CN112961161B - 一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法 - Google Patents

一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法 Download PDF

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CN112961161B
CN112961161B CN202110198332.5A CN202110198332A CN112961161B CN 112961161 B CN112961161 B CN 112961161B CN 202110198332 A CN202110198332 A CN 202110198332A CN 112961161 B CN112961161 B CN 112961161B
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黄威
支欣茹
高闯
张广维
陈海燕
焦子豪
陈赞
陈仁锁
顾萌
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Nanjing University of Posts and Telecommunications
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Abstract

本发明公开了一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法，所述荧光探针是一种以二苯基为角顶端基团的大环分子。将荧光探针分子对二氯甲烷中Br‑、I‑、PF6 ‑、NO3 ‑、ClO4 ‑、BF4 ‑、COO‑、SCN‑和H2PO4 ‑的四丁基铵(TBA+)盐分别进行检测，只有H2PO4 ‑的加入同时引起吸收和荧光谱图的红移，并且发生峰型的改变，其他离子不能引起谱图的上述变化。

Description

一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法
技术领域
本发明具体属于阴离子识别的技术领域，特别是涉及一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法。
背景技术
自1967年pedersen教授首次合成冠醚分子后，大环化合物逐渐引起科学家们的广泛关注。其中大环化合物主要包括冠醚、环番、葫芦脲、杯芳烃等。此类大环化合物用于离子识别具有以下的主要优势：(1)大环效应，柔性链主客体结合克服焓损失；(2)预组装作用，通过分子内氢键作用，进行预组织，极大提高结合强度；(3)形状持久性，避免发生构象转变从而导致能量损失，提高络合强度；(4)尺寸和形状选择性。
咔唑类化合物具有良好的发光性能，强的给电子能力以及空穴传输能力，已经成为制备优异的荧光探针的理想材料之一。
磷在许多化学和生物过程中都扮演着重要的角色。在生物体中，磷酸类化合物对遗传信息的储存、转录和能量传导等过程都具有都至关重要的作用，并且磷酸盐对现代农业的发展同样起着非常大的作用。因此自然界进化出了磷阴离子选择性受体，包括磷酸盐结合蛋白、蛋白质激酶、磷酸酶等，以实现高效的磷酸盐识别。在过去的几十年中，大量的传感器或探针被合成开发(如吡咯，吲哚，咔唑，芘，尿素等)用于检测磷酸盐和其他相关阴离子。然而，由于磷酸阴离子的重要性，新的荧光探针化合物仍在开发中。
发明内容
针对上述现有技术以及改进需求，本发明提供了一种用于磷酸二氢根离子特异性检测的荧光探针及检测方法。
本发明采用如下技术方案：
一种用于磷酸二氢根离子特异性检测的荧光探针，所述荧光探针是一种以二苯基为角顶端基团的大环分子，其化学结构如下：
Figure BDA0002947000530000021
所述的荧光探针对磷酸二氢根离子特异性检测的方法，包括如下步骤：
1)将所述荧光探针溶于二氯甲烷配成浓度为1×10-4mol/L的溶液A；
2)将四丁基磷酸二氢铵溶于二氯甲烷配成浓度为1×10-2mol/L的溶液B，将其分成若干等分，分别加入不同的阴离子；
3)将溶液A分成若干等分，分别滴加含不同阴离子的溶液B，并逐渐增加浓度，使得加入四丁基磷酸二氢铵的浓度是探针分子的1～30倍；
4)分别测定不同阴离子在不同倍数下的混合溶液的吸收光谱和激发波长为330nm的荧光光谱，并作出波长-吸收和波长-荧光强度的曲线。
进一步的，所述的荧光探针对磷酸二氢根离子特异性检测的方法，其特征在于：所述加入的阴离子包括Br-、I-、PF6 -、NO3 -、ClO4 -、BF4 -、COO-、SCN-和H2PO4 -。
附图说明
图1、荧光探针化合物MBG的单晶结构图；
图2、荧光探针化合物MBG的核磁氢谱图；
图3、荧光探针化合物DBG的单晶结构图；
图4、荧光探针化合物DBG的核磁氢谱图；
图5、荧光探针化合物MBG对不同阴离子的溶液吸收和荧光谱图；
图6、荧光探针化合物DBG对不同阴离子的溶液吸收和荧光谱图。
有益效果
本发明合成了一种构象明确且形状稳定的封闭格状结构荧光探针，在纳米尺度上具有明确的边长和顶点，长宽高尺寸明确，分子刚性大。此荧光探针为π-共轭打断型分子，具有良好的热稳定性、电化学稳定性和光谱稳定性。该荧光探针通过格氏反应，傅克反应得到，原材料简单易得，合成步骤简单，安全性稳定，环境污染性小。通过对该荧光探针的单晶结构进行解析，其具有空腔结构及咔唑基单元，为阴离子响应提供结构基础。在加入阴离子室温放置24h后，该荧光探针的二氯甲烷溶液会发生颜色变化，为可视化检测奠定基础。
具体实施方式
实施例1荧光探针MBG的合成及其对磷酸二氢根离子的特异性检测
荧光探针MBG结构如下：
Figure BDA0002947000530000031
荧光探针MBG的制备方法如下：
在室温下，取1,3-苯基双(二苯甲醇)(442.56mg，1mmol)和咔唑(183.7mg，1.1mmol)加入到超干的二氯甲烷(250ml)中，然后加入三氟甲磺酸(420.2mg，2.5mmol)剧烈搅拌，在常温条件下反应12-15h后，向反应液中加入碳酸氢钠溶液中和后加入二氯甲烷萃取，收集有机相并经无水硫酸镁干燥，减压蒸馏去除溶剂得到粗产品，最后通过层析柱分离得到目标产物MBG，收率为28％(320mg，28％)。1H NMR(400MHz,CDCl3)δ7.94(s,4H),7.86(s,2H),7.21–7.06(m,30H),6.92(m,26H).
荧光探针MBG对磷酸二氢根离子的特异性检测如下：
将探针化合物溶于二氯甲烷配成浓度为1×10-4mol/L的溶液A，Br-、I-、PF6 -、NO3 -、ClO4 -、BF4 -、COO-、SCN-和H2PO4 -的四丁基铵(TBA+)溶于二氯甲烷分别配成浓度为1×10-2mol/L的溶液B。向溶液A中分别加入不同的阴离子，使得加入后的四丁基阴离子铵盐的溶度是探针化合物的10倍，并且分别测定各种混合溶液的吸收和荧光光谱(如图5)。从图5中看到大部分离子对探针化合物的刺激响应不明显，不能引起吸收和荧光谱图的变化，只有磷酸二氢根离子同时引起吸收和荧光谱图的红移，并且发生峰型的改变。以上结果说明其荧光探针化合物对磷酸二氢根离子具有特异性检测性。以上结果说明该荧光探针对磷酸二氢根离子具有特异性检测。
实施例2荧光探针DBG的合成及其对磷酸二氢根离子的特异性检测
荧光探针DBG结构如下：
Figure BDA0002947000530000041
荧光探针DBG的制备方法如下：
在室温下，将[1,1'-联苯]-4,4'-二基双(二苯基甲醇)(400mg，0.77mmol)和咔唑(128.95mg，0.77mmol)加入到250ml的双口反应瓶中，加入二氯甲烷(110ml)搅拌均匀，然后加入三氟甲磺酸(324.24mg，1.93mmol)，在室温下反应24h，然后向反应液中加入碳酸氢钠溶液中和后加入二氯甲烷萃取，收集有机相并经无水硫酸镁干燥，减压蒸馏去除溶剂得到粗产品，最后通过层析柱分离得到目标产物DBG，收率为30％(299mg，30％)。1H NMR(400MHz,CDCl3,ppm)δ7.95(s,2H),7.91(s,4H),7.47(d,J＝8.5Hz,8H),7.39(d,J＝8.5Hz,8H),7.29(d,J＝7.5Hz,16H),7.22(t,J＝7.6Hz,24h),7.16(d,J＝7.1Hz,8H).
荧光探针DBG对磷酸二氢根离子的特异性检测如下：
将探针化合物溶于二氯甲烷配成浓度为1×10-4mol/L的溶液C，Br-、I-、PF6 -、NO3 -、ClO4 -、BF4 -、COO-、SCN-和H2PO4 -的四丁基铵(TBA+)溶于二氯甲烷分别配成浓度为1×10-2mol/L的溶液B。向溶液C中分别加入不同的阴离子，使得加入后的四丁基阴离子铵盐的溶度是探针化合物的10倍，并且分别测定各种混合溶液的吸收和荧光光谱(如图6)。当加入10倍当量磷酸二氢根阴离子盐时，通过谱图发现459nm处出现一个新的吸收峰，而其他阴离子盐并没有相应的变化，说明在二氯甲烷溶液中DBG能特异性识别磷酸二氢根离子。并且对应的荧光光谱发生明显的荧光淬灭，而其他阴离子只有较弱的淬灭效应，进一步说明对磷酸二氢根离子的响应。

Claims (2)

1.一种用于磷酸二氢根离子特异性检测的荧光探针，其特征在于，所述荧光探针是一种以二苯基为角顶端基团的大环分子，其化学结构如下：
Figure FDA0003574565600000011
2.根据权利要求1所述的荧光探针在制备特异性检测磷酸二氢根离子的荧光探针中的用途。
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