CN106010508B - 一种中氮茚羧酸类pH荧光探针及其应用 - Google Patents

一种中氮茚羧酸类pH荧光探针及其应用 Download PDF

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CN106010508B
CN106010508B CN201610349416.3A CN201610349416A CN106010508B CN 106010508 B CN106010508 B CN 106010508B CN 201610349416 A CN201610349416 A CN 201610349416A CN 106010508 B CN106010508 B CN 106010508B
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indolizine
fluorescence
carboxylic acids
fluorescence probes
probe
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CN106010508A (zh
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葛燕青
段桂运
曹晓群
董建
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Taishan Medical University
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Abstract

本发明公开了一种中氮茚羧酸类pH荧光探针，所述探针是2‑乙酰基中氮茚‑7‑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

一种中氮茚羧酸类pH荧光探针及其应用
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2-乙酰基中氮茚-7-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,凋亡,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。
中氮茚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荧光探针新分子中氮茚羧酸及其应用。
本发明的技术方案是：一种中氮茚羧酸pH荧光探针，其化学结构式如式（1）所示：
本发明还包括中氮茚羧酸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。
本发明还包括中氮茚羧酸pH荧光探针的合成方法，在95%的乙醇溶液中，将2-乙酰基中氮茚-7-羧酸乙酯与氢氧化钠按照1:2投料比例，80度下回流反应2-5小时，得到2-乙酰基中氮茚-7-羧酸。
配制中氮茚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有2.6变化至7.5的过程中，460 nm处荧光强度明显减弱，如图1所示。因此，中氮茚羧酸作为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2.31g（10.0 mmol）2-乙酰基中氮茚-7-羧酸乙酯，0.80g（20.0 mmol）氢氧化钠，20 mL95%的乙醇，80度下回流反应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1.86g黄色固体产品，产率91.6%。
核磁共振氢谱测定：1H NMR(400 MHz，DMSO-d6):δ12.96 (s, 1H), 8.31 (m, 2H),8.39 (s, 1H), 7.13 (s, 1H), 7.04(m, 1H),2.51 (s, 3H). 13C NMR(100 MHz，DMSO-d6): 194.37, 166.79, 131.61, 129.65, 126.48, 124.23, 121.21, 118.98, 111.41,104.44, 28.09.
如图2，图3所示。
实施例2：
取中氮茚羧酸0.0020g，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有2.6变化至7.5的过程中，430 nm处荧光强度明显增强，如图1所示。

Claims (2)

1.一种中氮茚羧酸类pH荧光探针，其特征在于：它是2-乙酰基中氮茚-7-羧酸，其化学结构式如式（1）所示：
F:\专利\6be06081-bba2-48d6-a656-3dad02910466\100002\dest_path_image001.jpg
式（1）化合物在二甲基亚砜的水溶液中对pH有荧光选择性。
2.权利要求1所述中氮茚羧酸类pH荧光探针的合成方法，其特征在于：在95%的乙醇溶液中，将2-乙酰基中氮茚-7-羧酸乙酯与氢氧化钠按照1:2投料比例，80度下回流反应2-5小时，得到2-乙酰基中氮茚-7-羧酸。
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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
CN109749734A (zh) * 2017-11-07 2019-05-14 泰山医学院 一种可以检测亚硫酸根离子的比率型荧光探针及应用
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
CN114276343B (zh) * 2020-09-27 2023-07-07 中国石油化工股份有限公司 用于检测氯化苯中微量铁离子的荧光探针的制备方法
CN113444067B (zh) * 2021-06-04 2022-06-07 西华大学 一种苯并噻吩羧酸盐的制备方法及应用

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