CN108226106B - 基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光探针 - Google Patents

基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光探针 Download PDF

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CN108226106B
CN108226106B CN201711081903.7A CN201711081903A CN108226106B CN 108226106 B CN108226106 B CN 108226106B CN 201711081903 A CN201711081903 A CN 201711081903A CN 108226106 B CN108226106 B CN 108226106B
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曹晓群
葛燕青
吉瑞雪
刘爱坤
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Abstract

本发明公开了一种中氮茚哌嗪氰基呋喃半花菁类的比率型亚硫酸根荧光分子探针，其中化学结构如式（1）所示。本发明的比率型荧光探针在乙醇/水（体积比3:7）溶液中对亚硫酸根离子有着明显的荧光强度的改变，灵敏度高，响应迅速，有着广阔的应用前景。

Description

基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光 探针
背景技术
在众多的阴离子中，亚硫酸根离子得到人们广泛的重视。不仅仅是因为在工业生产中大量的二氧化硫的排放引起酸雨的形成给环境带来很大的破坏，更重要的是因为随着人们对食品安全要求的提高，对亚硫酸的含量要求也渐渐提高。亚硫酸盐作为一种食品添加剂，常常用于食物或酒水中来阻止氧化、细菌发酵。而且在制药和造纸工业中也有大量是应用。过量的亚硫酸盐对人体是有害的，容易引起过敏和哮喘等疾病。 因此寻找一种有效的检测方法是一箱非常有意义的工作。
目前用于检测亚硫酸盐的方法有很多种，比如分光光度法、磷光光度法、化学发光法、离子选择性电机法以及受到广泛关注的荧光检测法。荧光检测法针对上述几种方法而言操作简单，不需要进行复杂的样品预处理，选择性好。所以运用荧光探针方法来检测亚硫酸根离子是目前使用最为广泛的一种方法。
发明内容
荧光检测法目前大多为单峰显示，受到环境影响比较大，会降低检测的准确性，同时灵敏度也较低，对于一些含量较低的检测结果不理想。为了解决上述问题本发明提供了一种新型的基于FRET形式的能量传递的比率型荧光探针。。
本发明设计的方案如下：一种中氮茚取代的氰基呋喃半花菁的比率型荧光探针，用于检测亚硫酸根离子，其化学结构式如下式（1）所示：
Figure 853186DEST_PATH_IMAGE001
（1）
本发明主要是提供一种检测亚硫酸根离子的比率型荧光探针分子，即中氮茚取代的氰基呋喃半花菁的比率型荧光探针的应用，即式（1）化合物在乙醇/水溶液中（体积比3:7）对亚硫酸根离子有着独特的荧光选择性。
本发明还包括中氮茚取代的氰基呋喃半花菁的荧光探针分子的合成方法，在乙醇溶液中，将2-乙酰基-中氮茚-7-甲酸与2-（4-（4-（哌嗪基）苯乙烯基）-5,5-二甲基呋喃基）丙二腈，按照1:1.1摩尔比的投料比例，加热回流12h，得到由中氮茚取代的氰基呋喃半花菁的比率型荧光探针。
得到式（1）化合物。
配置式（1）化合物的乙醇/水（体积比3:7）溶液，分别加入10当量的NaCl、MgCl·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、F-，Br-，I-，HCO3-，NO3-，ClO-，SO4 2-，SCN-，S2O3 2-，S2-，Cys，Hcy，GSH，HSO3-，SO3 2- 的水溶液，通过荧光光谱测试来研究对不同离子的选择性，观察荧光发射光谱的强度变化：本发明所述的 类的荧光探针分子即式（1）化合物对亚硫酸根有独特的荧光选择性，如图1所示。逐渐加入亚硫酸根离子至10当量后，化合物1在464nm处荧光明显增强，在638nm处荧光明显减弱，如图2所示。因此，分子荧光探针即式（1）化合物作为检测亚硫酸根离子的荧光探针具有较为明显的现象。
本发明提供了一种荧光探针分子即式（1）化合物，本实验证明本发明所述式（1）化合物可与亚硫酸根离子在乙醇/水（体积比3:7）溶液中以化学计量比1:10反应，在反应过程中，由于式（1）化合物加入亚硫酸根离子后，双键断裂，大的共轭体系破坏，从而使荧光强度在464nm处明显增加，而在638nm处明显降低。由此可证实本发明所述式（1）化合物在乙醇/水（体积比3:7）溶液中对亚硫酸根离子有独特的荧光选择性，较高的灵敏度，广阔的应用前景。
附图说明
图1：式（1）化合物（5×10-6M）的乙醇/水（体积比3:7）溶液中加入10当量的不同离子的荧光强度变化图。
图2：式（1）化合物（5×10-6M）的乙醇/水（体积比3:7）溶液中进行SO3 2-荧光滴定图。图中FL Intensity为荧光强度，Wavelength为波长，equ.为倍数。
图3：式（1）化合物（5×10-6M）的乙醇/水（体积比3:7）溶液中在不同pH条件下的荧光强度比例图。
图4是式（1）化合物合成方法反应式图。
具体实施方法
实施例：式（1）化合物合成方案如下是所示：
Figure 120219DEST_PATH_IMAGE002
具体合成步骤如下：
在25 mL圆底烧瓶中依次加入0.1 g（0.26 mmol) 2-乙酰基-中氮茚-7-甲酸，0.06g（0.28 mmol) 2-（4-（4-（哌嗪基）苯乙烯基）-5,5-二甲基呋喃基）丙二腈, 20 mL乙醇，3滴哌啶，加热回流反应12小时。TLC检测反应完成，冷却析出大量结晶，洗涤，对溶液进行浓缩，柱层析得到0.09 g浅黄色固体，产率52.6% 。
核磁共振氢谱测定：1H NMR（400MHz，CDCl3）：. 1H NMR (400 MHz, dmso) δ 8.24(d, 1H), 8.16 (s, 1H), 7.86 (d, 1H), 7.73 (d, 2H), 7.57 (s, 1H), 6.97 (d,2H), 6.91 (d,1H), 6.87 (s,1H), 6.66 (d,1H), 3.71 (s,4H), 3.54 (s, 4H),3.302(m, 11H) 2.47 (s, 3H), 1.75 (s, 5H), 1.62 (s, 1H), 1.23 (d,5H), 1.00 (d, 1H),0.82 (t, 1H).
实施例1
式（1）化合物（5×10-6M）的乙醇/水（体积比3:7）溶液,分别加入不同当量的亚硫酸根离子的水溶液，来检测不同浓度下探针的荧光强度的变化，测得其荧光强度在464nm处荧光增强，在638nm处荧光减弱，如图1。
实施例2
式（1）化合物（5×10-6M）的乙醇/水（体积比3:7）溶液，分别加入10当量的NaCl、MgCl·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、F-，Br-，I-，HCO3 -，NO3 -，ClO-，SO4 2-，SCN-，S2O3 2-，S2-，Cys，Hcy，GSH，HSO3-，SO3 2- 的水溶液，测得其荧光强度在464nm处荧光明显增强，在638nm处荧光明显减弱，如图2所示。
实施例3
式（1）化合物（5×10-6M）与式（1）化合物（5×10-6M）中加入10当量的亚硫酸根离子的的乙醇/水（体积比3:7）溶液，在不同pH溶液条件下，464nm与638nm处荧光强度的比较图，如图3所示。

Claims (2)

1.基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光探针，其特征在于，所述荧光探针的化学结构式如式(1)所示：
Figure FDA0002591841720000011
2.根据权利要求1所述的基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光探针的合成方法，其特征在于，包括如下步骤：在乙醇溶液中，将2-乙酰基-中氮茚-7-甲酸与2-(4-(4-(哌嗪基)苯乙烯基)-5,5-二甲基呋喃基)丙二腈，按照1:1.1摩尔比的投料比例，加热回流12h，得到基于中氮茚-氰基呋喃半花菁的比率型亚硫酸根离子荧光探针。
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