的分离效率。

  3 新型固相萃取填料的应用

  传统固相萃取填料的选择性较强,存在使用范围小、对某些物质的吸附能力弱、萃取效率低等缺点[12],为了满足食品检测行业的发展,近年来,分子印迹技术[13]、碳纳米管材料[14]以及磁性材料[15]作为固相萃取小柱的填料发挥了重要的作用。

  3.1 分子印迹固相萃取技术

  分子印迹技术(molecular imprinting technology,MIT)针对模板分子制备的具有特定空间形状和功能集团且对目标化合物具有选择识别能力聚合物的技术[16].在食品检测领域,将MIT技术所制备的化合物作为固相萃取小柱的填料,用来吸附目标化合物的技术称为分子印迹固相萃取技术[17](molecular imprinted solid-phase extraction,MISPE)。近年来,该技术的研究报道见表2.

  Table 1 Application of several adsorbents of solid-phase extraction   

  表1 几种固相萃取吸附剂联用技术的应用

  Table 2 Applications of MISPE    

  表2 分子印迹固相萃取技术的应用

  MISPE技术自Sellergrn[22]引入悬浮法制备分子印迹聚合物作为提取尿液中戊咪所使用的固相萃取剂之后,得到研究者的广泛研究。随着研究的深入,该技术选择性和特异性强、基质干扰少、分离效率高等优点[23]越来越凸显。但由于功能单体种类较少,且分子印迹聚合物的模板分子针对性较强,不利于固相萃取柱大批量商业化生产,且成品柱相对来说价格昂贵,而实验室自行制备操作步骤比较繁琐,因此该技术在食品检测实验室没有得到广泛应用。

  将分子印迹技术和磁性材料[18]和碳纳米材料[21]等技术联用,克服上述缺点是以后的发展趋势。

  3.2 碳纳米管填料

  纳米材料的出现为食品检测行业的发展提供了新的思路和途径[24].碳纳米管(carbon nanotubes)是一种新型的纳米材料[25],中间是一个中空的大圆管,侧壁由碳六元环组成,碳原子之间形成大π键[26].独特的结构和优良的性能,使该材料在生物[27]、医学[28]、化学[29]等众多领域发挥了重要的作用。但由于碳纳米管的分散性、溶解性较差,限制了其在食品领域的发展[30].碳纳米管进行功能性改性[31]完成后,在食品检测领域得到了广泛应用。近年来,碳纳米管材料作为食品检测样品前处理中固相萃取小柱填料的应用研究见下表:

  综上所述,碳纳米管固相萃取技术具有萃取效率高、灵敏度高等优点,加之碳纳米管材料价格低廉,环保易得,该技术被广泛应用于食品安全检测领域。表中可知,多壁碳纳米管单独使用,多用于分散固相萃取吸附剂;联合其他技术,对碳纳米材料进行改性,扩大碳纳米材料在食品行业的使用范围,是当前的研究热点。该技术能够对农产品[31,32,33]以及动物源性食品[34,35]中的相当部分农药[31,32,33]、抗生素[34]、重金属[35]等进行高效分离提纯,并具有良好的发展前景。

  3.3 磁固相萃取技术

  在外部磁场的作用下磁性功能材料可进行移动和导向,以该材料作为吸附剂可实现目标化合物与样品基质进行磁性分离[36].磁响应性能良好的磁核,是实现快速、高效分离的保障,最常见的磁性载体(磁核)为铁系元素铁、钴、镍以及它们相应的氧化物[37].磁固相萃取技术(magnetic solid-phase extraction,MSPE)是以磁性材料作为固相萃小柱的新填料对样品中的目标化合物进行分离提纯。由于以Fe3O4为纳米骨架的磁性材料[38]具有易于制备,易于改性,磁性强等优点,被广泛应用,但一般的磁性材料疏水性差,表面容易团聚[39],功能化的非磁性材料可以增强吸附的选择性[40],从此,表面修饰的磁性材料被越来越多的应用到食品检测领域。表4着重介绍不同表面修饰的磁性材料在食品检测领域的应用。

  由表4可知,MSPE技术具有分离效果好,检出限低等优点,被广泛应用于各类食品的前处理中[47].但由于磁性材料的磁性容易在有机溶剂中被洗去[48],该技术在适用范围上有一定的选择性。相对于传统的固相萃取技术,MSPE技术不需要填柱子,操作简单,可实现自动化的在线样品前处理[49],这也是该技术在食品检测行业的发展趋势。

  4 结论与展望

  综上可知,这4种技术虽有各自的局限性,但相对于传统的吸附剂具有分离速度快、效率高、环境友好、适用于痕量化合物检测等优点。当前,食品安全问题层出不穷,食品中的有害残留物和添加剂的种类越来越多,面对日益严峻的食品安全形势,开发出能够高效快速提取分离目标物的吸附剂是固相萃取技术在食品检测行业的发展趋势。

  Tabel 3 Application of carbon nanotubes solid-phase extraction    

  表3 碳纳米管固相萃取技术的应用

  Table 4 Applications of MSPE    

  表4 MSPE的应用

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作者单位:陕西省产品质量监督检验研究院
原文出处:范芳芳,魏宁果,邹力,安瑜.新型固相萃取吸附技术在食品分析中的应用[J].食品安全质量检测学报,2020,11(14):4672-4677.
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