CN108562561B - 一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液及其制备方法 - Google Patents

一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液及其制备方法 Download PDF

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CN108562561B
CN108562561B CN201810190269.9A CN201810190269A CN108562561B CN 108562561 B CN108562561 B CN 108562561B CN 201810190269 A CN201810190269 A CN 201810190269A CN 108562561 B CN108562561 B CN 108562561B
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熊华玉
王升富
张修华
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Abstract

本发明涉及一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液及其制备方法，其中制备方法包括如下步骤:S1.将多巴胺溶解于水中得多巴胺水溶液；S2.向多巴胺水溶液中加入铝盐水溶液和双氧水并充分混合得反应液；S3.反应液于室温下反应5‑8h，然后装入截留分子量为100‑500Da的透析袋中，透析36‑48h，即得。有益效果是：加入铝离子后，只需要使用双氧水一步氧化即可得到具有荧光特性的聚多巴胺纳米粒子，制备方法相对更简单；该有机荧光聚多巴胺纳米粒子溶液对Fe2+和Fe3+有显著的荧光效应且在一定范围内待测离子浓度增加与溶液荧光强度增加有正相关性，可用于检测溶液中的Fe2+和Fe3+。

Description

一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒 子溶液及其制备方法
技术领域
本发明属于化学及生物科学技术领域，具体涉及一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液及其制备方法。
背景技术
有机荧光纳米材料在生物降解、生物兼容性和光稳定性等方面具有突出的优势。多巴胺是一种神经传导物质，用来帮助细胞传送脉冲的化学物质，在人体内广泛存在。多巴胺是一种在氧气条件下很容易发生自聚的小分子，用它来制备有机荧光纳米材料是一种很具吸引力及应用前景的材料。
目前为止，关于荧光聚多巴胺纳米材料的合成相关的报道还比较少。所报道的文献中一般是采用两步法进行合成。第一步：多巴胺在碱性条件下被水中的氧气氧化成大的聚多巴胺纳米粒子；第二步：加入大量的H2O2，将大的聚多巴胺纳米粒子蚀刻成小的具有荧光性能的荧光聚多巴胺纳米粒子[X.Zhang,S.Wang,L.Xu,L.Feng,Y.Ji,L.Tao,S.Li andY.Wei,Nanoscale,2012,4,5581-5584]。其不足之处在于，以氧气对多巴胺进行氧化聚合时聚合程度很难控制，故现有技术中所合成的荧光聚多巴胺纳米材料均是由不同聚合程度组成的混合物[A.Yildirim and M.Bayindir,Anal.Chem.,2014,86,5508-5512..J.-H.Lin,C.-J.Yu,Y.-C.Yang and W.-L.Tseng,Phys.Chem.Chem.Phys.,2015,17,15124-15130]。
发明内容
本发明提供一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液及其制备方法，旨在提供一种制备有机荧光聚多巴胺纳米粒子溶液的新方法并拓展其应用。
本发明解决上述技术问题的技术方案如下：一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其包括如下步骤:
S1.将多巴胺溶解于水中得多巴胺水溶液；
S2.向多巴胺水溶液中加入铝盐水溶液和双氧水并充分混合得反应液，反应液中多巴胺、Al3+和H2O2的物质的量之比为2：0.005-0.02：0.5-1.2；
S3.反应液于室温下反应5-8h，然后装入截留分子量为100-500Da的透析袋中，透析36-48h，即得。
在上述技术方案的基础上，本发明还可以做如下进一步的具体选择或最佳选择。
具体的，S1中多巴胺水溶液的浓度为10-50mM。
具体的，S2中铝盐水溶液的浓度为5-20mM。
具体的，S2中的铝盐为氯化铝或硫酸铝。
具体的，S2中的双氧水的浓度为0.5-1.5M。
最佳的，S2的反应液中多巴胺、Al3+和H2O2的物质的量之比为2：0.01：1。
此外，本发明还提供了一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液，其通过上述方法制备得到。
与现有技术相比，本发明的有益效果是：
在多巴胺水溶液中加入铝离子后，只需要使用适量的双氧水一步氧化即可得到具有荧光特性的聚多巴胺纳米粒子，制备方法相对更简单；本发明制备的有机荧光聚多巴胺纳米粒子溶液对Fe2+和Fe3+有显著的荧光效应且在Fe2+和Fe3+的浓度较低时浓度增加与荧光强度增加有较好的正相关性，可用于检测溶液中的Fe2+和Fe3+。
附图说明
图1为本发明实施例1中用到的原料及制得的聚多巴胺纳米粒子溶液的激发图和发射图，其中a为聚多巴胺纳米粒子溶液的激发图(Ex.＝342nm)、b为聚多巴胺纳米粒子溶液的发射图(Em.＝453nm)、c为原料多巴胺水溶液和铝盐水溶液混合且室温静置6h后在342nm激发下的发射图，d为原料多巴胺水溶液和双氧水混合且室温静置6h后在342nm激发下的的发射图；
图2为本发明实施例1得到的聚多巴胺纳米粒子溶液的透射电镜图；
图3为本发明实施例1得到的聚多巴胺纳米粒子溶液的对不同金属离子的荧光响应情况；
图4为本发明实施例1得到的聚多巴胺纳米粒子溶液作为荧光探针测定Fe3+时，荧光强度与Fe3+浓度的变化关系；
图5为本发明实施例1得到的聚多巴胺纳米粒子溶液作为荧光探针测定Fe2+时，荧光强度与Fe2+浓度的变化关系；
具体实施方式
以下结合附图及具体实施例对本发明提供的技术方案作进一步的详细描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
以下实施例中用到的药品若无特别说明则均为市售产品，用到的方法若无特别说明则均为本领域技术人员使用的常规方法。
实施例1
一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液，其通过如下步骤制备得到：
S1.将多巴胺溶解于水中得多巴胺水溶液，多巴胺水溶液的浓度为0.005g/mL，也即32mM；
S2.向600μL多巴胺水溶液中加入10μL浓度为10mM的氯化铝水溶液和10μL浓度为1M的双氧水并充分混合得反应液，反应液中多巴胺、Al3+和H2O2的物质的量之比约为2：0.01：1；
S3.反应液于室温下反应6h，然后装入截留分子量为100-500Da的透析袋中，透析40h，即得。
实施例2
一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液，其通过如下步骤制备得到：
S1.将多巴胺溶解于水中得多巴胺水溶液，多巴胺水溶液的浓度为10mM；
S2.向2000μL多巴胺水溶液中加入10μL浓度为20mM的氯化铝水溶液和10μL浓度为1.2M的双氧水并充分混合得反应液，反应液中多巴胺、Al3+和H2O2的物质的量之比约为2：0.02：1.2；
S3.反应液于室温下反应8h，然后装入截留分子量为100-500Da的透析袋中，透析36h，即得。
实施例3
一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液，其通过如下步骤制备得到：
S1.将多巴胺溶解于水中得多巴胺水溶液，多巴胺水溶液的浓度为50mM；
S2.向400μL多巴胺水溶液中加入10μL浓度为5mM的氯化铝水溶液和10μL浓度为0.5M的双氧水并充分混合得反应液，反应液中多巴胺、Al3+和H2O2的物质的量之比约为2：0.005：0.5；
S3.反应液于室温下反应5h，然后装入截留分子量为100-500Da的透析袋中，透析48h，即得。
分别以实施例1至3制得的可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液为测试样品，经检测各样品均具有明显的荧光效应并且能够用于对溶液中亚铁及铁离子进行检测。以实施例1制得的有机荧光聚多巴胺纳米粒子溶液为代表，测试了其荧光效应如图1所示，从图1中可知本发明成功合成了聚多巴胺纳米粒子且其具有荧光效应(a和b有明显的激发峰和发射峰，作为对比的c和d无发射峰)；从图2可知，本发明实施例1制备的聚多巴胺纳米粒子样品具有纳米尺寸且其尺寸相对比较均一；从图3可知，本发明实施例1制备的聚多巴胺纳米粒子溶液对亚铁及铁离子具有明显强于其他金属离子的荧光效应，故其可用于检测亚铁和铁离子；从图4和图5可知，当亚铁及铁离子的浓度相对较低时，检测时聚多巴胺纳米粒子溶液的荧光强度随相应的检测离子的浓度增加而增强，相关性较好，即其不仅可以对亚铁及铁离子进行定性检测而且还可以进行定量检测。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，包括如下步骤:
S1.将多巴胺溶解于水中得多巴胺水溶液；
S2.向多巴胺水溶液中加入铝盐水溶液和双氧水并充分混合得反应液，反应液中多巴胺、Al3+和H2O2的物质的量之比为2：0.005-0.02：0.5-1.2；
S3.反应液于室温下反应5-8h，然后装入截留分子量为100-500Da的透析袋中，透析36-48h，即得。
2.根据权利要求1所述的一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，S1中多巴胺水溶液的浓度为10-50mM。
3.根据权利要求1所述的一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，S2中铝盐水溶液的浓度为5-20mM。
4.根据权利要求1所述的一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，S2中的铝盐为氯化铝或硫酸铝。
5.根据权利要求1所述的一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，S2中的双氧水的浓度为0.5-1.5M。
6.根据权利要求1所述的一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液的制备方法，其特征在于，S2的反应液中多巴胺、Al3+和H2O2的物质的量之比为2：0.01：1。
7.一种可选择性识别亚铁及铁离子的有机荧光聚多巴胺纳米粒子溶液，其特征在于，通过如权利要求1至6任一项所述的方法制备得到。
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