CN106166481B - 单壁碳纳米角修饰的毛细管电色谱整体柱及其制备方法 - Google Patents
单壁碳纳米角修饰的毛细管电色谱整体柱及其制备方法 Download PDFInfo
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种单壁碳纳米角修饰的毛细管电色谱整体柱,其制备方法为:将单壁碳纳米角与苯乙烯混合,超声分散得到单壁碳纳米角的苯乙烯分散液;将所得分散液与环己醇混合,超声分散后,加入二乙烯苯、甲苯、自由基引发剂、2‑丙烯酰胺基‑2‑甲基丙磺酸,继续超声分散,之后通入氮气,得到反应混合液;将所得反应混合液引入预处理过的毛细管内预设固定相的位置,然后将毛细管两端用硅胶封口,置于40~100℃下进行固化反应2~8h,之后毛细管经后处理,制得所述单壁碳纳米角修饰的毛细管电色谱整体柱;本发明首次将单壁碳纳米角应用于毛细管电色谱整体柱中,并且制备过程简单,步骤少,反应条件可控,制备效果更理想。
Description
(一)技术领域
本发明涉及一种毛细管电色谱整体柱及其制备方法,特别涉及一种单壁碳纳米角修饰的毛细管电色谱整体柱及其制备方法。
(二)背景技术
单壁碳纳米角(Single-Walled Carbon Nanohorns,SWNHs)是lijima(lijima etal.,Chemical Physics Letters,309(1999)165)等人在室温下用CO2激光消融法制得并命名的。SWNHs是一端呈封闭的锥形(锥角约20°),而其余部分类似于单壁碳纳米管(SWNTs)的一种新型纳米材料。自1999年被发现以来,因自身独特的结构已引起科研者关注。单根SWNHs直径为2-5nm,长度为20-50nm,正常状态约2000个单根SWNHs聚集在一起会形成直径100nm左右的球形粒子。
SWNHs具有很多独特性质:(1)构成SWNHs的碳原子大多数都镶嵌在纳米角表面,因此SWNHs具有较大的比表面积;(2)SWNHs热稳定性非常好,当在真空中温度高达到1400℃左右时,SWNHs结构才稍微有变化;(3)SWNHs具有多孔性,有内在孔和外在孔,有利于对小分子的选择性吸附;(4)SWNHs具有优良的电子特性,修饰电极能使电子得到较好的传递,并且表面能非常高,可以在其表面连接更多的官能团。目前为止,修饰SWNHs有共价键修饰和非共价键修饰。综上所述,SWNHs具有较高的比表面积、良好的热稳定性、高产率、内孔和外孔多孔性等优点,因此在很多领域有潜在的应用价值。
碳纳米角在分析化学领域的应用主要为电化学传感器和预富集吸附剂。如Zhang(Zhang et al.,Analytical Chemistry,82(2010)1117)等用SWNHs构建了电化学免疫传感器来检测环形七肽微囊藻毒素。Dai(Dai et al.,Chemical Communications,47(2011)11915)等人利用β-环糊精修饰的SWNHs构建了电化学发光生物传感器用来检测柚皮苷。Ran(X.Ran et al,Anal.Chim.Acta 892(2015)85)等先利用3,4,9,10-苝四羧酸酐、金纳米粒子和磺化环糊精同时修饰碳纳米角,再将此修饰后的纳米角修饰玻璃碳电极作为电化学传感器,同时高灵敏地检测了杨梅素和芦丁。Liu(Liu et al.,Biosensors andBioelectronics,23(2008)1887)等人用阳离子交换剂Naficon,将SWNHs固定在铂碳电极上,制备出了无酶葡萄糖电化学传感器,最终成功完成了对葡萄糖的无霉测定。Xu(Xu etal.,Chromatogr.A,1284(2013)180)等人用SWNHs修饰电极检测对苯二酚、儿茶酚和间苯二酚三种同分异构体,实现了对邻、间、对苯二酚异构体的分离,并可同时检测。尿酸、多巴胺和抗坏血酸这三种物质的氧化电位非常接近,并且通常会共同存在,所以,分别测定这三种物质呈现一定的困难,Zhu(Zhu et al.,Sensors and Actuators B:Chemical,198(2014)388)等人采用SWNHs修饰铂碳电极,实现了对尿酸、多巴胺和抗坏血酸三种物质的同时测定,并极大地增强了测定的灵敏度。SWNHs兼具较大的比表面积和较高的位点结合能,故可以使其作为一种吸附剂。Murata(Murata et al.,Biosensors&Bioelectronics,55(2014)360)等人探究了氙气和氢气在SWNHs上的物理吸附机制,并得到SWNHs对氙气的吸附能力远远大于平面石墨。M.Roldán-Pijuán,(M.Roldán-Pijuán,et al.,Microchemical Journal115(2014)87)将氧化的单壁碳纳米角修饰在一个搅拌棒上作为微固相萃取器,对水样中二苯甲酮进行预富集。至此碳纳米角在分析化学中的应用主要集中在电化学传感器和吸附剂等方面,直接将其作为分离功能基团的应用尚未见报导。
(三)发明内容
本发明的目的在于利用碳纳米角特殊的结构和性质,尤其是大的比表面积、强的疏水性和π-π电子堆积效应等,将其作为苯系物和稠环芳烃类物质的分离选择试剂,提供一种单壁碳纳米角修饰的毛细管电色谱整体柱及其制备方法。
本发明制备方法的原理是:先将单壁碳纳米角分散在反应单体苯乙烯中,再将单壁碳纳米角的苯乙烯分散液加入到交联剂二乙烯苯反应物中,以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为产生电渗流单体,在自由基引发剂作用下进行一步原位双键聚合反应,制备包含单壁碳纳米角功能基团的聚苯乙烯毛细管电色谱整体柱。该方法应用了柱内双键聚合反应,反应条件易于控制,一步完成,较大程度地保证了单壁碳纳米角稳定地修饰在整体柱固定相中。
为实现上述目的,本发明采用如下技术方案:
一种单壁碳纳米角修饰的毛细管电色谱整体柱,其按如下方法制备得到:
(1)将单壁碳纳米角与苯乙烯混合,于20~30KHz超声分散2~3h,得到单壁碳纳米角的苯乙烯分散液;
步骤(1)中,所述苯乙烯的体积用量以单壁碳纳米角的质量计为1~10mL/mg,优选2~5mL/mg,特别优选2mL/mg;
(2)将步骤(1)所得单壁碳纳米角的苯乙烯分散液与环己醇混合,于20~30KHz超声分散1~4h,再加入二乙烯苯(DVB)、甲苯、自由基引发剂、2-丙烯酰胺基-2-甲基丙磺酸(AMPS),继续于20~30KHz超声分散10~60min,之后通入氮气5~30min,得到反应混合液;
步骤(2)中,所述单壁碳纳米角的苯乙烯分散液与环己醇、二乙烯苯、甲苯、自由基引发剂、2-丙烯酰胺基-2-甲基丙磺酸的投料质量比为1:9.5~6.3:4.0~1.0:4.3~2.9:0.05~0.03:0.02,优选1:8.4:2.0:3.8:0.04:0.02;所述的自由基引发剂为偶氮二异丁腈(AIBN)、偶氮二异庚腈或过氧化苯甲酰,优选偶氮二异丁腈;
(3)将步骤(2)所得反应混合液引入预处理过的毛细管内预设固定相的位置,然后将毛细管两端用硅胶封口,置于40~100℃下进行固化反应2~8h,之后毛细管经后处理,制得所述单壁碳纳米角修饰的毛细管电色谱整体柱。
本发明中,所述的毛细管是本领域毛细管电色谱分析中常规使用的毛细管,可商购获得,通常为熔融石英毛细管,内径为50~150μm,外径为350~400μm,且其表面涂有20μm厚的聚酰亚胺涂层。
所述预处理过的毛细管,是指毛细管在制备本发明所述的整体柱前,需要经过预处理,所述预处理可采用本领域的常规方法,即:石英毛细管依次用甲醇、水各冲洗0.5h,0.1mol/L盐酸冲洗1h,水冲洗至中性,1mol/L NaOH水溶液冲洗2h,纯水洗涤至中性后,再用甲醇冲洗0.5h,最后置于70℃气相色谱炉中用氮气吹干,用硅胶塞封口备用。
步骤(3)中,将反应混合液引入到预处理过的毛细管中,并使反应混合液占居的位置与预设固定相位置一致,根据现有技术存在不同的操作方法:(1)使用注射泵驱动注射器内的反应混合液,使之输出到毛细管;(2)将毛细管的一端插入反应混合液,用注射器从毛细管的另一端抽吸使反应混合液进入毛细管;(3)将毛细管的一端插入反应混合液,使反应混合液在毛细作用下进入毛细管。本发明适用于各种操作方法来制备毛细管电色谱整体柱的固定相。
步骤(3)中固化反应后,所述毛细管的后处理方法也是本领域的常规方法,通常为:反应结束后,用甲醇冲洗1~8h以除去未参与反应的单体(即苯乙烯)及有机致孔剂溶剂(即环己醇与甲苯的混合溶剂),再置于100℃气相色谱炉中用N2吹干,最后在预设检测窗口的位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,即得所述单壁碳纳米角修饰的毛细管电色谱整体柱。
一般情况下,所制备的电色谱整体柱的毛细管长度为35~175cm,预设固定相的长度为10~150cm,其起点为石英毛细管的一端(与进样阀连接的一端),终点接近检测窗口,预设的检测窗口在固定相后1~4mm处。
本发明的有益效果在于:首次将单壁碳纳米角应用于毛细管电色谱整体柱中,并且制备过程简单,步骤少,反应条件可控,制备效果更理想。
(四)附图说明
图1为单壁碳纳米角分散在苯乙烯中的TEM图;
图2为实施例1制备的毛细管电色谱整体柱的固定相扫描电镜图;
图3为实施例2制备的毛细管电色谱整体柱的固定相扫描电镜图;
图4为实施例3制备的毛细管电色谱整体柱的固定相扫描电镜图;
图5为实施例4中毛细管电色谱整体柱分离中性苯系物分离谱图;
图6为实施例5中毛细管电色谱整体柱分离碱性苯系物分离谱图;
图7为含单壁碳纳米角功能基团和不含单壁碳纳米角功能基团的毛细管电色谱整体柱分离中性苯系物的分离对比谱图。
(五)具体实施方式
下面通过具体实施例对本发明作进一步描述,但本发明的保护范围并不仅限于此。
以下实施例中使用的单壁碳纳米角购自:先丰纳米(江苏,南京)。
毛细管(100μm i.d.×365μm o.d.,河北永年锐沣色谱器件有限公司)预处理:
石英毛细管依次用甲醇,水各冲洗0.5h,0.1mol/L盐酸冲洗1h,水冲洗至中性,1mol/LNaOH水溶液冲洗2h,纯水洗涤至中性后,再用甲醇冲洗0.5h,于70℃气相色谱炉中用氮气吹干(通常吹扫4h),用硅胶塞封口,备用。
实施例1
单壁碳纳米角修饰的毛细管电色谱整体柱的制备
(1)称取15mg单壁碳纳米角至试管中,加入30mL苯乙烯,25KHz超声波处理2.5h使单壁碳纳米角均匀分散在苯乙烯中,得到单壁碳纳米角的苯乙烯分散液(图1是单壁碳纳米角的苯乙烯分散液的TEM图)。
(2)称取步骤(1)所得单壁碳纳米角的苯乙烯分散液(50μL,45.56mg)加入到450μL环己醇(432mg)中,25KHz超声2.5h直至分散均匀。再加入DVB(50μL,45.95mg)、甲苯(225μL,194.85mg)、AIBN(1.8mg)和AMPS(0.9mg),继续于25KHz超声分散35min,之后通入氮气15min,得到反应混合液。
(3)用注射器将步骤(2)所得反应混合液注入预处理好的45cm毛细管,控制液体注入长度为25cm(预设固定相的位置)。然后将毛细管两端用硅胶封口,置于70℃水浴中加热反应3h,反应结束后,用甲醇冲洗色谱柱4.5h以除去未参与反应的单体与有机致孔剂溶剂,再置于气相色谱炉中于100℃下用N2吹干(通常吹扫4h)。最后在设定检测窗口位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,得到所述单壁碳纳米角修饰的毛细管电色谱整体柱。图2为该整体柱固定相的扫描电镜图。
实施例2
单壁碳纳米角修饰的毛细管电色谱整体柱的制备
(1)称取15mg单壁碳纳米角至试管中,加入30mL苯乙烯,25KHz超声波处理2.5h使单壁碳纳米角均匀分散在苯乙烯中,得到单壁碳纳米角的苯乙烯分散液。
(2)称取步骤(1)所得单壁碳纳米角的苯乙烯分散液(50μL,45.56mg)加入到400μL环己醇(384mg)中,25KHz超声2.5h直至分散均匀。再加入DVB(100μL,91.9mg)、甲苯(200μL,173.2mg)、AIBN(2mg)和AMPS(1mg),继续于25KHz超声分散35min,之后通入氮气15min,得到反应混合液。
(3)用注射器将步骤(2)所得反应混合液注入预处理好的45cm毛细管,控制液体注入长度为25cm(预设固定相的位置)。然后将毛细管两端用硅胶封口,置于70℃水浴中加热反应4h,反应结束后,用甲醇冲洗色谱柱4.5h以除去未参与反应的单体与有机致孔剂溶剂,再置于气相色谱炉中于100℃下用N2吹干(通常吹扫4h)。最后在设定检测窗口位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,得到所述单壁碳纳米角修饰的毛细管电色谱整体柱。图3为该整体柱固定相的扫描电镜图。
实施例3
单壁碳纳米角修饰的毛细管电色谱整体柱的制备
(1)称取15mg单壁碳纳米角至试管中,加入30mL苯乙烯,25KHz超声波处理2.5h使单壁碳纳米角均匀分散在苯乙烯中,得到单壁碳纳米角的苯乙烯分散液。
(2)称取步骤(1)所得单壁碳纳米角的苯乙烯分散液(50μL,45.56mg)加入到300μL环己醇(288mg)中,25KHz超声2.5h直至分散均匀。再加入DVB(200μL,183.8mg)、甲苯(150μL,129.9mg)、AIBN(2.2mg)和AMPS(1.1mg),继续于25KHz超声分散35min,之后通入氮气15min,得到反应混合液。
(3)用注射器将步骤(2)所得反应混合液注入预处理好的45cm毛细管,控制液体注入长度为25cm(预设固定相的位置)。然后将毛细管两端用硅胶封口,置于70℃水浴中加热反应6h,反应结束后,用甲醇冲洗色谱柱4.5h以除去未参与反应的单体与有机致孔剂溶剂,再置于气相色谱炉中于100℃下用N2吹干(通常吹扫4h)。最后在设定检测窗口位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,得到所述单壁碳纳米角修饰的毛细管电色谱整体柱。图4为该整体柱固定相的扫描电镜图。
实施例4
取实施例2制备的毛细管电色谱整体柱,分离5种中性和1种碱性苯系物。
仪器与试剂:TriSepTM-2100加压电色谱仪(上海通微仪器公司,美国),PDA检测器;石英毛细管(100μm i.d.,375μm o.d.,河北永年)。硫脲(AR,上海化学试剂公司);苯胺;苯;甲苯;乙基苯;萘;联苯(纯度≥98%,上海百灵威化学试剂公司)。分别配成浓度为1mg/mL的乙腈溶液,然后等体积混合,进行测试。
加压电色谱条件:整体柱总长45cm,有效长度21cm,整体柱分离末端接高压,以5mmol/L pH 7.0的磷酸盐溶液与乙腈按体积比3:7混合配成运行缓冲溶液,采用六通进样阀进样,样品环体积为2μL,分离电压-15kV,分离温度25℃,压力流速为0.2mL/min,整体柱分离入口端背压为9.5MPa,硫脲为电渗流标记物,检测波长为254nm。
得到的分离谱图如附图5。
实施例5
取实施例2制备的毛细管电色谱整体柱,分离4种碱性苯系物。
仪器与试剂:TriSepTM-2100加压电色谱仪(上海通微仪器公司,美国),PDA检测器;石英毛细管(100μm i.d.,375μm o.d.,河北永年)。对苯二胺;苯胺;间硝基苯胺;邻硝基苯胺(纯度≥98%,上海百灵威化学试剂公司)。分别配成浓度为1mg/mL的乙腈溶液,然后等体积混合,进行测试。
加压电色谱条件:整体柱总长45cm,有效长度21cm,整体柱分离末端接高压,以5mmol/L pH 8.0的磷酸盐溶液与乙腈按体积比1:1混合配成运行缓冲溶液,采用六通进样阀进样,样品环体积为2μL,分离电压-15kV,分离温度25℃,压力流速为0.2mL/min,整体柱分离入口端背压为10.2MPa,检测波长为254nm。
得到的分离谱图如附图6。
对比例
不含单壁碳纳米角的毛细管电色谱整体柱(聚苯乙烯柱)的制备:
取0.4mL环己醇,加入苯乙烯(50μL)、DVB(100μL)、甲苯(200μL)、AIBN(2mg)和AMPS(1mg),于25KHz超声分散35min,之后通入氮气15min,得到反应混合液。用注射器将其注入预处理好的45cm毛细管,控制液体注入长度为25cm(预设固定相的位置)。然后将毛细管两端用硅胶封口,置于70℃水浴中加热反应4h,反应结束后,用甲醇冲洗色谱柱4.5h以除去未参与反应的单体与有机致孔剂溶剂,再置于气相色谱炉中于100℃下用N2吹干(通常吹扫4h)。最后在设定检测窗口位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,得到不含单壁碳纳米角的毛细管电色谱整体柱。
取实施例2制备的单壁碳纳米角修饰的毛细管电色谱整体柱和对比例制备的不含单壁碳纳米角的毛细管电色谱整体柱,分离5种中性和1种碱性苯系物。
仪器与试剂:TriSepTM-2100加压电色谱仪(上海通微仪器公司,美国),PDA检测器;石英毛细管(100μm i.d.,375μm o.d.,河北永年)。硫脲(AR,上海化学试剂公司);苯胺;苯;甲苯;乙基苯;萘;联苯(纯度≥98%,上海百灵威化学试剂公司)。分别配成浓度为1mg/mL的乙腈溶液,然后等体积混合,进行测试。
加压电色谱条件:整体柱总长45cm,有效长度21cm,整体柱分离末端接高压,以10mmol/L pH 7.0的磷酸盐溶液与乙腈按体积比1:4混合配成运行缓冲溶液,采用六通进样阀进样,样品环体积为2μL,分离电压-15kV,分离温度25℃,压力流速为0.1mL/min,整体柱分离入口端背压为9.6MPa,硫脲为电渗流标记物,检测波长为214nm。
得到的分离谱图如附图7。
Claims (7)
1.一种单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,所述的单壁碳纳米角修饰的毛细管电色谱整体柱按如下方法制备得到:
(1)将单壁碳纳米角与苯乙烯混合,于20~30KHz超声分散2~3h,得到单壁碳纳米角的苯乙烯分散液;
步骤(1)中,所述苯乙烯的体积用量以单壁碳纳米角的质量计为1~10mL/mg;
(2)将步骤(1)所得单壁碳纳米角的苯乙烯分散液与环己醇混合,于20~30KHz超声分散1~4h,再加入二乙烯苯、甲苯、自由基引发剂、2-丙烯酰胺基-2-甲基丙磺酸,继续于20~30KHz超声分散10~60min,之后通入氮气5~30min,得到反应混合液;
步骤(2)中,所述单壁碳纳米角的苯乙烯分散液与环己醇、二乙烯苯、甲苯、自由基引发剂、2-丙烯酰胺基-2-甲基丙磺酸的投料质量比为1:9.5~6.3:4.0~1.0:4.3~2.9:0.05~0.03:0.02;所述的自由基引发剂为偶氮二异丁腈、偶氮二异庚腈或过氧化苯甲酰;
(3)将步骤(2)所得反应混合液引入预处理过的毛细管内预设固定相的位置,然后将毛细管两端用硅胶封口,置于40~100℃下进行固化反应2~8h,之后毛细管经后处理,制得所述单壁碳纳米角修饰的毛细管电色谱整体柱。
2.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(1)中,所述苯乙烯的体积用量以单壁碳纳米角的质量计为2~5mL/mg。
3.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(1)中,所述苯乙烯的体积用量以单壁碳纳米角的质量计为2mL/mg。
4.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(2)中,所述单壁碳纳米角的苯乙烯分散液与环己醇、二乙烯苯、甲苯、自由基引发剂、2-丙烯酰胺基-2-甲基丙磺酸的投料质量比为1:8.4:2.0:3.8:0.04:0.02。
5.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(2)中,所述的自由基引发剂为偶氮二异丁腈。
6.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(3)中,所述预处理过的毛细管,是指毛细管在制备所述的整体柱前经过预处理,所述预处理的方法为:毛细管依次用甲醇、水各冲洗0.5h,0.1mol/L盐酸冲洗1h,水冲洗至中性,1mol/L NaOH水溶液冲洗2h,纯水洗涤至中性后,再用甲醇冲洗0.5h,最后置于70℃气相色谱炉中用氮气吹干,用硅胶塞封口备用。
7.如权利要求1所述的单壁碳纳米角修饰的毛细管电色谱整体柱,其特征在于,步骤(3)中固化反应后,所述毛细管的后处理方法为:反应结束后,用甲醇冲洗1~8h,再置于100℃气相色谱炉中用N2吹干,最后在预设检测窗口的位置烧去3mm柱长的表面聚酰亚胺涂层制备检测窗口,即得所述单壁碳纳米角修饰的毛细管电色谱整体柱。
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