CN112960666B - 叠氮官能化碳纳米管的制备方法 - Google Patents
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Abstract
本发明属于生物化学材料技术领域,具体涉及一种叠氮官能化碳纳米管的制备方法。本发明基于碳纳米管的结构特性,通过SWNTs‑COOH的制备和活化、SWNTs‑N3的制备,逐步制备出叠氮官能化的碳纳米管,从而应用于复合物的制备以及作为荧光传感器中的优良淬灭剂实现对有关靶标的检测,从而应用于临床、医药等领域。
Description
技术领域
本发明属于生物化学材料技术领域,具体涉及一种叠氮官能化碳纳米管的制备方法。
背景技术:
纳米材料和生物分子的结合在生物传感器领域发挥着越来越重要的作用,碳纳米管作为一种新型的纳米材料由于其具有独特的光电性能和机械性能而得到广泛研究及应用。碳纳米管是由一层或多层石墨烯薄片制成的中空石墨纳米管,通常分为单壁碳纳米管(single-walled carbon nanotubes,SWNTs)和多壁碳纳米管(multi-walled carbonnanotubes,MWNTs)两种类型。SWNTs相对于MWNTs来说,仅由一层石墨烯薄片制备而成,因此更具有优良的性能,比如超轻的重量、高的热稳定性和机械性能、大的表面积比以及易于表面官能化等,因此常常被用构建纳米生物传感器。此外,经研究表明SWNTs在荧光适体传感器中可通过充当FRET的能量受体而被认为是优良的淬灭剂。因此,基于SWNTs对适体DNA的独特吸附能力以及比较宽泛的能量传递范围的特性,该纳米材料在DNA分析以及蛋白质测定方面具有一定的研究意义和实践应用价值。
发明内容
叠氮官能化单壁碳纳米管的制备方法,包括如下步骤:
(1)SWNTs-COOH的制备:
将碳纳米管SWNTs超声分散,制得SWNTs溶液;
在SWNTs溶液中,依次加入NaOH和氯乙酸超声,将SWNTs表面的-OH官能团转化为–COOH官能团;然后用NaOH中和掉未反应的氯乙酸,离心纯化,冷冻干燥,羧基官能化的SWNTs,即SWNTs-COOH;
(2)活化SWNTs-COOH;
将步骤(1)制备的SWNTs-COOH固体溶于超纯水中,超声分散均匀,得到SWNTs-COOH溶液,然后加入含NHS和EDC的溶液,室温下温育,离心,得到活化的SWNTs-COOH;
(3)SWNTs-N3的制备:
将步骤(2)制得的活化SWNTs-COOH溶于甲醇溶液中,超声分散得SWNTs-COOH的甲醇溶液,然后与N3-PEG-NH2一起加入到HEPES缓冲溶液中充分混合,室温下反应发生共价结合作用,离心,冷冻干燥,得到叠氮官能化的碳纳米管。
步骤(1)中,SWNTs溶液、NaOH和氯乙酸的用量比例为5mL:0.6g:0.5g;其中,SWNTs溶液的浓度为2mg/mL;超声时间为2h。
步骤(2)中,SWNTs-COOH溶液、含NHS和EDC的溶液的体积比为1:1,其中,SWNTs-COOH溶液的浓度为4mg/mL;含NHS和EDC的溶液中,NHS的浓度为50mM,EDC的浓度为200mM。
步骤(2)中,室温下温育的时间为12h。
步骤(3)中,SWNTs-COOH的甲醇溶液、N3-PEG-NH2和HEPES缓冲溶液的用量比为5mL:100mg:10mL,其中,SWNTs-COOH的甲醇溶液浓度为2mg/mL,N3-PEG-NH2的聚合度为6,HEPES缓冲溶液的浓度为0.1M,pH为7.4。
步骤(3)中,甲醇溶液中,甲醇的体积百分数为10%,超声时间为3h;室温下反应时间为12h。
本发明具有以下优点:
(1)本发明过程中所需如氯乙酸、氢氧化钠等试剂是实验室容易获得的常备试剂,比较容易获得。
(2)本发明通过羧基官能团与氨基官能团之间的共价结合作用获得叠氮官能化的碳纳米管,二者结合所需要的剂量较少,是一种实现高效合成该纳米材料的方法。
(3)本发明制备所得的纳米材料与典型的荧光淬灭剂氧化石墨烯(GrapheneOxide)相似,同样能够广泛的应用于荧光生物传感器领域,实现对待测物的灵敏性检测。
附图说明
图1为官能化的碳纳米管的FT-IR光谱图。
具体实施方式
以下结合实施例对本发明做进一步说明,实施例是用于说明本发明,而不是用于限制本发明的范围。
实施例1:
(1)SWNTs-COOH的制备:
使用超声清洗机将SWNTs分散均匀并配制成在2mg/mL的溶液。
在5mL初始的SWNTs溶液中,分别加入0.6g NaOH和0.5g氯乙酸并水浴超声2h,能够将SWNTs表面的-OH转化为–COOH,然后NaOH中和并通过多次冲洗和离心进一步纯化,将溶液通过冷冻真空干燥机中干燥得到羧基官能化的SWNTs,即SWNTs-COOH;
(2)活化SWNTs-COOH;
称取一定量的SWNTs-COOH固体溶于超纯水中,配制成浓度为4mg/mL的溶液,并超声使其分散均匀。
2mL含NHS(50mM)和EDC(200mM)的溶液中加入2mL的SWNTs-COOH(4mg/mL),室温下温育12h,经离心活化羧基官能团,冻干得到固体,即活化的SWNTs-COOH。
(3)SWNTs-N3的制备:
将活化的羧基官能化单壁碳纳米管溶解于10%的甲醇溶液中超声3h左右,然后将5mL SWNTs-COOH(2mg/mL)和100mg N3-PEG-NH2加入到10mL HEPES缓冲溶液(0.1M,pH 7.4)中并充分混合,室温下反应12h,通过-COOH和-NH2的共价结合形成叠氮官能化单壁碳纳米管(SWNTs-N3)。通过离心(12000rpm,30min)除去过量的N3-PEG-NH2等游离分子,然后用冷冻真空干燥机进行干燥后称取一定量SWNTs-N3固体。
图1为官能化的碳纳米管的FT-IR光谱。从图1我们可以明显的观察到未经修饰的SWNTs具有4个具有代表性的特征峰,分别是3438、2925、2852和1633cm-1处的峰值,分别对应于-OH拉伸振动、C-H不对称拉伸振动、C-H对称拉伸振动和C-OH拉伸振动。相对于SWNTs,1633cm-1处的峰值移动到1617cm-1处标志着羧基官能化的单壁碳纳米管(SWNTs-COOH)的成功合成。在SWNTs-COOH的基础上,2104cm-1处的峰值标志着叠氮官能团(-N3)的成功合成,与SWNTs相比,两者在1633cm-1处的峰值几乎未发生明显变化。从整体的FT-IR光谱上我们可以观察到初始的SWNTs、羧化以及叠氮化的SWNTs三者的基本结构并未发生明显的变化。
Claims (6)
1.叠氮官能化碳纳米管的制备方法,其特征在于,包括如下步骤:
(1)SWNTs-COOH的制备:
将碳纳米管SWNTs超声分散,制得SWNTs溶液;
在SWNTs溶液中,依次加入NaOH和氯乙酸超声,将SWNTs表面的-OH官能团转化为–COOH官能团;然后用NaOH中和掉未反应的氯乙酸,离心纯化,冷冻干燥,羧基官能化的SWNTs,即SWNTs-COOH;
(2)活化SWNTs-COOH;
将步骤(1)制备的SWNTs-COOH固体溶于超纯水中,超声分散均匀,得到SWNTs-COOH溶液,然后加入含NHS和EDC的溶液,室温下温育,离心,得到活化的SWNTs-COOH;
(3)SWNTs-N3的制备:
将步骤(2)制得的活化SWNTs-COOH溶于甲醇溶液中,超声分散得SWNTs-COOH的甲醇溶液,然后与N3-PEG-NH2一起加入到HEPES缓冲溶液中充分混合,室温下反应发生共价结合作用,离心,冷冻干燥,得到叠氮官能化的碳纳米管。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,SWNTs溶液、NaOH和氯乙酸的用量比例为5mL:0.6g:0.5g;其中,SWNTs溶液的浓度为2mg/mL;超声时间为2h。
3.如权利要求1所述的制备方法,其特征在于,步骤(2)中,SWNTs-COOH溶液、含NHS和EDC的溶液的体积比为1:1,其中,SWNTs-COOH溶液的浓度为4mg/mL;含NHS和EDC的溶液中,NHS的浓度为50mM,EDC的浓度为200mM。
4.如权利要求1所述的制备方法,其特征在于,步骤(2)中,室温下温育的时间为12h。
5.如权利要求1所述的制备方法,其特征在于,步骤(3)中,SWNTs-COOH的甲醇溶液、N3-PEG-NH2和HEPES缓冲溶液的用量比为5mL:100mg:10mL,其中,SWNTs-COOH的甲醇溶液浓度为2mg/mL,N3-PEG-NH2的聚合度为6,HEPES缓冲溶液的浓度为0.1M,pH为7.4。
6.如权利要求1所述的制备方法,其特征在于,步骤(3)中,甲醇溶液中,甲醇的体积百分数为10%,超声时间为3h;室温下反应时间为12h。
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