CN114019068B - 一种固相微萃取器及其制备方法 - Google Patents
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Abstract
本发明公开了一种固相微萃取器及制备方法,属于分析化学与环境化学的交叉领域。该固相微萃取器采用新型晶态多孔聚合物与环氧树脂复合涂层作为功能萃取头,利用晶态多孔聚合物与环氧树脂的协同作用,显著提高了对拟除虫菊酯类农药的固相微萃取效率。可达到各种商品化SPME萃取器萃取效率的1.5~150倍。从而显著提高拟除虫菊酯类物质检测的灵敏度,很好地实现对水体中拟除虫菊酯类农药的定性、定量检测。
Description
技术领域
本发明涉及一种用于SPME-GC/MS的固相微萃取器,实现对水体中拟除虫菊酯类农药检测,属于分析化学与环境化学的交叉领域。
背景技术
拟除虫菊酯类农药是一种在世界范围内广泛使用的广谱杀虫剂。虽然与传统的有机氯和有机磷等农药相比,拟除虫菊酯具有半衰期短,毒性小的优点。但随着农业和水产业的快速发展,拟除虫菊酯类农药的使用规模也日趋增大,暴露于环境中的拟除虫菊酯容易引起人类和动物慢性毒性效应。并且,通过大气中干湿沉降、降水径流、直接施用以及农药生产工厂排放等途径,水环境中的拟除虫菊酯含量也不断增加。而拟除虫菊酯对水生生物具有较高的毒理学活性,水环境中大量的拟除虫菊酯势必影响水环境质量,危害水体生态系统,造成水产品的质量下降。此外,通过进食,拟除虫菊酯会进入处于生物链顶端的哺乳动物包括人类体内,并构成累积风险,引起人体相关器官和功能的损害,如内分泌系统、生殖系统、免疫系统及中枢神经系统等。
因此,水体中拟除虫菊酯类农药的检测对于环境水监控、饮用水的质量检测,拟除虫菊酯类农药的使用以及风险评估都具有重要意义。目前,拟除虫菊酯类农药的检测方法主要包括气相色谱法和液相色谱法。主要的样品前处理方法有液-液萃取,索氏提取,微波辅助萃取,超临界流体萃取,固相萃取、固相微萃取、加速溶剂萃取等。固相微萃取技术是集采样、萃取、浓缩和进样于一体的样品前处理技术,稳定高效的萃取头能有效提高分析的灵敏度和准确性。目前研究开发稳定高效的萃取头或萃取器是实现固相微萃取检测水体中拟除虫菊酯类农药的重要途径。
发明内容
本发明旨在对固相微萃取的功能萃取头进行改进,提供一种灵敏度高,准确性高的固相微萃取器,用于SPME-GC/MS中,实现对水体中拟除虫菊酯类农药检测。
为实现本发明目的,本发明采用涂有晶态多孔聚合物/环氧树脂复合涂层的萃取头制备固相微萃取器,然后进行采样、萃取、浓缩和进样,采用固相微萃取(SPME)技术联合气相色谱-质谱(GC-MS)法,实现对水体中拟除虫菊酯类农药检测。
所述固相微萃取器为涂层纤维,由晶态多孔聚合物/环氧树脂复合涂覆而成,其制备方法如下:将表面羟基化的不锈钢纤维基底一端插入稀释的环氧树脂中,缓慢取出后,再插入到制备的晶态多孔聚合物粉末中干燥,重复上述操作,直到达到所需的涂层厚度。最后将上述纤维置于微量进样器中,得到SPME萃取器。使用前,在230-280℃条件下老化1-5小时。
所述的涂层厚度为10-100μm。
所述的晶态多孔聚合物的制备方法:将刚性多胺和苯并[1,2-b:3,4-b’:5,6-b’]三噻吩-2,5,8-三醛(摩尔比为0.5-2:1)充分混合,加入至耐压玻璃管中,依次注入二氧六环、均三甲苯和乙酸。将混合物在液氮中冷冻,抽真空,氮气回填。最后将玻璃管在真空条件下熔封,加热反应。反应结束后,固体产物经清洗,烘干,最终得到目标物,为棕黑色固体粉末。
所述刚性多胺为:三(4-氨基苯基)胺,1,3,5-三(4-氨苯基)苯,1,3,5-三氨基苯,三聚氰胺,对苯二胺,5,5'-二氨基-2,2'-联吡啶。
所述环氧树脂为:双酚A型环氧树脂,双酚S型环氧树脂。
对水体中拟除虫菊酯类农药的检测方法包括以下步骤:
(1)将拟除虫菊酯类农药用水稀释至所需浓度作为标准溶液;
(2)取标准溶液,浓度由低至高依次测试,置于玻璃萃取瓶中,搅拌均匀,封口;
(3)将基于晶态多孔聚合物/环氧树脂复合涂层的固相微萃取器插入萃取瓶中,推出纤维头,全部置于样品溶液中,搅拌下,进行富集(50-80℃);
(4)富集结束后,将萃取头抽回微量进样器中,随后将微量进样器拔出,立刻插入气相色谱进样口,再次推出萃取头,进样口温度为240-280℃,解吸时间为1-10min;
(5)经气相色谱-质谱分析,将测得的峰面积(y)与标准溶液的质量浓度(x)进行线性回归分析,得到各目标化合物的标准曲线方程。
(6)取含有拟除虫菊酯类农药的水体样品,倍数稀释,按照上述2-5步骤中标准工作溶液的测试方法,对水体样品进行分析,测得目标物峰面积值,代入标准曲线方程,求得样品中的各种拟除虫菊酯类农药的含量。
所述的拟除虫菊酯类农药标准溶液的浓度为1,10,50,100,500,1000μg/L。
所述的步骤2中标准溶液的体积为5-50mL。
所述的色谱条件为:SH-Rtx-5MS型毛细管柱(30m×0.25m×0.25μm)。载气He流速为1.5mL/min;进样温度为260-280℃;色谱柱升温程序:在70℃保持1分钟,以25℃/min上升到250℃,保持17分钟。
所述的质谱条件为:离子源温度230℃;接口温度;200℃。
本发明与现有技术相比具有以下优点:
本发明所使用的SPME萃取器是基于一种新型晶态多孔聚合物/环氧树脂复合材料的涂层纤维。其一,环氧树脂不仅有助于晶态多孔聚合物在纤维上成膜,同时也对拟除虫菊酯类农药有一定的富集能力(如图1所示,以氯氰菊酯为例),二者的协同效应使得所述SPME萃取器对除虫菊酯类物质具有良好的萃取性能。因此,与其他树脂材料与晶态多孔材料的复合材料相比,所述的晶态多孔聚合物/环氧树脂复合材料涂层的SPME萃取器,萃取效率具有显著的优势,如图2所示。其二,所述晶态多孔聚合物是一种新型多孔吸附剂,其微观骨架中含有大量的N,S杂环结构,具有规则且尺寸可调节的孔道,较大的比表面积,对除虫菊酯类物质具有很好的富集和吸附能力。二者结合制备的适用于固相微萃取的功能萃取头能够有效提高SPME萃取效率,萃取效率可达到各种商品化SPME萃取器的1.5-150倍,如图3所示。从而显著提高拟除虫菊酯类物质检测的灵敏度,很好地实现对水体中拟除虫菊酯类农药的定性、定量检测。
附图说明
图1为实施例1所得环氧树脂涂层和晶态多孔聚合物/环氧树脂复合涂层SPME萃取器对氯氰菊酯萃取性能的柱状对比图。
图2为实施例1中所得晶态多孔聚合/硅酮树脂复合涂层与晶态多孔聚合/环氧树脂复合涂层对六种拟除虫菊酯农药的萃取性能的柱状对比图。
图3为实施例1所得晶态多孔聚合物/环氧树脂复合涂层SPME萃取器与五种商品化萃取器对氯氰菊酯萃取性能的对比。
图4为实施例1所得SPME萃取器的扫描电镜照片。
具体实施方式
为对本发明进行更好地说明,举实施例如下:
实施例1
所述固相微萃取器为涂层纤维,由晶态多孔聚合物/环氧树脂复合涂覆而成,其制备方法如下:将表面羟基化的不锈钢纤维基底一端插入稀释的环氧树脂中,缓慢取出后,再插入到制备的晶态多孔聚合物粉末中,80℃干燥10分钟,重复上述操作,直到达到所需的涂层厚度。最后将上述纤维置于5μL的微量进样器中。得到SPME萃取器。使用前,在250℃条件下老化2小时。
所述的涂层厚度为60μm。
所述的晶态多孔聚合物的制备方法:将三(4-氨基苯基)胺和苯并[1,2-b:3,4-b’:5,6-b’]三噻吩-2,5,8-三醛(摩尔比为0.5-2:1)充分混合,加入至耐压玻璃管中,依次注入二氧六环0.5mL、均三甲苯0.5mL和乙酸(6M)750μL mL。将混合物在液氮中冷冻30分钟,抽真空30分钟,氮气回填,反复5次。最后将玻璃管在真空条件下熔封,在120℃下反应5天。反应结束后,将固体产物用N,N-二甲基甲酰胺与四氢呋喃依次清洗3次。在100℃下烘干24小时。
其对水体中拟除虫菊酯类农药的检测方法包括以下步骤:
将氯氰菊酯用水稀释至所需浓度作为标准溶液,浓度为1,10,50,100μg/L;
取标准溶液10mL,浓度由低至高依次测试,置于玻璃萃取瓶中,搅拌均匀,封口;
将本发明基于晶态多孔聚合物/环氧树脂复合涂层的固相微萃取器插入萃取瓶中,推出纤维头,置于样品溶液中,在80℃条件下进行富集,保持30分钟,搅拌速度为600转/分钟;
富集结束后,立刻插入气相色谱进样口,再次推出萃取头,进样口温度为270℃,解吸时间为1min;
经GC/MS分析,将测得的峰面积(y)与标准溶液的质量浓度(x)进行线性回归分析,得到各目标化合物的标准曲线方程。
取含有氯氰菊酯农药的水体样品1mL,稀释至5mL,按照上述测试方法,对水体样品进行分析,测得目标物峰面积值,代入标准曲线方程,求得样品中的氯氰菊酯含量为89.23μg/L。
实施例2
拟溴氰菊酯用水稀释至所需浓度作为标准溶液,浓度为1,10,50,100μg/L;
取标准溶液10mL,浓度由低至高依次测试,置于玻璃萃取瓶中,搅拌均匀,封口;
将本发明基于晶态多孔聚合物/环氧树脂复合涂层的固相微萃取器插入萃取瓶中,推出纤维头,全部置于样品溶液中,在80℃条件下进行富集,保持30分钟,搅拌速度为600转/分钟;
富集结束后,将萃取头抽回微量进样器中,随后将微量进样器拔出,立刻插入气相色谱进样口,再次推出萃取头,进样口温度为270℃,解吸时间为1min;
经GC/MS分析,将测得的峰面积(y)与标准溶液的质量浓度(x)进行线性回归分析,得到各目标化合物的标准曲线方程。
取含有溴氰菊酯农药的水体样品1mL,稀释至5mL,按照上述测试方法,对水体样品进行分析,测得目标物峰面积值,代入标准曲线方程,求得样品中的溴氰菊酯的含量为102.23μg/L。
所述的晶态多孔聚合物/环氧树脂复合涂层的固相微萃取器的制备方法:将表面羟基化的不锈钢纤维基底一端插入稀释的环氧树脂中,缓慢取出后,再插入到制备的晶态多孔聚合物粉末中,60℃干燥20分钟,重复上述操作,直到达到所需的涂层厚度。最后将上述纤维置于5μL的微量进样器中。得到SPME萃取器。使用前,在260℃条件下老化5小时。
所述的涂层厚度为100μm。
所述的晶态多孔聚合物的制备方法:将1,3,5-三(4-氨苯基)苯和苯并[1,2-b:3,4-b’:5,6-b’]三噻吩-2,5,8-三醛(摩尔比为0.5-2)充分混合,加入至耐压玻璃管中,依次注入二氧六环0.5mL、均三甲苯0.5mL和乙酸(6M)750μL mL。将混合物在液氮中冷冻30分钟,抽真空30分钟,氮气回填,反复5次。最后将玻璃管在真空条件下熔封,在120℃下反应5天。反应结束后,将固体产物用N,N-二甲基甲酰胺与四氢呋喃依次清洗3次。在150℃下烘干12小时。
Claims (2)
1.由涂层纤维制成的固相微萃取器在农药检测中的应用,其特征在于,将其用于检测水体中拟除虫菊酯类农药;
所述固相微萃取器由晶态多孔聚合物和环氧树脂复合涂覆而成,通过如下方法制备而成:
(1)将表面羟基化的不锈钢纤维基底一端插入稀释的环氧树脂中,缓慢取出后,再插入到晶态多孔聚合物粉末中干燥;
(2)重复步骤(1)操作,直到达到所需的涂层厚度;最后将上述纤维置于微量进样器中,得到固相微萃取器;
所述的晶态多孔聚合物通过如下方法制备而成:将刚性多胺和苯并[1,2-b:3,4-b’:5,6-b’]三噻吩-2,5,8-三醛混合,加入至耐压玻璃管中,依次注入二氧六环、均三甲苯和乙酸;将混合物在液氮中冷冻,抽真空,氮气回填;最后将玻璃管在真空条件下熔封,加热反应;反应结束后,固体产物经清洗,烘干,最终得到目标物;
所述刚性多胺为:三(4-氨基苯基)胺,1,3,5-三(4-氨苯基)苯,1,3,5-三氨基苯,三聚氰胺,对苯二胺,5,5'-二氨基-2,2'-联吡啶;
所述环氧树脂为:双酚A型环氧树脂,双酚S型环氧树脂。
2.如权利要求1所述的由涂层纤维制成的固相微萃取器在农药检测中的应用,其特征在于,所述的涂层厚度为10~100 μm。
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