CN112547031A - 一种固相微萃取探针纤维及其制备方法和应用 - Google Patents
一种固相微萃取探针纤维及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于污染物检测技术领域,尤其涉及一种固相微萃取探针纤维及其制备方法和应用,本发明采用不锈钢丝纤维为基质,通过溶胶凝胶技术将共价有机框架材料TpDA固定到不锈钢丝纤维上,最终制得基于共价有机框架的固相微萃取探针纤维,并用于内分泌干扰物的富集测定;本发明结合了固相微萃取溶剂用量少,操作简便与共价有机框架材料比表面积大,热稳定性高和吸附能力强的特点,且共价有机框架材料所具有的大的π共轭体系与内分泌干扰物的苯环结构之间存在π‑π作用力,使制备的固相微萃取探针纤维增强了对内分泌干扰物的吸附作用,提高了对内分泌干扰物的富集能力,有效检测内分泌干扰物,对进一步检测内分泌干扰物打下坚实基础。
Description
技术领域
本发明属于污染物检测技术领域,尤其涉及一种固相微萃取探针纤维及其制备方法和应用。
背景技术
内分泌干扰物是一类持久性和生物累积性污染物,可以干扰人体内分泌系统,对人类的发育、生殖、心血管、神经、新陈代谢和免疫产生不利影响;另外,内分泌干扰物在畜牧业和水产养殖中经常被用来增加饲料转化率和动物生长速度,因此,开发快速、准确、廉价的内分泌干扰物的分析方法是必要的。
目前对于内分泌干扰物的分析方法主要为基于色谱法的“三步”策略,即样品前处理-分离-检测,合适的前处理方法,可以减少目标物损失及误差来源,对目标物进行富集,在现有的分离检测条件下提高准确性和灵敏度。固相微萃取(SPME)作为前处理方法中的一种,由于其溶剂用量少、对系统干扰小、操作简便等优点,目前已经被广泛应用于环境保护、食品检测和药物分析等领域,而固相微萃取探针纤维的涂层被认为是SPME的核心部分,SPME技术的广泛应用和高灵敏性、高选择性依赖于涂层材料的发展和制备,尽管目前一些固相微萃取探针纤维的涂层已经实现商用化,但是这些探针价格昂贵(800-900元/支),热稳定性也不理想。
发明内容
为了解决上述问题,本发明提供了一种固相微萃取探针纤维的制备方法,包括以下步骤:
(1)制备表面粗糙的不锈钢丝纤维;
(2)将获得的所述表面粗糙的不锈钢丝纤维伸入中性硅酮胶稀释液中,取出后得到表面有中性硅酮胶的不锈钢丝纤维;
(3)在上一步得到的表面有中性硅酮胶的不锈钢丝纤维表面均匀涂覆一层共价有机框架材料TpDA,得到固相微萃取探针纤维。
作为上述方案的进一步说明,所述步骤(1)中表面粗糙的不锈钢丝纤维的处理操作为:将不锈钢丝一端浸泡在王水中,然后将其在超纯水中浸泡、超声并晾干,得到表面粗糙的不锈钢丝。
作为上述方案的进一步说明,所述步骤(2)中的中性硅酮胶稀释液的质量浓度为0.4~0.6g/mL。
作为上述方案的进一步说明,所述步骤(3)中使用的共价有机框架材料TpDA的制备方法如下:将三醛基间苯三酚和2,6-二氨基蒽醌分散到1,4-二氧六环中,混合均匀后置于反应釜中120℃加热3天;离心收集产物,用N,N-二甲基甲酰胺和四氢呋喃依次洗涤数次,并在真空干燥箱中80℃干燥24小时,得到共价有机框架材料TpDA。
作为上述方案的进一步说明,所述三醛基间苯三酚、2,6-二氨基蒽醌和1,4-二氧六环的物质的量之比为0.3:0.45:35mmol。
作为上述方案的进一步说明,所述步骤(3)得到的表面有中性硅酮胶的不锈钢丝纤维表面均匀涂覆一层共价有机框架材料TpDA后,在真空干燥箱中60℃干燥48小时。
本发明还提供了一种固相微萃取探针纤维,其由权利要求1~6任一项方法制得。
本发明还提供了上述的固相微萃取探针纤维的应用,其特征在于,将其用于吸附内分泌干扰物;应用时利用七氟丁酸酐作为衍生试剂,将所述内分泌干扰物洗脱后进行衍生形成挥发性较大的衍生物,然后使用气相色谱电子捕获检测器(GC-ECD)进行检测。
本发明的有益效果:本发明采用不锈钢丝纤维为基质,通过溶胶凝胶技术将共价有机框架材料TpDA固定到不锈钢丝纤维上,最终制得基于共价有机框架的固相微萃取探针纤维,并用于内分泌干扰物的富集测定;本发明结合了固相微萃取溶剂用量少,操作简便与共价有机框架材料比表面积大,热稳定性高和吸附能力强的特点,且共价有机框架材料所具有的大的π共轭体系与内分泌干扰物的苯环结构之间存在π-π作用力,使制备的固相微萃取探针纤维增强了对内分泌干扰物的吸附作用,提高了对内分泌干扰物的富集能力,对进一步检测内分泌干扰物打下坚实基础。
附图说明
图1:实施例1中的以不锈钢丝为基底制备的TpDA固相微萃取探针纤维的流程图;
图2:实施例1的TpDA固相微萃取探针纤维的扫描电镜图;
图3:实施例2的固相微萃取探针纤维用于食品中内分泌干扰物检测的气相色谱图;其中OP为辛基酚、NP为壬基酚、BPA为双酚A、DES为己烯雌酚、E1为雌酮、E2为17β-雌二醇、E3为雌三醇。
具体实施方式
下面将结合附图和实施方式对本发明作进一步说明。
实施例1
本实施例提供了一种固相微萃取探针纤维的制备方法,制备流程如图1,具体包括以下步骤:
(1)不锈钢丝纤维的制备:将17cm长的不锈钢丝纤维置于王水中刻蚀约30min,刻蚀长度为3cm,然后将其在超纯水中浸泡、超声并晾干。
(2)中性硅酮胶稀释液的制备:将1g中性硅酮胶与2mL邻二甲苯混合搅匀后,超声处理5min,得到中性硅酮胶稀释液。
(3)将刻蚀的不锈钢丝纤维伸入中性硅酮胶稀释液中,取出后用滤纸擦干不锈钢丝纤维表面可见的液滴,得到表面涂有中性硅酮胶的不锈钢丝纤维。
(4)共价有机框架材料TpDA的制备:将63.0mg三醛基间苯三酚和107.2mg 2,6-二氨基蒽醌分散到3mL 1,4-二氧六环中,混合均匀后置于反应釜中120℃加热3天。离心收集产物,用N,N-二甲基甲酰胺和四氢呋喃依次洗涤3次,并在真空干燥箱中80℃干燥24小时,得到共价有机框架材料TpDA。
(5)表面涂覆TpDA材料的固相微萃取纤维的制备:将涂有硅酮胶的不锈钢丝纤维置于共价有机框架材料TpDA中滚动并涂覆一层共价有机框架材料TpDA;用镊子敲击不锈钢丝纤维上未涂覆TpDA的部分,使得未粘附严实的TpDA从不锈钢丝纤维上掉下,得到表面涂覆TpDA材料的固相微萃取探针纤维;然后将固相微萃取探针纤维置于真空干燥箱中60℃干燥48小时。
用扫描电镜表征以上方法制备的固相微萃取探针纤维的微观形貌,如图2所示。
实施例2
本实施例提供了一种基于实施例1中制备的固相微萃取探针纤维应用于猪肉中内分泌干扰物的分析,按照以下步骤进行:
第一步,进行标准品的制备:采用甲醇配制内分泌干扰物标准溶液;7种内分泌干扰物分别为辛基酚(OP)、壬基酚(NP)、双酚A(BPA)、己烯雌酚(DES)、雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)。
第二步,进行样品的制备:5g猪肉加入3mL 10%碳酸钠水溶液和20mL乙酸乙酯,漩涡混匀,超声提取10min,4000rpm离心10min,取上清液,残渣再加入10mL乙酸乙酯重复提取一次,4000rpm离心10min,合并两次上清液,40℃水浴中氮气吹干,用10mL甲醇溶解残留物,备用。
第三步,选择吸附方式:采用直接浸入萃取。
第四步内分泌干扰物衍生:将吸附到固相微萃取探针纤维上的内分泌干扰物洗脱到具塞玻璃离心管中,加入30μL七氟丁酸酐和70μL丙酮,盖紧盖,漩涡混合30秒,30℃衍生30min,氮气吹干,加入0.5mL正己烷,旋涡混合10秒,溶解残余物。
第五步,气相色谱-电子捕获检测器检测:选用HP-5MS(30m×0.25mm×0.25μm)为色谱柱,进样口温度设为260℃,升温程序为:120℃保持2min,以15℃/min升温至250℃,最后以5℃/min升温至280℃保持5min。此外,采用不分流模式,载气为高纯度氦气(99.999%),流速为1mL/min进行气相色谱-电子捕获检测器(GC-ECD)分析(参考图3)。
第六步,进行定量测定:取猪肉所制备的样品溶液加入蒸馏水配制富集溶液,将固相微萃取探针纤维直接浸入溶液内,吸附温度为70℃,不添加NaCl,吸附30min后,以甲醇为洗脱剂将吸附在固相微萃取探针纤维上的内分泌干扰物洗脱下来并进行衍生,最后检测实际样品中内分泌干扰物的含量,如表1。
表1固相微萃取检测猪肉中内分泌干扰物
注:and未检出
通过上述实验可证明,所制备TpDA涂层固相微萃取探针纤维可用于猪肉中的内分泌干扰物的检测,且在加标量为5μg/kg时,回收率均在80~110%之间,证明所合成的TpDA材料在食品中内分泌干扰物富集方面的潜力,同时该方法很好的适用于肉类等实际样品中内分泌干扰物的检测。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (8)
1.一种固相微萃取探针纤维的制备方法,其特征在于,包括以下步骤:
(1)制备表面粗糙的不锈钢丝纤维;
(2)将获得的所述表面粗糙的不锈钢丝纤维伸入中性硅酮胶稀释液中,取出后得到表面有中性硅酮胶的不锈钢丝纤维;
(3)在上一步得到的表面有中性硅酮胶的不锈钢丝纤维表面均匀涂覆一层共价有机框架材料TpDA,得到固相微萃取探针纤维。
2.根据权利要求1所述的一种固相微萃取探针纤维的制备方法,其特征在于,所述步骤(1)中表面粗糙的不锈钢丝纤维的处理操作为:将不锈钢丝一端浸泡在王水中,然后将其在超纯水中浸泡、超声并晾干,得到表面粗糙的不锈钢丝。
3.根据权利要求1所述的一种固相微萃取探针纤维的制备方法,其特征在于,所述步骤(2)中的中性硅酮胶稀释液的质量浓度为0.4~0.6g/mL。
4.根据权利要求1所述的一种固相微萃取探针纤维的制备方法,其特征在于,所述步骤(3)中使用的共价有机框架材料TpDA的制备方法如下:将三醛基间苯三酚和2,6-二氨基蒽醌分散到1,4-二氧六环中,混合均匀后置于反应釜中120℃加热3天;离心收集产物,用N,N-二甲基甲酰胺和四氢呋喃依次洗涤数次,并在真空干燥箱中80℃干燥24小时,得到共价有机框架材料TpDA。
5.根据权利要求4所述的一种固相微萃取探针纤维的制备方法,其特征在于,所述三醛基间苯三酚、2,6-二氨基蒽醌和1,4-二氧六环的物质的量之比为0.3:0.45:35mmol。
6.根据权利要求1所述的一种固相微萃取探针纤维的制备方法,其特征在于,所述步骤(3)得到的表面有中性硅酮胶的不锈钢丝纤维表面均匀涂覆一层共价有机框架材料TpDA后,在真空干燥箱中60℃干燥48小时。
7.一种固相微萃取探针纤维,其特征在于,由权利要求1~6任一项方法制得。
8.一种固相微萃取探针纤维的应用,其特征在于,将其用于吸附内分泌干扰物;应用时利用七氟丁酸酐作为衍生试剂,将所述内分泌干扰物洗脱后进行衍生形成挥发性较大的衍生物,然后使用气相色谱电子捕获检测器进行检测。
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Cited By (1)
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CN114019068A (zh) * | 2021-11-08 | 2022-02-08 | 烟台大学 | 一种固相微萃取器及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001004611A (ja) * | 1999-06-25 | 2001-01-12 | Toyo Ink Mfg Co Ltd | 選択的固相抽出法 |
US20120164286A1 (en) * | 2002-03-11 | 2012-06-28 | Pawliszyn Janusz B | Solid-phase microextraction coatings and methods for their preparation |
US20160208047A1 (en) * | 2015-01-20 | 2016-07-21 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
CN108034055A (zh) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | 一种共价有机骨架固相微萃取纤维及其制备方法 |
CN108579708A (zh) * | 2018-04-28 | 2018-09-28 | 江南大学 | 一种多环芳烃富集检测用固相微萃取纤维及制作方法 |
CN109342613A (zh) * | 2018-09-18 | 2019-02-15 | 山东省分析测试中心 | 一种用于分析饮料中酚类内分泌干扰物的方法 |
CN109621911A (zh) * | 2019-01-31 | 2019-04-16 | 烟台大学 | 一种多孔有机骨架涂层的spme萃取纤维及其制备方法 |
CN109772268A (zh) * | 2019-02-15 | 2019-05-21 | 河北大学 | 一种固相微萃取纤维及其制备方法 |
CN110133125A (zh) * | 2019-05-07 | 2019-08-16 | 曲阜师范大学 | 一种磁性固相萃取检测果蔬中植物生长调节剂的方法 |
-
2020
- 2020-09-29 CN CN202011049825.4A patent/CN112547031A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001004611A (ja) * | 1999-06-25 | 2001-01-12 | Toyo Ink Mfg Co Ltd | 選択的固相抽出法 |
US20120164286A1 (en) * | 2002-03-11 | 2012-06-28 | Pawliszyn Janusz B | Solid-phase microextraction coatings and methods for their preparation |
US20160208047A1 (en) * | 2015-01-20 | 2016-07-21 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
CN108034055A (zh) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | 一种共价有机骨架固相微萃取纤维及其制备方法 |
CN108579708A (zh) * | 2018-04-28 | 2018-09-28 | 江南大学 | 一种多环芳烃富集检测用固相微萃取纤维及制作方法 |
CN109342613A (zh) * | 2018-09-18 | 2019-02-15 | 山东省分析测试中心 | 一种用于分析饮料中酚类内分泌干扰物的方法 |
CN109621911A (zh) * | 2019-01-31 | 2019-04-16 | 烟台大学 | 一种多孔有机骨架涂层的spme萃取纤维及其制备方法 |
CN109772268A (zh) * | 2019-02-15 | 2019-05-21 | 河北大学 | 一种固相微萃取纤维及其制备方法 |
CN110133125A (zh) * | 2019-05-07 | 2019-08-16 | 曲阜师范大学 | 一种磁性固相萃取检测果蔬中植物生长调节剂的方法 |
Non-Patent Citations (2)
Title |
---|
NING LI ET AL.: "Effective enrichment and detection of plant growth regulators in fruits and vegetables using a novel magnetic covalent organic framework material as the adsorbents", 《FOOD CHEMISTRY》, vol. 306, 4 September 2019 (2019-09-04), pages 3, XP085874438, DOI: 10.1016/j.foodchem.2019.125455 * |
WEI GAO ET AL.: "Covalent organic framework-graphene oxide composite: A superior adsorption material for solid phase microextraction of bisphenol A", 《TALANTA》, vol. 222, 12 August 2020 (2020-08-12), pages 2, XP086319783, DOI: 10.1016/j.talanta.2020.121501 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114019068A (zh) * | 2021-11-08 | 2022-02-08 | 烟台大学 | 一种固相微萃取器及其制备方法 |
CN114019068B (zh) * | 2021-11-08 | 2024-02-09 | 烟台大学 | 一种固相微萃取器及其制备方法 |
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