CN113106744B - 一种固相微萃取纤维涂层及应用 - Google Patents
一种固相微萃取纤维涂层及应用 Download PDFInfo
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Abstract
本发明属于分析化学及材料萃取技术领域,具体涉及一种固相微萃取纤维涂层及应用。本发明充分结合了共价有机骨架材料低密度、高比表面积、良好的热稳定性、优异的结构规则性以及易于定制的特点和固相微萃取集分离、浓缩和进样为一体的无溶剂和简便高效的优异特点,提供了一种基于磁性共价有机骨架复合材料的SPME萃取纤维涂层用于检测三氯生和甲基三氯生的新方法。与拟除虫菊酯类农药相比,该方法提取三氯生类污染物的效率更高。与其他商品化纤维涂层PDMS、PDMS/DVB和PDMS/DVB/CAR相比,本发明所制的磁性共价有机骨架复合材料涂层取得了更优的萃取效果,且可重复使用150次后萃取效率从基本未变。
Description
技术领域
本发明属于分析化学及材料萃取技术领域,具体涉及一种固相微萃取纤维涂层及应用。
背景技术
三氯生(Triclosan, TCS)一种相对亲脂性化合物,其在水中溶解度较低,是药品及个人护理品(PPCPs)中常用的一种广谱抗菌剂,广泛应用于牙膏、漱口水等日化产品中,也常用于手术器械等医疗用品和纺织品的消毒,TCS在厌氧环境下性质稳定,易在水体沉积物中积累。其生物毒性、类似于内分泌干扰物的特征、降解过程的中间和最终产物的高毒性等引起了研究者们的极大重视。甲基三氯生(Methyltriclosan, MTCS)是三氯生酚羟基上的氢原子被甲基取代所形成的,是三氯生的重要衍生物。甲基三氯生具有很强的疏水性和稳定性,极容易在环境和生物体内积累。近年来研究发现,TCS对藻类等水生生物有一定的毒害作用,且残留在环境中会转化成二噁英、氯仿等有毒有害物质,造成间接危害。TCS由于价格低廉、除菌效果显著的优势,短时间内不可能完全停止使用。因此,研究其对环境中的影响及可能引起的生态效应,就显得十分重要。
固相微萃取(Solid phase microextraction, SPME)是集萃取、分离、浓缩和进样为一体的一种无溶剂和简便高效的预处理技术,具有很高的灵敏度和抗干扰能力。SPME技术是基于待测物和萃取头表面的吸附剂涂层之间的吸附平衡来实现的。因此,纤维涂层是SPME的核心部件。通常,用于SPME的商品化的萃取纤维有聚二甲基硅氧烷(PDMS),聚二甲基硅氧烷/二乙烯基苯(PDMS/DVB)和聚二甲基硅氧烷/二乙烯基苯/碳分子筛(PDMS/DVB/CAR)等。然而,这些商品化的纤维仍然存在一些不足,比如热或者溶剂稳定性不好,以及萃取选择性差等,限制了它们的广泛应用。为了解决上述问题,发展新型的SPME吸附剂具有重要的意义,也是研究的重要发展方向。
近年来,许多新型功能材料被广泛用作SPME涂层,如沸石、碳纳米管(CNTs)、分子印迹聚合物(MIPs)、金属氧化物、金属-有机骨架(MOFs)等。共价有机骨架材料(Covalentorganic frameworks,COFs)是由轻元素(碳、氧、氮、硼等)通过共价键连接形成的是一种新兴的多孔晶体结构材料。与其他多孔材料相比,COFs材料具有低密度、高比表面积、良好的热稳定性、优异的结构规则性、可调节的孔结构以及易于定制等优点,现已发展已成为现代材料科学领域最新颖的材料之一,在催化、化学传感器、气体吸附、污染物去除和色谱分离的预处理材料等领域具有广阔的应用前景。然而,将COF材料功能化用于制作SPME涂层,并将其用于复杂基质中痕量三氯生和甲基三氯生的灵敏分析的报道较少。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种固相微萃取纤维涂层及应用。
本发明所采取的技术方案如下:一种固相微萃取纤维涂层,包括纤维载体和附着在纤维载体上的萃取涂层,所述萃取涂层中包含磁性共价有机骨架复合材料。
所述磁性共价有机骨架复合材料以NiFe2O4磁性纳米粒子为内核。
所述NiFe2O4磁性纳米粒子的制备过程包括以下步骤:
(1.1)分别将一定量的FeCl3·6H2O,NiCl2·6H2O和尿素溶于水中,搅拌使其完全溶解,然后将其混合溶液转移到不锈钢高温高压反应釜中的聚四氯乙烯内胆中,并将其放置在恒温鼓风干燥箱中,温度设定为160-180 ℃,反应时间为9-16 h;
(1.2)待反应结束后,冷却至室温,用磁铁收集固体反应物,依次用超纯水、乙醇分别洗涤三次后,真空干燥,待所得固体冷却至室温后研磨,得到NiFe2O4磁性纳米粒子。
FeCl3·6H2O、NiCl2·6H2O和尿素投料的物质的量之比5:2:8。
所述磁性共价有机骨架复合材料的制备过程包括以下步骤:
(2.1)以NiFe2O4磁性纳米粒子、1,3,5-三(4-氨基苯基)苯(TAPB)和对苯二甲醛(TPA)为原料,溶解在二甲基亚砜中,再加入乙酸催化剂后恒温孵育;
(2.2) 待反应结束后,所得黄绿色固体用磁铁分离,依次用四氢呋喃和甲醇分别洗涤三次,所得固体真空干燥,待样品冷却至室温后研磨,得到磁性共价有机骨架复合材料。
NiFe2O4磁性纳米粒子、1,3,5-三(4-氨基苯基)苯(TAPB)和对苯二甲醛(TPA)投料的物质的量之比为3:2:1。
其制备过程包括以下步骤:
(3.1)将磁性共价有机骨架复合材料、聚二甲基硅氧烷(PDMS)与硅橡胶固化剂混合均匀形成混合液;
(3.2)在纤维载体表面均匀涂布步骤(3.1)所得混合液,干燥,得到附着有涂层的纤维载体;
(3.3)将步骤(3.2)得到的附着有涂层的纤维载体固定在SPME不锈钢套管的内管内;
(3.4)将步骤(3.3)固定好的附着有涂层的纤维载体插入气相色谱进样口中进行老化,直到获得稳定的色谱基线即可得到固相微萃取纤维涂层。
步骤(3.1中)聚二甲基硅氧烷(PDMS)与硅橡胶固化剂的使用比例为10:1。步骤(3.4)中气相色谱进样口的温度为300℃。
如上所述的固相微萃取纤维涂层用于检测三氯生和/或甲基三氯生的痕量检测的应用。
本发明的有益效果如下:本发明充分结合了共价有机骨架材料低密度、高比表面积、良好的热稳定性、优异的结构规则性以及易于定制的特点和固相微萃取集分离、浓缩和进样为一体的无溶剂和简便高效的优异特点,提供了一种基于磁性共价有机骨架复合材料的SPME萃取纤维涂层用于检测三氯生和甲基三氯生的新方法。与拟除虫菊酯类农药相比,该方法提取三氯生类污染物的效率更高。与其他商品化纤维涂层PDMS、PDMS/DVB和PDMS/DVB/CAR相比,本发明所制的磁性共价有机骨架复合材料涂层取得了更优的萃取效果,且可重复使用150次后萃取效率基本未变。总之,该纤维涂层具有吸附性能优异,选择性高以及使用寿命长等特点,适用于液体基质中痕量组分的富集与萃取。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,根据这些附图获得其他的附图仍属于本发明的范畴。
图1A是本发明实施例1提供的NiFe2O4@COF的合成方法流程图;
图1B是本发明实施例1提供的SPME纤维涂层制备与萃取流程图;
图2是本发明实施例2提供的合成的NiFe2O4@COFs及SPME涂层的表征:(A)和(B)SPME涂层的SEM图像;(C)NiFe2O4@COFs及COF的TGA;(D)NiFe2O4@COF接触角的测定;(E)COF的N2-吸附脱附曲线;(F)COF的孔径分布图;(G)NiFe2O4@COFs的N2-吸附脱附曲线;(H)NiFe2O4@COFs的孔径分布图;
图3是本发明实施例2提供的NiFe2O4@COFs的表征:(A)XRD;(B)傅里叶变换红外光谱;
图4是本发明实施例2提供的NiFe2O4@COFs的XPS表征;
图5是本发明实施例2提供的NiFe2O4@COFs的EDS mapping表征;
图6是本发明实施例3提供的SPME萃取过程中重要参数的优化:(A)萃取温度;(B)萃取时间;(C)盐效应;(D)pH;(E)热解吸时间;
图7 是本发明实施例4提供的基于NiFe2O4@COFs的SPME纤维涂层循环使用次数;
图8是本发明实施例4提供的基于NiFe2O4@COFs的SPME纤维涂层的萃取选择性;
图9是本发明实施例提供的基于NiFe2O4@COFs的SPME纤维涂层与其他商品化纤维涂层萃取效率的比较;
图10是本发明实施例6提供的空白样品和加标的水样(A)/尿样(B)(20.0 µg L-1)的高效液相典型色谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作进一步地详细描述。
实施例1:基于NiFe2O4@COFs的SPME纤维涂层的微萃取联用技术
步骤1:NiFe2O4@COFs磁性纳米复合材料的制备(图1A)
1)以FeCl3·6H2O(0.5406 g)和NiCl2·6H2O(0.2377 g)和脲(0.8 g)作为原料,溶于超纯水中20 min强烈的磁力搅拌使其完全溶解,然后将此混合溶液转移至具有100 mL聚四氯乙烯内胆的不锈钢高温高压反应釜中,并将其放置在恒温鼓干燥箱中,温度设定为180℃,反应时间为10 h; 待其反应结束后,冷却至室温,用磁铁收集固体反应物,依次用超纯水、乙醇分别洗涤三次,所得固体真空干燥;待样品冷却至室温后研磨并称量,最终标记为NiFe2O4磁性纳米粒子。
2)将NiFe2O4 (0.15g)、1,3,5-三(4-氨基苯基)苯(0.106g)和对苯二甲醛(0.06g)溶解在二甲基亚砜中超声5 min,再加入1.5 mL乙酸,然后恒温孵育,用磁铁分离,然后依次用四氢呋喃和甲醇分别洗涤三次,所得固体真空干燥;待样品冷却至室温后研磨并称量,最终标记为NiFe2O4@COF磁性纳米复合材料。
步骤2:SPME纤维涂层的制备(图1B)
1)以石英纤维为载体,将一定量NiFe2O4@COFs、聚二甲基硅氧烷(PDMS)与硅橡胶固化剂(比例约为10:1)混合均匀后转移至10 μL的移液枪头中;
2)将一段熔融石英纤维丝匀速穿过1)中的混合液,使熔融石英纤维丝表面均匀涂布了一层NiFe2O4@COFs材料,之后将制作好的纤维涂层丝悬挂在50℃真空干燥箱中干燥4h;
3)将环氧树脂AB结构胶水按2:1的比例混合,将制作好的纤维涂层截取约1.5 cm,涂层一端蘸取约0.3 cm的混合胶水,然后插入SPME不锈钢套管的内管,常温固化24 h即可;
4)将此纤维涂层插入300℃气相色谱进样口中进行老化,直到获得稳定的色谱基线即可使用。
步骤3:基于NiFe2O4@COFs的SPME纤维涂层的微萃取联用技术(图1B)
将此技术用于检测三氯生和甲基三氯生的方法包括以下步骤:
1)于20 mL顶空瓶内加入15 mL含一定浓度待测物质的水样,放于60 ℃水浴中并磁力搅拌,;
2)将带有纤维涂层的固相微萃取萃取手柄置于顶空瓶上方并固定;
3)将带有涂层的纤维萃取头缓慢推出暴露在水样中,萃取一定时间后,将萃取头收回于带有不锈钢外套的萃取手柄中;
4)将3)中的不锈钢钢管插入带有电子捕获检测器的气相色谱进样口中,缓慢推出吸附了待测物质的纤维涂层置于气化室中进行热解吸;
5)热解吸一定时间后,待测物完全挥发,可将此纤维涂层缓拉回收于不锈钢外套内,用于下一个萃取循环中。
实施例2:基于NiFe2O4@COFs的SPME纤维涂层的表征
将制备好的基于NiFe2O4@COFs的SPME纤维涂层进行了SEM表征,如图图2A所示,在100倍的放大倍数下,可以明显的观察到SPME萃取头是呈现出圆柱状,且可明显观察到涂层包裹均匀,形貌良好。进一步在1万倍的放大倍数下扫描(图2B)可清楚看到丝状的COFs相互交联并附着在涂层上,这为吸附待测物提供了有利的吸附位点。
热重分析(TGA)可以证明材料的热稳定性,且在气相色谱检测中具有重要参考价值。如果材料的热分解温度高于解析温度,即该材料适合运用于SPME。如图2C示,NiFe2O4@COFs涂层的在27-60 ℃之间发生了约7%的重量损失,而单纯的COF材料却没有明显的重量损失,这可能由于在合成NiFe2O4的过程中,一些小分子(如水分、洗脱用的甲醇等)残留在纳米材料中,在受热后挥发,从而导致NiFe2O4@COFs重量的损失。NiFe2O4@COFs与单纯的COF在60至400°C时几乎没有材料损失,且完全满足在本次实验的热解析温度。当温度超过400 ℃时,观察到NiFe2O4@COFs与单纯的COFs的重量急剧减少,这由于COFs层的热分解所导致的。
通过测定接触角(θ),测定了NiFe2O4@COFs的亲水性/疏水性。如图2D所示,NiFe2O4@COFs的接触角为139.195±3.375°,说明所制备的NiFe2O4@COFs涂层具有疏水倾向,有利于根据“相似相溶”原理吸附/萃取疏水性分析物。
为了确定NiFe2O4@COF磁性纳米材料的比表面积和孔结构性质,我们测定了材料的N2吸附-脱附等温线。如图2E和2F所示,COF和NiFe2O4@COFs均表现出典型的Ⅳ型等温线,表明具有中孔特性。随着N2相对压力的逐渐增加(0.1 <P/P0 <1),增加的吸附量可能是由于N2在中孔中的凝结所致。孔径分布曲线表明,COF和NiFe2O4@COF纳米复合材料的平均孔径为1.2 nm 和3.9 nm(图2F和2G内插图),通过Brunauer-Emmett-Teller(BET)模型计算,NiFe2O4@ COF纳米复合材料的比表面积和孔体积分别为169.7 m2 g-1和0.276 cm3 g-1,远高于裸露的NiFe2O4纳米颗粒(分别为32 m2 g-1和0.1684 cm3 g-1)和单独COF(58.4 m2 g-1和0.148 cm3 g-1)。大的比表面积和孔径可以改善吸附性能,并为三氯生和甲基三氯生提供更多的活性位点,从而提高萃取效率。
NiFe2O4和NiFe2O4@COFs的晶相通过广角X-射线衍射分析(图3A)。 NiFe2O4和NiFe2O4@COF在广角上具有相同的峰(18.45°,30.35°,35.72°,43.39°,57.44°和62.96°),与粉末衍射标准联合委员会(JCPDS 10-325)的(111),(220),( 311),(400),(511)和(440)的NiFe2O4的XRD衍射峰相对应。这些衍射数据表明,NiFe2O4@COF结晶良好,涂覆后具有高结晶度。与NiFe2O4相比,NiFe2O4@COF在11.30°~21.29°处的宽衍射峰是由于COF壳的低结晶度造成的。
傅里叶变换红外光谱(图3B)用于确认NiFe2O4纳米颗粒(曲线a),TPA(曲线b),TAPB(曲线c)和NiFe2O4@COF(曲线d)的特定官能团。如图3B所示,对于NiFe2O4和NiFe2O4@COFs,Fe-O-Fe振动在587 cm-1处具有典型的能带(曲线a和d)。与它的前体(TPA和TAPB)相反,NiFe2O4@COF醛基的特征官能团C=O(1693 cm-1,曲线b), 醛基的拉伸振动C-H带2869 cm-1,曲线b)和氨基的N-H带(3353 cm-1和3431 cm-1,曲线c)均完全消失了。1501 cm-1和1515 cm-1处的吸收带应归因于苯中C-C键的拉伸振动(曲线d)。同时,一些新的特征峰在1620 cm-1(曲线d)处归因于C=N拉伸振动。一些基团的消失和新的基团的生成可以证明TPA和TAPB的缩合反应形成了COF壳,并成功地将其涂覆在NiFe2O4纳米颗粒表面。
XPS经常被用来量化纳米复合材料外层和内层的元素分布。从图4A可以看出,NiFe2O4@COFs在高分辨率XPS光谱中有五个峰,结合能284.4、398.9、529.9、711.2和855.3eV可以分配给C 1s,N 1s,O 1s,Ni 2p和Fe 2p。其中XPS总图计算得到C 的含量为42.1%,N的含量为19.0%,O 的含量为23.8%,Ni 2p的含量为6.2%和Fe 2p的含量为8.8%。XPS光谱中的C 1s分为三个峰,分别位于284.6、284.8、285.6和286.2,可以分别归因于C-C,C=C,C-N和C=N(图4B)。在图4C处观察到的结合能显示出C=N和C-N的出现,其特征峰在398.6和399.1eV。 通过以上分析,可以得出结论,NiFe2O4@COFs分别包含大量C=C和C-N=C基团,它们有助于与含苯环的三氯生和甲基三氯生进行π-π共轭。
通过EDS图谱的元素分析表明NiFe2O4@COFs中存在C、N、Ni、Fe和O(图5)。COFs中的C和N原子均匀分布在NiFe2O4表面。这些结果证实了COF壳层均匀分布在NiFe2O4外表面,并形成了NiFe2O4@COF磁性纳米复合材料的核壳结构。
实施例3:SPME萃取过程中各影响因素的优化
对SPME萃取过程中有着重要影响的因素进行了优化,比如:萃取温度,萃取时间,盐效应,pH值和热解吸时间等。
温度是整个萃取实验中最关键的因素之一,SPME过程实际上是动力学反应的过程。SPME涂层对于温度的变化非常敏感,适宜的温度可以吸附更多的待测物质。温度太低不利于有机分子与固相萃取涂层的布朗运动和相互吸附,而温度的升高会使待测物的扩散速度加快,使萃取反应加速达到平衡;但如果温度过高会使平衡分配系数K减小、萃取涂层的吸附量减小、灵敏度降低,因此萃取效率会有所降低。从图6A显示了萃取温度的影响,在30-60℃的温度范围内,萃取效率随着温度的升高而逐渐升高。然而,当温度高到60℃后,观察到相反的变化趋势,萃取效率明显降低,可能是温度过高影响了涂层的萃取性能,所以选择60 ℃为最佳萃取温度。
萃取时间也是影响萃取效率的重要因素之一。最佳的萃取时间能使涂层吸附达到最优反应平衡,如果萃取时间过短,那么就会导致材料未能充分吸附待测物而导致萃取效果变差。但是,如果萃取时间过长又会使吸附在材料上的部分待测物又脱附重新溶解到水溶液中,导致萃取效率降低,浪费实验时间。如图6B所示,从20 min到30 min之间,萃取效率逐渐上升并且在30 min时达到峰值;大于30 min后,萃取效率不再升高,并且明显降低。所以选择萃取时间30 min为最佳萃取时间。
溶液中离子强度与萃取效率息息相关。一般来说,离子强度增加可以降低溶液中对目标分析物的溶解度,从而更有利于目标物被萃取出来。但是,随着离子强度的增加会增大反应的盐析效应,减少待测物在溶液中的溶解度。而随着盐浓度的增加,竞争效应可能对萃取实验影响较大,Na+和Cl-会占据萃取涂层的吸附位点,使得待测物不能完全占据涂层的吸附位点,致使萃取效率减小。如图6C所示,盐浓度为0-10 %时,萃取效率逐渐升高,说明一定盐浓度的盐析效应可促进萃取反应的进行;当盐浓度为10-70 %时萃取效率下降,说明盐浓度过高离子的竞争效应占据吸附位点使得萃取效率减小,所以选择10%为最佳盐浓度。
由于溶液的pH值决定了待测物的分子或离子状态,适宜的pH能促进待测物在基质和吸附涂层中的分配,进而增加萃取效率。如图6D所示,酸性和碱性的溶液都不利于萃取三氯生和甲基三氯生,而pH在7-8之间的萃取效率都相对较高。原因可能在于过高的离子浓度会使涂层的吸附位点减少,从而对待测物的吸附能力减小。因此,选择接近于电中性的超纯水pH做为溶液最佳pH值。
一般情况下,解吸时间越长解吸越充分,但若解吸时间变短解吸不充分,纤维涂层上会残留待测物,从而导致影响下一次萃取实验的结果。解吸时间对萃取效率的影响如图6E所示,从2-10 min时,萃取效率逐渐增加,到10 min时萃取效率达到峰值,10 min之后萃取效率明显降低,所以选择10 min为实验的最佳解析时间。
实施例4:基于NiFe2O4@COFs的SPME涂层的性能评价
所制备的基于NiFe2O4@COFs的SPME纤维涂层的重复性是实际应用中的关键指标。为了研究其重复性,将萃取过的基于NiFe2O4@COFs的SPME纤维涂层插入300℃的气相色谱进样口中热解吸10 min,直至待测物的色谱峰未检出,才可将其重新用于下一次的萃取循环中。如图7所示,基于NiFe2O4@COFs的SPME纤维涂层可反复使用150次后待测物的萃取效率没有太大的改变,这证明了基于NiFe2O4@COFs的SPME纤维涂层具有出色的重现性和稳定性。
本实施例选取五种拟除虫菊酯类农药和两种三氯生类污染物用来评价所制作SPME涂层的萃取选择性。如图8所示,基于NiFe2O4@COFs涂层的固相微萃取技术萃取七种环境污染物,即三氯生、甲基三氯生、甲氰菊酯、联苯菊酯、氯菊酯、氰戊菊酯和溴氰菊酯的萃取效率分别为88.80%、91.82%、36.57%、43.74%、25.07%、32.73%和46.51%,萃取效率的高低顺序如下:甲基三氯生>三氯生>溴氰菊酯>联苯菊酯>甲氰菊酯>氰戊菊酯>氯菊酯。说明NiFe2O4@COFs涂层对于七种环境污染物中的三氯生和甲基三氯生的吸附性能最好。以上事实可以解释为:SPME涂层中的COFs层与三氯生及其衍生物的苯基之间的强π-π相互作用有助于高效吸附。通过XPS分析可以得出,通过2.3.2.8节的XPS分析的第一张总图分析可以得出磁性共价有机骨架其中XPS总图计算得到C 的含量为42.1%,N 的含量为19.0%,O 的含量为23.8%,Ni 2p的含量为6.2%和Fe 2p的含量为8.8%,说明实施例1合成的磁性共价有机骨架是一种基于碳基的一种复合材料,不利于与水发生竞争吸附时萃取吸附极性特别强的物质。而通过对比七种分析物的Log kow值(见表1),可以得出三氯生和甲基三氯生的极性远远低于拟除虫菊酯的极性,所以,三氯生和甲基三氯生的萃取效率高于拟除虫菊酯类农药。NiFe2O4@COFs涂层的提取效率取与其本身的一系列物理和化学结构性质有关。
为了考察本专利自制的NiFe2O4@COFs纤维涂层的萃取性能,选择商品化纤维涂层以作对比。选择的商品化纤维涂层有:聚二甲基硅氧烷(PDMS)、聚二甲基硅氧烷/二乙烯基苯(PDMS/DVB)和聚二甲基硅氧烷/二乙烯基苯/碳分子筛(PDMS/DVB/CAR)。结果如图9所示,三种商品化纤维涂层对于三氯生和甲基三氯生的萃取效率均低于60.10%,而自制NiFe2O4@COFs纤维涂层的催效率均大于99.37%,实验结果表明,本专利自制的NiFe2O4@COFs纤维涂层对于三氯生和甲基三氯生的有着优异的萃取性能。
实施例5:NiFe2O4@COFs-SPME-GC/ECD的方法学性能评价
为评价该方法的分析性能,在上述最佳条件下,严格研究了一系列分析参数,包括线性范围(LR),回归方程,决定系数(R2),检测限(LODs),定量限(LOQs),富集因子(EFs)和相对标准偏差(RSD)。如表2所示,对于TCS和MTCS,LR均为0.1-1000 µg L-1, R2值分别为0.9995和0.9998。 LOD和LOQ分别为0.001-0.007 µg L-1(S/N=3)和0.003-0.023 µg L-1(S/N=10)。日内、日间及不同批次纤维涂层间的RSD(n=6)分别为2.53-3.55%、2.37-5.06%和3.52-7.64%。这些数据表明,该方法具有较宽的测定范围,较高的灵敏度和精密度,从而满足了复杂基质中三氯生甲基三氯生痕量检测的要求。
实施例6:实际样品的分析
实验中的实际液体基质样品的主要来源:自来水样品取自温州医科大学环境化学实验室。河流水取自温瑞塘河(浙江温州瓯海)。桶装水购自温州嘉辉超市(中国温州瓯海)。所有收集到的水样均用0.45 μm滤膜过滤。尿液样本(男性、女性和儿童)由温州医科大学附属第一医院临床实验室捐赠。本研究经温州医科大学伦理委员会批准。用0.22 μm PTFE膜过滤尿液样品,并在4 ℃下保存。
为了评估基于NiFe2O4@COFs涂层的SPME技术的适用性,选择水和人体液样品进行了萃取,联用GC/ECD进行了分析。收集的实际样本包括水(自来水、桶装水和河水)和人体液体(男性尿液、女性尿液和儿童尿液)。如表3所示,在自来水、桶装水、河水、男性尿液、女性尿液和儿童尿液样品中均未检测到三氯生和甲基三氯生。为了评估该方法的萃取效果,所有实际样品均以低中高三种添加浓度(0.2、2.0和20.0 µg L-1)进行加标回收率实验(图10)。自来水、桶装水、河水、男性尿液、女性尿液和儿童尿液样品中对TCS和MTCS的相对回收率范围分别为 86.2-115.4%、85.7-116.5%、89.3- 121.9%、81.9-103.9%、84.8-129.1%和100.2-113.2%。以上数据表明,本发明所开发的基于NiFe2O4@COFs涂层的SPME/GC-ECD技术灵敏可靠、高校绿色,可用于测定液体基质中痕量三氯生和甲基三氯生的检测与分析。
实施例7:NiFe2O4@COFs-SPME-GC/ECD方法与其他方法的比较
将NiFe2O4@COF-SPME/GC-ECD方法与之前报道的其他SPME方法在涂层材料、样品类型、萃取时间、LRs、LODs和RSDs等方面的分析性能进行了比较。如表4所示,本方法的萃取时间和LODs均低于商业化纤维PDMS/DVB、CW-DVB/PDMS-DVB、CAR/PDMS、PDMS/DVB/PDMS和PDMS和自制的萃取纤维涂层benzoxy-C6/OH-TSO和MWCNT@PS。在LRs和RSDs方面,本方法优于或等效于以上报道的方法。综上所述,NiFe2O4@COF-SPME/GC-ECD方法具有简单、高效、成本低、使用方便、环境友好等优点,在环境水体和人体尿液中三氯生类污染物的痕量监测中具有广阔的应用前景。
综上所述,本发明公开了一种磁性共价有机骨架复合材料、固相微萃取纤维涂层及其制备方法和应用。该磁性共价有机骨架复合材料以NiFe2O4磁性纳米粒子为内核,其外包覆由1,3,5-三(4-氨基苯基)苯(TAPB)和对苯二甲醛(TPA)发生席夫碱缩合反应形成含C=N双键的共价有机骨架聚合物。利用该磁性共价有机骨架复合材料(NiFe2O4@COFs)作为涂层,以石英丝作为载体,与聚二甲基硅氧烷(PDMS)和硅橡胶固化剂混合制成基于NiFe2O4@COFs复合材料的SPME萃取纤维涂层,与GC-ECD联用,构建了基于环境水样和人体尿液样品中三氯生和甲基三氯生的痕量检测技术。与拟除虫菊酯类农药相比,该方法提取三氯生类污染物的效率更高,推测可能的原因是NiFe2O4@COFs包含大量C=C和C-N=C基团,它们有助于与含苯环的三氯生和甲基三氯生进行π-π共轭,从而增加了其选择性。与其他商品化纤维涂层PDMS、PDMS/DVB和PDMS/DVB/CAR相比,本发明所制的NiFe2O4@COFs涂层取得了更优的萃取效果,且可重复使用150次后萃取效率基本未变。总之,该纤维涂层具有吸附性能优异,选择性高以及使用寿命长等特点,适用于液体基质中痕量组分的富集与萃取。
本领域普通技术人员可以理解实现上述实施例方法中的全部或部分步骤是可以通过程序来指令相关的硬件来完成,所述的程序可以存储于一计算机可读取存储介质中,所述的存储介质,如ROM/RAM、磁盘、光盘等。
以上所揭露的仅为本发明较佳实施例而已,当然不能以此来限定本发明之权利范围,因此依本发明权利要求所作的等同变化,仍属本发明所涵盖的范围。
Claims (8)
1.一种固相微萃取纤维涂层,其特征在于:所述固相微萃取纤维涂层包括纤维载体和附着在纤维载体上的萃取涂层,所述萃取涂层中包含磁性共价有机骨架复合材料;
其制备过程包括以下步骤:
(3.1)将磁性共价有机骨架复合材料、聚二甲基硅氧烷(PDMS)与硅橡胶固化剂混合均匀形成混合液;
(3.2)在纤维载体表面均匀涂布步骤(3.1)所得混合液,干燥,得到附着有涂层的纤维载体;
(3.3)将步骤(3.2)得到的附着有涂层的纤维载体固定在SPME不锈钢套管的内管内;
(3.4)将步骤(3.3)固定好的附着有涂层的纤维载体插入气相色谱进样口中进行老化,直到获得稳定的色谱基线即可得到固相微萃取纤维涂层;
所述磁性共价有机骨架复合材料以NiFe2O4磁性纳米粒子为内核。
2.根据权利要求1所述的固相微萃取纤维涂层,其特征在于:所述NiFe2O4磁性纳米粒子的制备过程包括以下步骤:
(1.1)分别将一定量的FeCl3·6H2O,NiCl2·6H2O和尿素溶于水中,搅拌使其完全溶解,然后将其混合溶液转移到不锈钢高温高压反应釜中的聚四氯乙烯内胆中,并将其放置在恒温鼓风干燥箱中,温度设定为160-180 ℃,反应时间为9-16 h;
(1.2)待反应结束后,冷却至室温,用磁铁收集固体反应物,依次用超纯水、乙醇分别洗涤三次后,真空干燥,待所得固体冷却至室温后研磨,得到NiFe2O4磁性纳米粒子。
3.根据权利要求2所述的固相微萃取纤维涂层,其特征在于:FeCl3·6H2O、NiCl2·6H2O和尿素投料的物质的量之比5:2:8。
4.根据权利要求1所述的固相微萃取纤维涂层,其特征在于:所述磁性共价有机骨架复合材料的制备过程包括以下步骤:
(2.1)以NiFe2O4磁性纳米粒子、1,3,5-三(4-氨基苯基)苯(TAPB)和对苯二甲醛(TPA)为原料,溶解在二甲基亚砜中,再加入乙酸催化剂,然后恒温孵育;
(2.2) 待反应结束后,所得黄绿色固体用磁铁分离,依次用四氢呋喃和甲醇分别洗涤三次,所得固体真空干燥,待样品冷却至室温后研磨,得到磁性共价有机骨架复合材料。
5.根据权利要求4所述的固相微萃取纤维涂层,其特征在于:NiFe2O4磁性纳米粒子、1,3,5-三(4-氨基苯基)苯(TAPB)和对苯二甲醛(TPA)投料的物质的量之比为3:2:1。
6.根据权利要求1所述的固相微萃取纤维涂层,其特征在于:聚二甲基硅氧烷(PDMS)与硅橡胶固化剂的使用比例为10:1。
7.根据权利要求1所述的固相微萃取纤维涂层,其特征在于:步骤(3.4)中气相色谱进样口的温度为300℃。
8.如权利要求1-7任一项所述的固相微萃取纤维涂层用于检测三氯生和/或甲基三氯生的痕量检测的应用。
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CN111420638B (zh) * | 2020-03-03 | 2021-05-11 | 温州医科大学 | 一种磁性纳米复合材料、磁泡腾片以及磁泡腾增强微萃取方法和应用 |
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