CN112409228A - 一种手性硫氮共掺杂石墨烯量子点的制备方法 - Google Patents
一种手性硫氮共掺杂石墨烯量子点的制备方法 Download PDFInfo
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Abstract
本发明提供了一种手性硫氮共掺杂石墨烯量子点的制备方法，是以超纯水为溶剂，以氮掺杂石墨烯量子点和半胱氨酸为反应底物，以N‑羟基琥珀酰亚胺为脱水剂，以1‑(3‑二甲氨基丙基)‑3‑乙基碳二亚胺为交联剂，于常温下进行酰胺反应，反应完成后纯化，冷冻干燥，得到手性硫氮共掺杂石墨烯量子点。本发明采用氮掺杂石墨烯量子点和半胱氨酸作为原料，通过酰胺反应共价接枝，半胱氨酸上的氨基与石墨烯量子点边缘的羧基之间形成了共价键，得到手性硫氮共掺杂石墨烯量子点。该手性硫氮共掺杂石墨烯量子点尺寸均一，具有稳定的手性信号，且制备过程简单，条件温和，成本低，为制备手性碳纳米材料提供了新思路。
Description
技术领域
本发明涉及一种手性硫氮共掺杂石墨烯量子点的制备方法，尤其涉及一种通过酰胺反应共价接枝制备手性硫氮共掺杂石墨烯量子点的方法，属于纳米材料技术领域。
背景技术
近年来，手性这一话题引起了科学家的关注，在化学、材料、生命科学、生物等领域都呈现出它的优势。手性材料的制备和应用也成为了重要的研究课题，研究发现手性材料在手性识别、不对称催化及偏正光器件方面都具备很强的优势。
石墨烯量子点的制备是石墨烯纳米材料研究领域的重要课题，而不同的制备方法对石墨烯量子点的性能具有重要的影响，如晶粒的尺寸、晶粒的形貌、元素含量及表面微结构等方面都会影响量子点的物理性质和用途。正如我们所熟知的，手性关乎生命，碳又是生命体中含量最多的元素之一。将氧化石墨烯或者石墨烯量子进行修饰使其具有手性特征，会使石墨烯量子点具有更广阔的应用空间，而且还可以巧妙的将化学和生命科学连接在一起。尽管研究者在石墨烯量子点的制备、特性及应用方面已经做出了很大的突破且取得了一定成就，但是对于将氧化石墨烯及石墨烯量子点修饰为手性碳纳米材料的研究很少。
发明内容
本发明的目的是提供一种手性硫氮共掺杂石墨烯量子点制备方法，该手性硫氮共掺杂石墨烯量子点是通过酰胺反应将手性半胱氨酸共价接枝到石墨烯量子点边缘形成的。
一、手性硫氮共掺杂石墨烯量子点的制备
本发明中手性硫氮共掺杂石墨烯量子点的制备方法，是以超纯水为溶剂，以氮掺杂石墨烯量子点（NGQDs）和半胱氨酸为反应底物，以N-羟基琥珀酰亚胺（NHS）为脱水剂，以1-(3-二甲氨基丙基)-3-乙基碳二亚胺（EDC）为交联剂，于常温下进行酰胺反应，反应完成后纯化，冷冻干燥，得到手性硫氮共掺杂石墨烯量子点。其中，所述半胱氨酸为L-半胱氨酸或D-半胱氨酸；所述氮掺杂石墨烯量子点和半胱氨酸的质量比为1:1~1:2；所述半胱氨酸、N-羟基琥珀酰亚胺和1-(3-二甲氨基丙基)-3-乙基碳二亚胺的摩尔比为1:1:1~1:2:2；所述酰胺反应时间为20~24 h；所述纯化是将反应液旋转蒸发浓缩后，加入到截留分子量为500~1000Da的透析袋中透析除去未反应的半胱氨酸；冷冻干燥是在-45~-50 ℃冷冻干燥48 h。以L-半胱氨酸制备的手性硫氮共掺杂石墨烯量子点标记为L-SNGQDs，以D-半胱氨酸制备的手性硫氮共掺杂石墨烯量子点标记为D-SNGQDs。
所述氮掺杂石墨烯量子点的制备方法，是将网络状还原氧化石墨烯分散于浓硝酸中，磁力搅拌下油浴加热至140~160 ℃，循环水冷凝下恒温反应12~48 h；去掉循环冷凝水，继续恒温蒸发1~2 h，冷却至室温；然后加入超纯水超声分散10~15 min；过滤，滤液旋转蒸发浓 缩至原体积的1/9~1/10，装入3000~8000Da透析袋中透析24~48 h；透析液再次旋转蒸发浓缩，在-50~-60 ℃下真空冷冻干燥10~12 h，得到稳定的氮掺杂石墨烯量子点。其中，网络状还原氧 化石墨烯为含氮量丰富网络状还原氧化石墨烯；浓硝酸的质量浓度为63~68%。
二、手性硫氮共掺杂石墨烯量子点的结构及手性特征
下面通过透射电镜、红外光谱图，紫外可见吸收光谱和圆二色谱对本发明制备的手性硫氮共掺杂石墨烯量子点的结构和手性特征进行分析说明。
1、透射电镜分析
图1（a）和（b）为L-SNGQDs在不同放大倍数下的TEM图像，从图中可以看到手性硫氮共掺杂石墨烯量子点的尺寸约为10 nm，且出现了不同程度的团聚。
2、红外分析
图2（a）是L-SNGQDs、NGQDs和L-Cys的傅里叶变换红外光谱图。图2（b）是D-SNGQDs、NGQDs和D-Cys的傅里叶变换红外光谱图。从图中可以看到Cys在3420 cm-1 和3000 cm-1 处出现的两组峰分别对应N-H和O-H键的伸缩振动峰，在1585 cm-1处的峰为C=O的伸缩振动峰，而C－O键的伸缩振动峰在1390 cm-1处，1540 cm-1处的峰为伯胺（-NH2）的面内变形振动峰。与Cys不同的是，在NGQDs的红外光谱图中，在1720 cm-1处的峰为C=O的伸缩振动峰，而C－O键的伸缩振动峰在1385 cm-1处。用Cys修饰NGQDs之后形成的L-SNGQDs和D-SNGQDs在3420cm-1 和3000 cm-1 处出现的两组峰跟Cys、NGQDs相对应，归属于N－H和O－H键的伸缩振动峰；与半胱氨酸相比，L-SNGQDs和D-SNGQDs的C=O的伸缩振动峰发生了蓝移，出现在1700cm-1处，这是由于氮掺杂石墨烯量子点和半胱氨酸之间的相互作用的结果。基于以上结果，可以说明半胱氨酸成功地接枝到了NGQDs上，生成了手性硫氮共掺杂石墨烯量子点。
3、紫外可见吸收光谱图
图3是NGQDs和L-SNGQDs的紫外可见光谱图，图中290 nm处的吸收峰主要来自于含氧基团和sp2杂化原子的非键合电子的n→π*跃迁，而220~230 nm处最大吸收峰归因于手性硫氮共掺杂石墨烯量子点结构中多芳族体系（即C=C键）中的π→π*跃迁。
4、圆二色光谱图
图4为L-SNGQDs 和D-SNGQDs的圆二色光谱图，可以看到在210 nm~220 nm 处两者出现了完全相反的信号峰，表示其对映异构体性质，根据文献报道我们知道该处相反的信号峰来自于L-半胱氨酸或D-半胱氨酸，说明半胱氨酸共价接枝到氮掺杂石墨烯量子点之后，其手性中心保留了下来，形成我们所说的手性硫氮共掺杂石墨烯量子点。在图4中我们还发现除了保留半胱氨酸的手性信号外，在250 nm处出现一组新的信号峰，这说明L-SNGQDs 和D-SNGQDs通过手性继承和转移在其结构内诱导产生了新的手性中心。
综上所述，本发明对现有技术具有以下优点：本发明采用氮掺杂石墨烯量子点和半胱氨酸作为原料，通过酰胺反应共价接枝，半胱氨酸上的氨基与石墨烯量子点边缘的羧基之间形成了共价键，得到手性硫氮共掺杂石墨烯量子点。该手性硫氮共掺杂石墨烯量子点尺寸均一，具有稳定的手性信号，且制备过程简单，没有复杂的钝化处理和杂元素掺杂过程，条件温和，成本低，为制备手性碳纳米材料提供了新思路。
附图说明
图1为本发明制备的手性硫氮共掺杂石墨烯量子点的透射电镜图；
图2为本发明制备的手性硫氮共掺杂石墨烯量子点的红外光谱图；
图3为本发明制备的手性硫氮共掺杂石墨烯量子点的的紫外可见吸收光谱图；
图4为本发明制备的手性硫氮共掺杂石墨烯量子点的圆二色光谱图。
具体实施方式
实施例1
（1）氮掺杂石墨烯量子点的制备：取0.1 g网络状还原氧化石墨烯，分散于100 mL质量百分数 65%的浓硝酸中，磁力搅拌，油浴加热至150 ℃同时循环水冷凝，恒温反应12h；然后去掉冷凝水，继续恒温蒸发2 h；冷却至室温，然后加入超纯水超声分散15 min；过滤，滤液旋转蒸发浓缩至10 mL，装入3000Da透析袋中透析2天；所得透析液再次旋转蒸发浓缩，得到高浓度的氮掺杂石墨烯量子点；最后在-50~-60 ℃下真空冷冻干燥10 h，得到褐色氮掺杂石墨烯量子点NGQDs。
（2）手性硫氮共掺杂石墨烯量子点的制备：将50 mg NGQDs溶于50 mL超纯水中形成1 mg mL-1的均匀分散液；将3 mL EDC（6 mM）溶液添加到上述NGQDs溶液中，搅拌10分钟后，将NHS（6 mM）添加到混合溶液中，再搅拌30 min。最后，将3 mL L-半胱氨酸（6 mM）添加上述溶液中，并将该混合溶液常温下搅拌24 h。将反应液旋转蒸发浓缩后，加入到截留分子量为500~1000Da的透析袋中除去未反应的L-半胱氨酸，在-45~-50 ℃冷冻干燥48 h，获得最终产物L-SNGQDs。
实施例2
（1）氮掺杂石墨烯量子点的制备：同实施例1；
（2）手性硫氮共掺杂石墨烯量子点的制备：将50 mg NGQDs溶于50 mL超纯水中形成1mg mL-1的均匀分散液；将3 mL EDC（6 mM）溶液添加到上述NGQDs溶液中，搅拌10分钟后，将NHS（6 mM）添加到混合溶液中，再搅拌30 min。最后，将3 mL D-半胱氨酸（6 mM）添加上述溶液中，并将该混合溶液常温下搅拌24 h。将反应液旋转蒸发浓缩后，加入到截留分子量为500~1000Da的透析袋中除去未反应的D-半胱氨酸，在-45~-50 ℃冷冻干燥48 h，获得最终产物D-SNGQDs。
Claims (7)
1.一种手性硫氮共掺杂石墨烯量子点的制备方法，是以超纯水为溶剂，以氮掺杂石墨烯量子点和半胱氨酸为反应底物，以N-羟基琥珀酰亚胺为脱水剂，以1-(3-二甲氨基丙基)-3-乙基碳二亚胺为交联剂，于常温下进行酰胺反应，反应完成后纯化，冷冻干燥，得到手性硫氮共掺杂石墨烯量子点。
2.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述半胱氨酸为L-半胱氨酸或D-半胱氨酸。
3.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述氮掺杂石墨烯量子点和半胱氨酸的质量比为1:1~1:2。
4.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述半胱氨酸、N-羟基琥珀酰亚胺和1-(3-二甲氨基丙基)-3-乙基碳二亚胺的摩尔比为1:1:1~1:2:2。
5.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述酰胺反应时间为20~24 h。
6.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述纯化是将反应液旋转蒸发浓缩后，加入到截留分子量为500~1000Da的透析袋中透析除去未反应的半胱氨酸。
7.如权利要求1所述手性硫氮共掺杂石墨烯量子点的制备方法，其特征在于：所述冷冻干燥是在-45~-50 ℃冷冻干燥48 h。
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