CN105906623B - 一种吡啶并[1,2‑a]苯并咪唑羧酸类pH荧光探针及其应用 - Google Patents

一种吡啶并[1,2‑a]苯并咪唑羧酸类pH荧光探针及其应用 Download PDF

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CN105906623B
CN105906623B CN201610347388.1A CN201610347388A CN105906623B CN 105906623 B CN105906623 B CN 105906623B CN 201610347388 A CN201610347388 A CN 201610347388A CN 105906623 B CN105906623 B CN 105906623B
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benzimidazole
fluorescence
pyrido
carboxylic acids
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葛燕青
段桂运
曹晓群
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Taishan Medical University
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Abstract

本发明公开了一种吡啶并[1,2‑a]苯并咪唑羧酸类pH荧光探针，所述探针是4‑甲基吡啶并[1,2‑a]苯并咪唑‑3‑羧酸，其化学结构式如式（1）所示。本发明的荧光探针在二甲基亚砜的水溶液中对pH有独特的荧光选择性和较高的灵敏度，与现有探针相比，具有pH相应范围窄，不受背景干扰，适用于强酸性环境pH检测等显著优点，具有巨大的应用前景。

Description

一种吡啶并[1,2-a]苯并咪唑羧酸类pH荧光探针及其应用
技术领域
本发明涉及有机小分子荧光探针领域，尤其涉及一种新型pH荧光探针4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸及其应用。
背景技术
pH作为细胞健康的一个重要指标,在细胞生长,扩散,调亡,自噬,离子运输,以及其他细胞过程中起着重要作用。其微小变化便可能导致细胞功能素乱和严重疾病,如大肠癌,乳腺癌,囊性纤维化,神经退行性疾病甚至阿尔茨海默氏症。但目前常用的玻璃电极测pH的方法不适用于生命领域pH的检测。
荧光探针选择性好,灵敏度高,操作简单,成本低并且可以实现实时监测,现已作为一种首选的测试工具应用于细胞内pH值的测定。尽管已有多种pH荧光探针被报道,但是目前对于酸性条件下细胞内pH的研究还不够深入。为此,开发新型理想的酸性pH探针,检测细胞内氢离子的浓度以及分布对研究细胞的生理、病理过程具有极为重要的意义。
吡啶并[1,2-a]苯并咪唑类化合物因受制于有限的合成方法，其在光学领域的应用报到很少，其而作为pH荧光探针的应用更是未见文献报道。
发明内容
针对现有技术的不足，本发明的目的在于提供一种pH荧光探针新分子吡啶并[1,2-a]苯并咪唑羧酸及其应用。
本发明的技术方案是：一种吡啶并[1,2-a]苯并咪唑羧酸pH荧光探针，其化学结构式如式（1）所示：
本发明还包括吡啶并[1,2-a]苯并咪唑羧酸pH荧光探针的应用，式（1）化合物在二甲亚砜的水溶液中对pH有独特的荧光选择性。
本发明还包括吡啶并[1,2-a]苯并咪唑羧酸pH荧光探针的合成方法，在95%的乙醇溶液中，将4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸乙酯与氢氧化钠按照1:2投料比例，80℃下回流反应2-5小时，得到4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸。
配制吡啶并[1,2-a]苯并咪唑羧酸的二甲亚砜溶液，分别加入到不同pH的二甲亚砜的水溶液中（二甲亚砜：水=2:8），通过荧光光谱测试来研究对不同pH的选择性，测其荧光发射波谱强度变化发现： pH由4.0变化至6.0的过程中，430 nm处荧光强度明显增强，如图1所示。因此，吡啶并[1,2-a]苯并咪唑羧酸作为pH荧光探针具有巨大的应用前景。
附图说明
图1：不同pH的二甲亚砜水溶液（二甲亚砜：水=2:8）的荧光光谱图。
图2：荧光探针新分子的核磁氢谱。
图3：荧光探针新分子的核磁碳谱。
具体实施方式
实施例1：式（1）化合物的合成方案如下式所示：
具体合成步骤如下：
在50 mL圆底烧瓶中依次加入2.54g（10.0 mmol）4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸乙酯，0.80g（20.0 mmol）氢氧化钠，20 mL95%的乙醇，80℃下回流反应2-5小时，倒入300 mL水中，浓盐酸调pH至5-6，析出大量固体，抽滤，干燥得1.32g黄色固体产品，产率58.4%。
核磁共振氢谱测定：1H NMR（400 MHz，DMSO-d6）：δ9.44 (d, J = 8.0 Hz, 1H),8.62 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.83-7.67(m, 3H),2.89 (s,3H). 13C NMR（100 MHz，CDCl3）：166.97, 129.25, 128.10, 126.24, 124.55, 115.69,114.91, 114.40, 15.01.
如图2，图3所示。
实施例2：
取吡啶并[1,2-a]苯并咪唑羧酸0.0023g，溶于10mL二甲亚砜，得探针母液，浓度为10-3M。分别取100微升探针母液，加入到10mL不同pH的二甲亚砜的水溶液中（二甲亚砜：水=2:8）测其荧光发射强度变化发现：pH由4.0变化至6.0的过程中，430 nm处荧光强度明显增强，如图1所示。

Claims (2)

1.一种吡啶并[1,2-a]苯并咪唑羧酸类pH荧光探针，其特征在于：它是4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸，其化学结构式如式（1）所示：
C:\Documents and Settings\Administrator\Local Settings\Temp\360zip$Temp\360$8\481105e3-09ec-4236-92d1-fb7eb6fb9654\100001\100001.xml.files\image001.jpg
式（1）化合物在二甲基亚砜的水溶液中对pH有独特的荧光选择性。
2.权利要求1所述4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸pH荧光探针的合成方法，其特征在于：在95%的乙醇溶液中，将4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸乙酯与氢氧化钠按照1:2投料比例，80℃下回流反应2-5小时，得到4-甲基吡啶并[1,2-a]苯并咪唑-3-羧酸。
CN201610347388.1A 2016-05-24 2016-05-24 一种吡啶并[1,2‑a]苯并咪唑羧酸类pH荧光探针及其应用 Expired - Fee Related CN105906623B (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108218863A (zh) * 2018-03-05 2018-06-29 泰山医学院 一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针及其应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106483113A (zh) * 2016-10-26 2017-03-08 华南师范大学 1‑芘甲酸作为pH荧光探针的应用
CN109694706A (zh) * 2017-10-20 2019-04-30 泰山医学院 一种氰基呋喃半花菁类so32-比率型荧光探针及其应用
CN109722238A (zh) * 2017-10-27 2019-05-07 泰山医学院 吡啶修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探针及其应用
CN108218866A (zh) * 2018-04-03 2018-06-29 泰山医学院 吡啶并苯并咪唑类汞离子比率荧光探针及其应用
CN110498794B (zh) * 2018-05-18 2022-02-01 山东第一医科大学(山东省医学科学院) 咪唑并[1,2-a]吡啶衍生物类Pd2+荧光探针及其应用
CN108570063A (zh) * 2018-05-30 2018-09-25 泰山医学院 一种能够检测onoo-的小分子荧光探针及其应用
CN116283968A (zh) * 2023-02-20 2023-06-23 广东省科学院测试分析研究所(中国广州分析测试中心) 一种乙酰氨基咪唑并吡啶类化合物及其制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755702A (zh) * 2014-01-29 2014-04-30 清华大学 菲并咪唑并异喹啉及其衍生物及其制备方法与应用
CN105586033A (zh) * 2015-12-31 2016-05-18 陈超 一种含有谷氨酸结构的罗丹明pH荧光探针及其应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103755702A (zh) * 2014-01-29 2014-04-30 清华大学 菲并咪唑并异喹啉及其衍生物及其制备方法与应用
CN105586033A (zh) * 2015-12-31 2016-05-18 陈超 一种含有谷氨酸结构的罗丹明pH荧光探针及其应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Modular Assembly of Ring-Fused andπ‑Extended Phenanthroimidazoles via C−H Activation and Alkyne Annulation;Liyao Zheng et al.;《The Journal of Organic Chemistry》;20140408;第79卷;第3930−3936页 *
The synthesis, characterization and optical properties of novel pyrido[1,2-a]benzimidazole derivatives;Yan Qing Ge et al.;《Dyes and Pigments 》;20100817;第88卷;第344-349页 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108218863A (zh) * 2018-03-05 2018-06-29 泰山医学院 一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针及其应用

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