CN100418622C - 一种聚噻吩固相微萃取头及其制备方法 - Google Patents
一种聚噻吩固相微萃取头及其制备方法 Download PDFInfo
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Abstract
一种新型聚噻吩固相微萃取头及其制备方法,属于环境监测仪器技术领域。其制备方法为将金属丝***注射装置中,使其形成简易固相微萃取装置;以金属丝前端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系;放入含有噻吩的无水BF3***溶液中;采用电化学方法形成粘附于金属丝前端表面的聚噻吩涂层;用二次蒸馏水和甲醇溶液洗涤,即制成新型固相微萃取头。制备的固相微萃取头对极性、非极性、挥发性、难挥发性的痕量有机污染物都有很好萃取选择性。同商用涂层相比较,有较好的物理和化学稳定性,且寿命长。该萃取头适合复杂样品中的多种有机物分析,在环境监测、食品卫生、检验检疫等领域有很好应用潜力。
Description
一、技术领域
本发明涉及一种应用于多种环境污染物分析的聚噻吩固相微萃取头及其制备方法。
二、背景技术
固相微萃取技术(SPME)是一种新型样品预分离富集技术,它无需溶剂,快速、便捷,对脂溶性有机物具有较高的选择性和较强的富集能力,特别适用于痕量物质的分析,已成为水体中持久有机污染物快速分析监测的强有力手段。SPME目前已应用于许多领域,如对农药、酚类、多氯联苯、多环芳烃(PAHs)等进行分析检测。
但是,商售SPME结构中附载在石英纤维上的高分子涂层(如:聚二甲基硅氧烷(PDMS)和聚丙烯酸酯(PA)等)装置易受损害、不耐高温、寿命短、且价格昂贵,难以在普通实验室推广使用。
聚噻吩是一种导电高分子,具有大的共轭∏-∏结构,因此具有很强的热稳定性和抗有机溶剂性。另外,浓密的颗粒结构和大的比表面积,这也决定了它有较大的吸附容量和快的萃取平衡。
通过文件检索,未发现有关聚噻吩用于固相微萃取技术的有关文献。
三、发明内容
1.发明目的:本发明的目的是提供一种能广泛用于环境中各种有机污染物分析的聚噻吩固相微萃取头及其制备方法。
2.技术方案:
本发明的技术方案为:
一种聚噻吩固相微萃取头的制备方法,其包括以下步骤:
(1)将金属丝***注射装置中,使其形成简易固相微萃取装置;
(2)以金属丝前端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系,放入含有噻吩的无水BF1***溶液中;
(3)采用电位扫描法、恒电位法、恒电流法或脉冲极化法形成粘附于金属丝前端表面的聚噻吩涂层;
(4)用二次蒸馏水和甲醇溶液洗涤,即制成聚噻吩固相微萃取头。
本发明步骤(1)中的金属丝只要硬度能满足***注射装置中,便于以后的取样即可,通常使用直径:0.1~0.5mm,长度:0.5~1.5cm的金属丝,常用的是不锈钢丝,价格便宜且易于取得。步骤(2)中的含有噻吩的无水BF3***溶液没有特殊要求,强调的是溶液中应不含水分或是含有的水分尽量少。噻吩的浓度为0.05~0.5摩尔/升时都可有较好的效果,根据试验,建议的噻吩浓度为0.1~0.2摩尔/升。
本发明的还提供一种聚噻吩固相微萃取头,包括注射装置和金属丝,金属丝前端表面有聚噻吩涂层。
这种固相微萃取头按照以上所述的方法制备而成。
这种固相微萃取头初次使用前在气相色谱气化室中200~280℃,升温老化2~3h,直到无杂质峰出现。
本发明的原理:
根据噻吩“电聚合原理”,采用电化学法,将聚噻吩电聚合在金属丝上,以形成聚噻吩涂层。
目前用于电化学合成聚噻吩的主要方法除了上述动电位扫描法,还有恒电位法、恒电流法、脉冲极化法以及等离子聚合法和真控蒸着法等,它们一般都是噻吩在对质子有惰性的溶剂(乙腈、苯基腈、硝基苯、三氟化硼***、碳酸丙烯酯等)中,而且含有强酸阴离子(如ClO4 -、PF6 -、BF4 -和AsF6 -)和Li+或四烷基铵阳离子的电解质存在下,电化学制备生成聚噻吩的.在阳极上进行聚合。实验表明,这些方法都可以在较短时间内制得性质类似,堆密度大、颗粒均匀、规整且化学性质稳定的聚噻吩薄膜。膜的厚度一般随着聚合时间的延长而增厚,聚噻吩膜越厚对痕量有机污染物的萃取量就越大,但萃取时间会延长,另外,***的针孔直径也限制了它不能太厚。电极材料、电极电位、电解质溶液种类对噻吩的聚合都有一定的影响。所以具体情况要跟据具体的实验条件来确定。
3.有益效果:
本方法的特点是聚噻吩是直接电聚合在金属丝上,在电聚合的过程中,有机-无机相(即固相涂层与金属丝表面)之间是通过化学键键合,所以比商用的石英纤维柱有更高的物理稳定性。在寿命方面,研究发现只要操作得当,数百次的重复使用和长时间的放置,都不会改变它的萃取效果。在污染物分析方面,无论是极性,非极性,挥发性和难挥发性的有机污染物都可用聚噻吩来分析,这打破了常规的相似相溶原理的限制。本发明结构简单、易于制作,应用前景广阔。
四、说明书附图
图1为本发明一种聚噻吩固相微萃取头使用时的结构示意图;
图2为本发明的聚噻吩固相微萃取头聚涂层扫描电镜图(A:100倍,B:500倍,C:2000倍);
图3为使用本发明聚噻吩固相微萃取头固相微萃取有机氯类农药气相色谱图。
五、实施例
实施例1
将直径为0.35毫米的金属丝11,***注射装置12中,使其形成简易的固相微萃取装置,以金属丝一端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系。然后放入含0.1mol 1-1噻吩的无水BF3***溶液中,在1V范围内,50mV s-1条件下,循环50~60圈数,得到黑红色的聚噻吩(PTh)涂层13。最后用二次蒸馏水和甲醇溶液冲刷洗涤1~2分钟,即制成聚噻吩涂层萃取头。这个固相微萃取头初次使用前在气相色谱气化室中200~280℃,升温老化2~3h,直到无杂质峰出现。
实施例2
将直径为0.25毫米的金属丝11,***注射装置12中,使其形成简易的固相微萃取装置,以金属丝一端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系。然后放入含0.05mol 1-1噻吩的无水BF3***溶液中,在0.6V范围内,40mV s-1条件下,循环40~50圈数,得到黑红色的聚噻吩(PTh)涂层13。最后用二次蒸馏水和甲醇溶液冲刷洗涤1~2分钟,即制成聚噻吩涂层萃取头。这个固相微萃取头初次使用前在气相色谱气化室中200~280℃,升温老化2~3h,直到无杂质峰出现。
实施例3
将直径为0.45毫米的金属丝,***注射装置中,使其形成简易的固相微萃取装置,以金属丝一端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系。把这个三电极体系放入含0.5mol 1-1噻吩的无水BF3***溶液中,在1.6V范围内,60mV s-1条件下,循环90~100圈数,得到黑红色的聚噻吩(PTh)涂层13。最后用二次蒸馏水和甲醇溶液冲刷洗涤1~2分钟,即制成聚噻吩涂层萃取头。这个固相微萃取头初次使用前在气相色谱气化室中200~280℃,升温老化2~3h,直到无杂质峰出现。
实施例4:
基本操作同实施例1,只是金属丝的直径为0.1毫米,然后放入含0.1mol 1-1噻吩的无水BF3***溶液中,在1V范围内,30mV s-1条件下,循环20圈数,得到黑红色的聚噻吩(PTh)涂层13。其余处理均相同。
实施例5:
采用恒电位法合成聚噻吩涂层,溶剂为乙腈、苯基腈、硝基苯、三氟化硼***、碳酸丙烯酯中的一种,其中含有强酸阴离子(如ClO4 -、PF6 -、BF4 -和AsF6 -),在Li+或四烷基铵阳离子的电解质存在下,可制备生成聚噻吩的涂层。
实施例6:
采用恒电流法合成聚噻吩涂层,溶剂为乙腈、苯基腈、硝基苯、三氟化硼***、碳酸丙烯酯中的一种,其中含有强酸阴离子(如ClO4 -、PF6 -、BF4 -和AsF6 -),在Li+或四烷基铵阳离子的电解质存在下,可制备生成聚噻吩的涂层。
实施例7:
采用电位极化法合成聚噻吩涂层,溶剂为乙腈、苯基腈、硝基苯、三氟化硼***、碳酸丙烯酯中的一种,其中含有强酸阴离子(如ClO4 -、PF6 -、BF4 -和AsF6 -),在Li+或四烷基铵阳离子的电解质存在下,可制备生成聚噻吩的涂层。
实施例8:
聚噻吩涂层对15种有机氯农药(浓度为200ppt,(1)α-BHC;(2)β-BHC;(3)γ-BHC;(4)δ-BHC;(5)HC;(6)Aldrin;(7)HE;(8)α-Endosulfan;(9)p,p’DDE;(10)Dieldrin;(11)β-Endosulfan;(12)p,p’-DDD;(13)Endrin aldehyde;(14)Endosulfan sulfate.)的萃取效果如图3。结果表明该萃取头具有很好的萃取效果,检测限达到ppt级,重现性很好。
GC/ECD操作条件:DB-17毛细管石英柱(30m×250μm×0.25μm),升温程序:60℃保持0min,以25℃/min升至170℃,4℃/min升至190℃,8℃/min升至230℃,保持4min,1℃/min升至240℃,25℃/min升至260℃,保持7min。进样口温度:260℃,检测器温度:320℃。氮气:11.79psi。
实施例9:
聚噻吩涂层萃取8种硝基苯类化合物,解析后的气相色谱图表明:该涂层具有很好的选择性,检测限达到ppt级,重现性很好。
GC/ECD操作条件:DB-17毛细管石英柱(30m×250μm×0.25μm),升温程序:60℃保持0min,以10℃/min升至100℃,保持6min,8℃/min升至160℃,3℃/min升至200℃,10℃/min升至250℃,保持2min。进样口温度:250℃,检测器温度:300℃。氮气:14.33psi。
实施例10:
聚噻吩涂层对6种菊酯类农药(浓度为5ppb)的萃取。结果表明该头具有很好的萃取效果,检测限达到ppt级,重现性很好。
GC/ECD操作条件:DB-17毛细管石英柱(30m×250μm×0.25μm),升温程序:80℃保持0min,以30℃/min升至200℃,4℃/min升至260℃,0.5℃/min升至280℃,保持5min。进样口温度:260℃,检测器温度:320℃。氮气:12.7psi。
Claims (6)
1. 一种聚噻吩固相微萃取头的制备方法,其特征在于包括以下步骤:
(1)将金属丝***注射装置中,使其形成简易固相微萃取装置;
(2)以金属丝前端作工作电极,结合铂片对电极,饱和甘汞参比电极,组成三电极体系,放入含有噻吩的无水BF3***溶液中;
(3)采用电位扫描法、恒电位法、恒电流法或脉冲极化法形成粘附于金属丝前端表面的聚噻吩涂层;
(4)用二次蒸馏水和甲醇溶液洗涤,即制成聚噻吩固相微萃取头。
2. 根据权利要求1所述的一种聚噻吩固相微萃取头的制备方法,其特征在于步骤(1)中所述的金属丝为不锈钢丝。
3. 根据权利要求1或2所述的一种聚噻吩固相微萃取头的制备方法,其特征在于步骤(2)中含有噻吩的无水BF3***溶液的噻吩浓度为0.1~0.2摩尔/升。
4. 根据权利要求1或2所述的一种聚噻吩固相微萃取头的制备方法,其特征在于步骤(3)中采用电位扫描法,工作条件为:0.6~1.6V,40~60mVs-1。
5. 一种聚噻吩固相微萃取头,包括注射装置和金属丝,其特征在于金属丝前端表面为聚噻吩涂层。
6. 根据权利要求5所述的一种聚噻吩固相微萃取头,其特征在于按照权利要求1或2所述的制备方法制得。
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