CN108191852A - 一种用于检测次氯酸的分子荧光探针及其应用 - Google Patents

一种用于检测次氯酸的分子荧光探针及其应用 Download PDF

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CN108191852A
CN108191852A CN201710306719.1A CN201710306719A CN108191852A CN 108191852 A CN108191852 A CN 108191852A CN 201710306719 A CN201710306719 A CN 201710306719A CN 108191852 A CN108191852 A CN 108191852A
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fluorescence probe
formula
fluorescence
compound
benzimidazole
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葛燕青
吉瑞雪
刘爱坤
邢旭娇
曹晓群
申世立
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Taishan Medical University
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract

本发明公开了一种吡啶[1.2‑a]苯并咪唑腙类衍生物的分子荧光探针，用于检测次氯酸分子的荧光探针及其应用，其化学结构如式（1）所示。本发明的荧光探针在乙醇/水（体积比1:9）溶液中对次氯酸有好的荧光选择性、较高的灵敏度，有广阔的应用前景。

Description

一种用于检测次氯酸的分子荧光探针及其应用
技术领域
活性氧化物广泛存在于细胞的新陈代谢中，有着非常重要的生物功能，了解活性氧化物在生物体的病理及生理过程中产生的影响成为研究的热点问题。活性氧化物中的一种次氯酸，可以与生物体内的氨基酸，蛋白质，核酸等生物大分子表面的官能团反应，进而参与生命活动，如物质、能量的合成代谢，免疫系统的调控等。在机体生长过程中起着举足轻重的作用。而且次氯酸也与许多疾病有关，如关节炎，肺损伤等疾病。所以如何检测次氯酸成为人们关注的重点。
用于检测次氯酸的方法有电化学分析法、化学发光法、分光光度法及荧光法等。其中荧光法具有高效、准确、快速等优点，所以近几年用于检测次氯酸的荧光探针越来越多。但已知用于检测次氯酸的探针仍有局限性。如罗丹明B的肼类衍生物监测的条件需要较强碱性的环境下才能响应。有些探针则在合成过程中条件要求比较苛刻，如需要避光反应。而现有的荧光探针的荧光团仅局限于几种染料，如香豆素、罗丹明、1，8-萘二甲基酰亚胺等。因此开发新的荧光团用于高选择性、高灵敏度检测次氯酸显得尤为重要。
背景技术
针对现有的不足，本发明设计了一个新的荧光团，合成新的荧光探针来检测次氯酸。该探针检测次氯酸选择性好，响应快，灵敏度高，制备方法简单快捷，成本低，应用广。。
发明内容
本发明的设计方案是：一种吡啶[1.2-a]苯并咪唑腙类衍生物的荧光探针，用于检测次氯酸，其化学结构是如式（1）所示：
(1)
本发明主要是提供一种检测次氯酸的分子荧光探针，即吡啶[1.2-a]苯并咪唑腙类衍生物荧光探针的应用，即式（1）化合物在乙醇/水溶液中（体积比1:9）对次氯酸有独特的荧光选择性。
本发明还包括吡啶[1.2-a]苯并咪唑腙类衍生物荧光探针的合成方法，在乙醇溶液中，将（4-（二乙氨基）-2-羟基苯甲酰基）苯甲醛与2-肼基吡啶按照1:2.5投料比例，加热回流12小时，得到式（1）化合物。
配置式（1）化合物的乙醇/水（体积比1:9）溶液，分别加入10当量的NaCl、MgCl·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、HO．、t-BuO·、KO2、1O2、NaOONO2、H2O2、t-BuOOH、HClO的水溶液，通过荧光光谱测试来研究对不同离子的选择性，测器荧光发射波普强度变化发现：本发明所述的吡啶[1.2-a]苯并咪唑腙类衍生物荧光探针即式（1）化合物对次氯酸有独特的荧光选择性，如图1所示。逐渐加入次氯酸至4当量后，化合物1在474nm处荧光明显增强，如图2所示。因此，分子荧光探针即式（1）化合物作为检测次氯酸的荧光探针具有较为明显的现象。
本发明提供了一种分子荧光探针即式（1）化合物，本实验证明本发明所述式（1）化合物可与次氯酸在乙醇/水（体积比1:9）溶液中以化学计量比1:4反应，在反应过程中，由于式（1）化合物加入次氯酸后，水解氧化成酸，从而使荧光强度明显增加。由此可证实本发明所述式（1）化合物在乙醇/水（体积比1:9）溶液中对次氯酸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1:9）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1:9）溶液中进行ClO-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（5×10-6M）的乙醇/水（体积比1:9）溶液中对不同倍的ClO-反应的时间。
图4是式（1）化合物合成方法反应式图。
具体实施方式
实施例：式（1）化合物合成方案如下是所示：
具体合成步骤如下：
在25 mL圆底烧瓶中依次加入0.1 g（0.36 mmol)（4-（二乙氨基）-2-羟基苯甲酰基）苯甲醛，0.11 g（0.91 mmol)2-肼基吡啶, 20 mL乙醇，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黄色固体，产率65% 。
核磁共振氢谱测定：1H NMR（400MHz,CDCl3）：δ 11.07 (s, 1H), 8.92 (d, J =7.1 Hz, 1H), 8.29 – 8.19 (m, 2H), 8.10 (d, J = 3.5 Hz, 1H), 8.01 (s, 1H),7.79 – 7.63 (m, 3H), 7.63 – 7.39 (m, 6H), 7.35 (t, J = 8.1 Hz, 2H)。
实施例2
向式（1）化合物（5×10-6M）的乙醇/水（体积比1:9）溶液，分别加入10当量的NaCl、MgCl·6H2O、Zn(CH3COO)2、FeCl3·6H2O、CuCl2、HO．、t-BuO·、KO2、1O2、NaOONO2、H2O2、t-BuOOH、HClO后，测其在474nm荧光发射强度变化发现，式（1）化合物对次氯酸有独特的荧光选择性，当加入10当量的ClO-后，化合物1在474nm处荧光强度明显增强。如图2所示。
实施例3
向式（1）化合物（5×10-6M）的乙醇/水（体积比1:9）溶液，分别加入0、2、4当量的ClO-后，测其反应时间的快慢。如图3所示。

Claims (2)

1.一种吡啶[1.2-a]苯并咪唑腙类衍生物的荧光探针，其化学结构式如式（1）所示：
（1）
式（1）化合物在乙醇/水溶液中（体积比1:9）对次氯酸有独特的荧光选择性。
2.权利要求1所述中吡啶[1.2-a]苯并咪唑腙类衍生物的荧光探针的合成方法在于：在乙醇溶液中，将（4-（二乙氨基）-2-羟基苯甲酰基）苯甲醛和2-肼基吡啶按照1:2.5投料比例，加热回流12小时，得到吡啶[1.2-a]苯并咪唑腙类衍生物的荧光探针。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593078A (zh) * 2018-12-29 2019-04-09 太原师范学院 N-丁基-4-羟基-1,8-萘二甲酰亚胺-3-甲醛-（2-吡啶）腙及应用
CN113004238A (zh) * 2021-03-19 2021-06-22 温州医科大学 一种多功能小分子荧光探针、制备方法及应用
CN113234046A (zh) * 2021-05-10 2021-08-10 安徽大学 一种检测次氯酸根离子的荧光探针及其应用
CN114539181A (zh) * 2022-04-06 2022-05-27 新乡医学院 一种用于铝离子和锌离子快速检测的荧光探针及其制备方法

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CN104710976A (zh) * 2015-01-06 2015-06-17 南京工业大学 次氯酸根离子荧光探针、制备方法及其应用
CN106544007A (zh) * 2015-09-23 2017-03-29 济南大学 一种检测生物体系内次氯酸的荧光探针及其应用

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CN109593078A (zh) * 2018-12-29 2019-04-09 太原师范学院 N-丁基-4-羟基-1,8-萘二甲酰亚胺-3-甲醛-（2-吡啶）腙及应用
CN113004238A (zh) * 2021-03-19 2021-06-22 温州医科大学 一种多功能小分子荧光探针、制备方法及应用
CN113004238B (zh) * 2021-03-19 2022-05-06 温州医科大学 一种多功能小分子荧光探针、制备方法及应用
CN113234046A (zh) * 2021-05-10 2021-08-10 安徽大学 一种检测次氯酸根离子的荧光探针及其应用
CN113234046B (zh) * 2021-05-10 2023-05-16 安徽大学 一种检测次氯酸根离子的荧光探针及其应用
CN114539181A (zh) * 2022-04-06 2022-05-27 新乡医学院 一种用于铝离子和锌离子快速检测的荧光探针及其制备方法
CN114539181B (zh) * 2022-04-06 2023-06-09 新乡医学院 一种用于铝离子和锌离子快速检测的荧光探针及其制备方法

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