CN113185965A - 用于水溶液氟离子检测的铽有机复合纳米探针的制备方法 - Google Patents
用于水溶液氟离子检测的铽有机复合纳米探针的制备方法 Download PDFInfo
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Abstract
本发明公开了用于水溶液氟离子检测的铽有机复合纳米探针的制备方法，包括以冠状铽镓双阳离子配合物为检测信号源；将冠状铽镓双阳离子配合物与嵌段共聚物F127混合自组装制备铽有机复合纳米探针。其制备方法具体包括如下步骤：S1将铽离子、镓离子、水杨羟肟酸和苯甲酸钠在甲醇中混合配位制成冠状铽镓双阳离子配合物。S2将步骤S1制得的冠状铽镓双阳离子配合物甲醇溶液与嵌段共聚物F127混合，在室温下搅拌得到澄清透明混合溶液。S3将步骤S2混合溶液注入去离子水，发生快速纳米自组装反应，便可得到铽有机复合纳米发光探针。通过本发明获得的铽有机复合纳米发光材料尺寸均一，发光强度高，无聚集和沉淀现象，能够在水溶液中实现氟离子快速检测，响应范围达到0.19 ppm~18.81 ppm。
Description
技术领域
本发明属于水溶液氟离子检测技术邻域，具体涉及一种用于水溶液氟离子检测的铽有机复合纳米探针的制备方法。
背景技术
一个正常成年人身体中约含有2.6g的氟元素，人体每日通过饮食和饮用水摄入少量的氟。然而，每日摄入量一旦超过4 mg便可能引起人体中毒，过量的氟离子是造成神经毒性的重要因素。因此，开发能够在水溶液中快速检测氟离子的技术成为当前迫切需求。
稀土铽离子具有发光半宽峰窄、寿命长、耐漂白能力强等优异的光学特征，在生物检测成像、太阳能转化、照明显示和通讯领域具有潜在的应用价值。但是铽离子因为拉波特定则消光能力弱、荧光量子效率低导致发光信号弱。
因此，本发明专利利用嵌段共聚物自组装制备铽有机复合纳米探针，提高铽离子发光信号强度和环境稳定性，将其作为荧光探针应用于水溶液氟离子检测，具有可靠性高、成本低和灵敏度高等特点。
发明内容
本发明的目的是提供一种用于水溶液氟离子检测的铽有机复合纳米探针的制备，可以解决上述技术问题中的一个或者多个。
为了达到上述目的，本发明提出的技术方案如下：
用于水溶液氟离子检测的铽有机复合纳米探针的制备，其特征在于，具体包含如下步骤：以冠状铽镓双阳离子配合物为检测信号源，将冠状铽镓双阳离子配合物与嵌段共聚物F127（泊洛沙姆）混合自组装制备铽有机复合纳米探针，利用嵌段共聚物快速纳米沉淀法获得复合纳米结构。
用于水溶液氟离子检测的铽有机复合纳米探针的制备，其特征在于，具体包括如下步骤：
S1配制冠状铽镓双阳离子配合物的甲醇溶液：五水硝酸铽、水杨羟肟酸、硝酸镓水合物、苯甲酸钠、甲醇和吡啶按照物质的量比0.25：1：1：3：980：25混合，搅拌12小时，过滤除去白色粉末，将滤液密封保存备用。
S2将步骤S1的滤液与嵌段共聚物F127按照体积比0.2～4：1混合，搅拌6～24小时。
S3将步骤S2的混合溶液缓慢注入去离子水，混合溶液与去离子水的体积比为1：10～20。
S4在步骤S3结束后按照总体积的3～10%添加自组装促进剂，得到用于水溶液氟离子检测的铽有机复合纳米探针。
优选的，步骤（4）中的自组装促进剂为具有非极性特征的溶剂包括：油酸、油胺、三正辛基膦、三正辛基氧化膦、环己烷、正己烷、石油醚。
本发明的技术效果是：
本发明中的用于水溶液氟离子检测的铽有机复合纳米探针固体或水分散液，在250～400 nm紫外光的激发下，产生中心波长为489～492、544～547、584～587、620～623nm的发光峰。铽有机复合纳米探针的水分散液中加入不同浓度的氟离子，发光强度信号发生不同程度地变化。该探针具有可靠性高、成本低和灵敏度高等特点。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
在附图中：
图1：铽有机复合纳米探针透射电子显微镜照片；
图2：Tb3+、Ga3+、水杨羟肟酸和苯甲酸组成的冠状铽镓双阳离子配合物的X射线衍射谱；
图3：室温下，铽有机复合纳米探针分散液的荧光发射光谱，溶剂为去离子水；
图4：Tb3+、Ga3+、水杨羟肟酸和苯甲酸组成的冠状铽镓双阳离子配合物在360 nm紫外灯下的发光照片；
图5：在加入不同浓度氟离子的情况下，稀土有机复合纳米探针分散液的荧光发射光谱；
图6：氟离子浓度与稀土有机复合纳米探针发光强度的关系，其中x为负离子浓度，y为发光强度。
具体实施方式
下面将结合附图以及具体实施例来详细说明本发明，其中的示意性实施例以及说明仅用来解释本发明，但并不作为对本发明的不当限定。
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
一种用于水溶液氟离子检测的铽有机复合纳米探针的制备，具体包含如下步骤：以冠状铽镓双阳离子配合物为检测信号源，将冠状铽镓双阳离子配合物与嵌段共聚物F127混合自组装制备铽有机复合纳米探针，利用嵌段共聚物快速纳米沉淀法获得复合纳米结构。铽有机复合纳米探针的水分散液中加入不同浓度的氟离子，发光强度信号发生不同程度地变化。
具体步骤如下：
S1配制冠状铽镓双阳离子配合物的甲醇溶液：五水硝酸铽、水杨羟肟酸、硝酸镓水合物、苯甲酸钠、甲醇和吡啶按照物质的量比0.25：1：1：3：980：25混合，搅拌12小时，过滤除去白色粉末，将滤液密封保存备用。
具体的是：将水杨羟肟酸（0.1531 g，1.0 mmol），Tb(NO3)3·5H2O (0.25 mmol，435.02 g/mol，0.10876 g)，Ga(NO3)3·xH2O（0.2557 g，1.0 mmol）溶于40 mL甲醇，加入苯甲酸钠（0.4323g，3 mmol），搅拌过夜，加入2 mL吡啶过滤除去白色粉末，将滤液密封保存备用。
S2将步骤S1的滤液与嵌段共聚物F127按照体积比0.2～4：1混合，搅拌6～24小时。
具体的是：取2 mL步骤S1的滤液，持续搅拌下加入2 mL嵌段共聚物F127，搅拌过夜。
S3将步骤S2的混合溶液缓慢注入去离子水，混合溶液与去离子水的体积比为1：10～20。
具体的是：将步骤S2的混合溶液缓慢注入15 mL去离子水。
S4在步骤S3结束后按照总体积的3～10%添加自组装促进剂，得到用于水溶液氟离子检测的铽有机复合纳米探针。
具体的是：步骤S3结束后，加入0.5 mL环己烷等非极性溶液促进自组装。
按上述方法制得的铽有机复合纳米探针，如图1透射电子显微镜照片显示，自组装获得的材料具有纳米结构，直径尺寸为60 nm，由更小的颗粒组装拼接而成。
如图2是冠状铽镓双阳离子配合物的X射线衍射谱，2Theta为7.5°、18.8°、21.3°和26.5°时，存在明显的衍射峰，说明Tb3+、Ga3+、水杨羟肟酸和苯甲酸配位后具有晶体结构。
如图3是在344 nm波长的紫外光激发下的荧光发射谱，光谱显示了491、546、585和622 nm的Tb3+特征发光，对应Tb3+电子跃迁：5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3。
如图4是冠状铽镓双阳离子配合物在360 nm紫外灯下的发光照片，可以观察到，明亮的绿光，对应图3荧光光谱中546 nm的发射波长。
如图5是水溶液中，随着氟离子浓度的增加，稀土有机复合纳米探针分散液的发光强度逐渐弱，说明该探针可以用于水溶液氟离子浓度检测。
如图6是氟离子浓度与稀土有机复合纳米探针发光强度的关系，校准曲线的回归方程为y = 25925.9 – 11886.8 Log x，相关系数R2 = 0.998。
本稀土有机复合纳米探针在水溶液中使用，以下是使用本探针在水溶液中检测氟离子的具体实施例：
将制得的稀土有机复合纳米探针用去离子水稀释32倍，测得如图5中0 ppm时的荧光光谱。相同条件下，加入浓度分别为0.19 ppm、0.95 ppm、3.42 ppm、8.55 ppm、11.97ppm、18.81 ppm的氟离子，测得如图5中的荧光光谱。分别读取荧光光谱中波长为546 nm时最高发光强度，如图6所示，发光强度与Log氟离子浓度呈线性关系，校准曲线的回归方程为y = 25925.9 – 11886.8 Log x，相关系数R2 = 0.998。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。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 (4)
1.用于水溶液氟离子检测的铽有机复合纳米探针的制备，其特征在于，具体包含如下步骤：以冠状铽镓双阳离子配合物为检测信号源，将冠状铽镓双阳离子配合物与嵌段共聚物F127混合自组装制备铽有机复合纳米探针，利用嵌段共聚物快速纳米沉淀法获得复合纳米结构。
2.用于水溶液氟离子检测的铽有机复合纳米探针的制备，其特征在于，具体包括如下步骤：
S1配制冠状铽镓双阳离子配合物的甲醇溶液：五水硝酸铽、水杨羟肟酸、硝酸镓水合物、苯甲酸钠、甲醇和吡啶按照物质的量比0.25：1：1：3：980：25混合，搅拌12小时，过滤除去白色粉末，将滤液密封保存备用；
S2将步骤S1的滤液与嵌段共聚物F127按照体积比0.2～4：1混合，搅拌6～24小时；
S3将步骤S2的混合溶液缓慢注入去离子水，混合溶液与去离子水的体积比为1：10～20；
S4在步骤S3结束后按照总体积的3～10%添加自组装促进剂，得到用于水溶液氟离子检测的铽有机复合纳米探针。
3.根据权利要求2用于水溶液氟离子检测的铽有机复合纳米探针的制备方法，其特征在于，自组装促进剂为具有非极性特征的溶剂包括：油酸、油胺、三正辛基膦、三正辛基氧化膦、环己烷、正己烷、石油醚。
4.根据权利要求2用于水溶液氟离子检测的铽有机复合纳米探针的制备方法，其特征在于，所述稀土有机复合纳米发光材料在250～400 nm紫外光的激发下，产生中心波长为489～492、544～547、584～587、620～623 nm的发光峰。
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