CN109261231A - 低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片及其制备方法 - Google Patents
低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片及其制备方法。原料组成为:甲基丙烯酸12.00%‑18.67%,对氨基苯乙烯修饰的氧化石墨烯0.01%‑0.20%,二甲基丙烯酸乙二醇酯8.02%‑12.49%,氯化胆碱/乙二醇15.00%‑51.00%,正丙醇23.08%‑54.40%,偶氮二异丁腈0.20%‑0.31%。使用低共熔溶剂制备的氧化石墨烯掺杂的高比表面积的整体柱微流控芯片,并将其用于多环芳烃固相微萃取。与传统的固相微萃取相比,本发明的微流控芯片固相微萃取具有微型化,低成本,快速,高通量等优势。含有适量氧化石墨烯掺杂的整体柱微流控芯片对多环芳烃的回收率富集效率明显提高,达90%以上,RSD均小于3%。
Description
技术领域
本发明涉及一种低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片及其制备方法,使用低共熔溶剂制备的氧化石墨烯掺杂的高比表面积的整体柱微流控芯片,并将其用于多环芳烃固相微萃取。与传统的固相微萃取相比,本发明的微流控芯片固相微萃取具有微型化,低成本,快速,高通量等优势。含有适量氧化石墨烯掺杂的整体柱微流控芯片对多环芳烃的回收率富集效率明显提高,达90%以上,RSD均小于3%。
背景技术
微流控芯片是21世纪七大前沿科学技术之一,具有低成本、快速、高通量等优势。固相微萃取技术(solid phase extraction,SPE) 是一种基于分析物在固态基质上的吸附和解吸,而实现液态样品的纯化和富集的样品前处理技术。微流控芯片上的固相微萃取具有传统固相萃取技术不可比拟的优势,既能提高系统集成度,又能消除接口带来的死体积。
原位聚合法是制备微流控芯片整体柱较常用的一种方法,可以避免微流控芯片加工中高度精密的技术要求。采用光引发聚合整体柱,可以有效的掌握整体柱的位置,长度。但是,原位聚合得到的整体柱并不总能达到令人满意的富集效果或者特定的色谱分离需求,目前,主要通过采用后修饰的方法(例如,表面衍生、纳米材料改性、有机-无机杂化改性等手段)在柱表面生成功能团改善这一问题。但有些修饰的反应条件往往不够温和,用于聚二甲基硅氧烷(PDMS)等化学耐受性不够好的芯片材料时会受到限制。
氧化石墨烯(GO)拥有大量的含氧基团,具有超大的比表面积和离域的电子结构,因此,GO具有较高吸附容量和吸附含苯环结构化合物的潜力。目前,毛细管整体柱中掺杂GO已经有报道。因此,将GO掺杂进入固相微萃取整体柱微流控芯片,借助GO超强的比表面积,有望增加萃取过程中的接触位点,提高固相微萃取中富集效率。但是GO通常在的溶剂中容易发生不可逆团聚,从而影响合成的整体柱芯片的均匀性,因此不利于目标物的富集和洗脱。
低共熔溶剂(DES)是一种绿色溶剂,具备挥发性低、无毒、可生物降解、廉价等优于传统溶剂特点。DES本质上是由一种离子混合物,通过两种或多种不同熔点的固体化合物按一定比例混合后形成。其中一类DES是的形成在于不同比例的的氢键供体(例如醇,羧酸和酰胺等)和氢键受体(例如季铵盐)组合形成的一种低共熔混合物。最常见的氢键受体是氯化胆碱(ChCl),氢键供体是醇。该DES体系具有均匀透明、纯度高、粘度大的特点。
中国专利CN 20161026860公开了一种氧化石墨烯型在线净化固相萃取整体柱及制备方法和用途。由于氧化石墨烯超强的比表面积,其集成在整体柱内可增加萃取过程中的接触位点,提高固相微萃取富集效率。但氧化石墨烯在通常的溶剂中容易聚沉,导致获得的GO掺杂整体柱不均匀,直接影响其效果。
发明内容
本发明的目的是提供一种低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片及其制备方法。利用低共熔溶剂粘度高的特点,制备氧化石墨烯掺杂的整体柱微流控芯片的制备及固相微萃取应用。将氧化石墨烯分散于低共熔溶剂中,获得均匀的整体柱微流控芯片中,可以明显提高富集效率,增加使用寿命。含有适量氧化石墨烯掺杂的整体柱与对照比较,对多环芳香烃固相微萃取的回收率有明显提高。
本发明提供的低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片的原料质量配比为:
甲基丙烯酸 12.00%-18.67%
对氨基苯乙烯修饰的氧化石墨烯 0.01%-0.20%
二甲基丙烯酸乙二醇酯 8.02%-12.49%
氯化胆碱/乙二醇 15.00%-51.00%
正丙醇 23.08%-54.40%
偶氮二异丁腈 0.20%-0.31%
上述的各原料的质量组成之和为100 %。
本发明提供的低共熔溶剂氧化石墨烯掺杂整体柱微流控芯片的制备方法,采用原位光引发聚合法制备,具体经过下列步骤:
1)首先用食人鱼溶液(V浓H2SO4:VH2O2 = 3:1)冲洗微流控芯片通道30秒,随后用水冲洗至pH = 7;然后用 1 mmol/L 的氢氧化钠溶液冲洗毛细管约 30 min;随后用水冲洗 30 min;再注入 50% γ-MPS/甲苯溶液冲洗 3 h,随后用水冲洗pH = 7后,用丙酮冲洗15 min;最后用氮气吹干。
2)称取20mg羧基化氧化石墨烯加入盛放50mL N,N’-二甲基甲酰胺的烧杯中,在150W的超声功率下超声20分钟。然后转入圆底烧瓶中,分别加入215μL对氨基苯乙烯和25mLN,N’-二异丙基碳化二亚胺,以1MPa/min通入N2 气5分钟除去溶液中的O2,再放入80℃水浴中,并以1000转/分钟转速磁力搅拌反应24h,随后以5000转/分钟离心5分钟弃去上清液。最后,分别用四氢呋喃,水,甲醇清洗三次,以5000转/分钟离心5分钟弃去上清液,自然风干。得到对氨基苯乙烯修饰的羧基化氧化石墨烯(pAS-COOH-GO)。
3)按计量将羧基化氧化石墨烯经对氨基苯乙烯(pAS)酰胺化得到对氨基苯乙烯修饰的羧基化氧化石墨烯(pAS-COOH-GO),分散在氯化胆碱/乙二醇中,即pAS-COOH-GO-氯化胆碱/乙二醇。
4)按计量分别单体甲基丙烯酸丁酯(BMA),交联剂二甲基丙烯酸乙二醇酯(EDMA),引发剂偶氮二异丁腈(AIBN),分散在二元致孔剂正丙醇和pAS-COOH-GO-氯化胆碱/乙二醇中。将上述混合液超声5 min,然后注入已经处理的微流控芯片通道中,使其完全填充预聚液并用胶带密封,芯片除了2 cm长窗口之外用锡箔纸箔覆盖。再把芯片放在装有两个365nm,8W UV管的反应器中,暴露于紫外灯下15 min。整体柱微流控芯片然后用乙腈冲洗去除整体柱内的致孔剂及未反应组分。
不含氧化石墨烯的基于低共熔溶剂的整体柱微流控芯片,除了不含氧化石墨烯外,其余步骤同上。
本发明得到的基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片可用于多环芳烃的富集。
通过微流控芯片固相微萃取技术,对多环芳烃进行富集。通过淋洗溶剂、洗脱溶剂、上样速率以及洗脱速率的考察,建立了较好的富集多环芳烃(以菲和蒽为研究对象)的方法。本发明中选用甲醇:水=5:5(v / v)作为淋洗溶剂,乙腈作为洗脱剂,上样流速为3 μl/ min,洗脱速率为3 μl / min,得到样品菲和蒽回收率分别为94.5%,97%,回收率的相对标准偏差(RSD)均小于3%。
本发明提供了以基于低共熔溶剂的氧化石墨烯掺杂制备整体柱微流控芯片,具体是先将对氨基苯乙烯修饰过的羧基化氧化石墨烯分散于低共熔溶剂中,然后以甲基丙烯酸丁酯为单体,二甲基丙烯酸乙二醇酯为交联剂,对氨基苯乙烯修饰的羧基化氧化石墨烯为掺杂剂,正丙醇和氯化胆碱/乙二醇为二元致孔剂,偶氮二异丁腈为引发剂,紫外光引发合成氧化石墨烯掺杂的整体柱芯片。该制备方法容易操作,制备过程简单,并通过调整氧化石墨烯的含量,正丙醇和DES的比例等获得富集效率高的整体柱芯片。本发明利用低共熔溶剂粘度高的特点,在预聚合液中有效分散了GO,获得均匀的GO掺杂整体柱微流控芯片。该方法合成的基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片与不含氧化石墨烯掺杂的整体柱微流控芯片相比,对多环芳烃回收率可达90%以上,RSD均小于3%,为多环芳烃的固相萃取提供了一种高效快速的方法。
附图说明
图1 为本发明制备的基于低共熔溶剂氧化石墨烯掺杂的整体柱微流控芯片与不含氧化石墨烯的微流控芯片对多环芳烃固相微萃取后的HPLC色谱图。
图2 为本发明制备的基于低共熔溶剂氧化石墨烯掺杂的整体柱微流控芯片考察氧化石墨烯含量对多环芳烃固相微萃取影响对比图。
图3 为本发明制备的基于低共熔溶剂的氧化石墨烯掺杂的整体柱与不含氧化石墨烯的整体柱微流控芯片的扫描电镜对比图。
图4 为本发明制备的基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片对湖水中多环芳烃固相微萃取后的HPLC色谱图。
具体实施方式
下面结合具体实施例,进一步详细阐述本发明。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制造厂商所建议的条件;所用的通用设备、材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
基于低共熔溶剂氧化石墨烯掺杂的整体柱微流控芯片与不含氧化石墨烯的微流控芯片对多环芳烃固相微萃取对比。具体操作步骤如下:
基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片的制备方法:
a. 首先用食人鱼溶液(V浓H2SO4:VH2O2 = 3:1)冲洗微流控芯片(聚二甲基硅氧烷-玻璃)通道30秒,随后用水冲洗至pH = 7;然后用 1 mmol/L 的氢氧化钠溶液冲洗毛细管约30 min;随后用水冲洗 30 min;再注入 50% γ-MPS/甲苯溶液冲洗 3 h,随后用水冲洗pH= 7后,用丙酮冲洗15 min;最后用氮气吹干。
b. 称取20mg羧基化氧化石墨烯(南京先丰纳米材料科技有限公司)加入盛放50mLN,N’-二甲基甲酰胺的烧杯中,在150W的超声功率下超声20分钟。然后转入圆底烧瓶中,分别加入215μL对氨基苯乙烯和25mL N,N’-二异丙基碳化二亚胺,以1MPa/min通入N2 5分钟除去溶液中的O2,再放入80℃水浴中,并以1000转/分钟转速磁力搅拌反应24h,随后以5000转/分钟离心5分钟弃去上清液。最后,分别用四氢呋喃,水,甲醇清洗三次,以5000转/分钟离心5分钟弃去上清液,自然风干。得到对氨基苯乙烯修饰的羧基化氧化石墨烯(pAS-COOH-GO)。
c. 将质量分数为0.05%的掺杂剂对氨基苯乙烯修饰的羧基化氧化石墨烯分散于49.43%的致孔剂氯化胆碱/乙二醇(1:3,w%/w%)中,再加入质量分数为30.3%的致孔剂正丙醇,12%的单体甲基丙烯酸丁酯,8.02%交联剂二甲基丙烯酸乙二醇酯为交联剂,0.2%的引发剂偶氮二异丁腈,然后,将混合液在150W的超声功率下超声5 min,注入已经处理的微流控芯片通道中,使其完全填充预聚液并用胶带密封,芯片除了2 cm长窗口之外用锡箔纸箔覆盖。再把芯片放在装有两个365 nm,8W UV管的反应器中,暴露于紫外灯下15 min。整体柱微流控芯片然后用乙腈冲洗去除整体柱内的致孔剂,未反应组分。
d. 将5mg菲和5mg蒽溶解在5mL甲醇中制备1mg/mL储备溶液。然后用甲醇和水混合物(50/50,v/v)稀释储备溶液,得到1μg/mL菲和蒽标品的混合液。
e. 上述得到整体柱微流控芯片固相微萃取菲和蒽标品的混合液,用3 μl/ min流速上样100μL,再用甲醇:水=5:5(v / v)以3 μl / min流速淋洗5 min,最后用乙腈以3 μl/ min流速洗脱10μL。取5 μl 洗脱液稀释10倍,通过高效液相色谱法进行检测分析。
无氧化石墨烯掺杂的整体柱微流控芯片,除不含氧化石墨烯外,为其余步骤同上。
结果表明,含氧化石墨烯掺杂剂的整体柱微流控芯片回收率明显提高(见图1)。
实施例2
为了明确基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片中氧化石墨烯的含量对多环芳烃固相微萃取回收率的影响,制备不同含量的氧化石墨烯整体柱进一步分析。具体操作步骤如下:
a.同上述方法(实施例1)合成含有不同含量氧化石墨烯的整体柱。除了掺杂剂在氯化胆碱/乙二醇中质量分数不同外,其余都相同。掺杂剂对氨基苯乙烯修饰的羧基化氧化石墨烯质量分数分别为0%,0.01%,0.05%,0.10%,0.15%。
b. 同上述方法(实施例1)用不同含量的氧化石墨烯整体柱对多环芳烃进行固相微萃取。
结果表明,随着氧化石墨烯含量不断增加,多环芳烃的回收率先升高后降低(见图2)。说明基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片,氧化石墨烯质量分数为0.05% 时,富集效率最高。
实施例3
扫描电镜表征。图3a和3b为氧化石墨烯掺杂的整体柱,图3c和3d为无氧化石墨烯掺杂的空白柱。
结果表明,氧化石墨烯掺杂的整体柱比无石墨烯掺杂的整体柱孔穴更多,背压更低(见图3a, 3c)。石墨烯成功的掺杂在整体柱中(见图 3b,3d)。
实施例4
基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片的应用。具体操作步骤如下:
a.同上述方法(实施例1)合成基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片。
b.上述得到基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片用于湖水(天津医科大学静怡湖)中多环芳烃的固相微萃取,同上述方法(实施例1)(见图4)。
结果表明,基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片成功的应用于实际样品中多环芳烃的固相微萃取。
Claims (4)
1. 一种基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片,其特征在于它的原料的质量组成:
甲基丙烯酸 12.00%-18.67%
对氨基苯乙烯修饰的氧化石墨烯 0.01%-0.20%
二甲基丙烯酸乙二醇酯 8.02%-12.49%
氯化胆碱/乙二醇 15.00%-51.00%
正丙醇 23.08%-54.40%
偶氮二异丁腈 0.20%-0.31%
上述的各原料的质量组成之和为100 %。
2.按照权利要求1所述的整体柱微流控芯片,其特征在于它的原料的质量组成:
甲基丙烯酸 12.00%
对氨基苯乙烯修饰的氧化石墨烯 0.05%
二甲基丙烯酸乙二醇酯 8.02%
氯化胆碱/乙二醇 49.43%
正丙醇 30.30%
偶氮二异丁腈 0.20%
上述的各原料的质量百分比组成之和为100 %。
3.权利要求1所述的基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片的制备方法,其特征在于经过下列步骤:
1)首先用食人鱼溶液,V浓H2SO4:VH2O2 = 3:1,冲洗微流控芯片通道30秒,随后用水冲洗至pH = 7;然后用 1 mmol/L 的氢氧化钠溶液冲洗毛细管约 30 min;随后用水冲洗 30 min;再注入 50% γ-MPS/甲苯溶液冲洗 3 h,随后用水冲洗pH = 7后,用丙酮冲洗15min;最后用氮气吹干;
2)按计量将掺杂剂对氨基苯乙基修饰的羧基化石墨烯分散于致孔剂氯化胆碱/乙二醇,然后按计量分别加入正丙醇,单体甲基丙烯酸丁酯,交联剂二甲基丙烯酸乙二醇酯,引发剂偶氮二异丁腈;将上述混合液超声5 min,然后注入已经处理的微流控芯片通道中,使其完全填充预聚液并用胶带密封,芯片除了2cm长窗口之外用锡箔纸箔覆盖;再把芯片放在装有两个365nm,8W UV管的反应器中,暴露于紫外灯下15 min,整体柱微流控芯片然后用乙腈冲洗去除整体柱内的致孔剂,未反应组分。
4.权利要求1所述的基于低共熔溶剂的氧化石墨烯掺杂的整体柱微流控芯片用于富集多环芳烃的应用。
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