CN108218863A - 一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针及其应用 - Google Patents

一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针及其应用 Download PDF

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CN108218863A
CN108218863A CN201810178819.5A CN201810178819A CN108218863A CN 108218863 A CN108218863 A CN 108218863A CN 201810178819 A CN201810178819 A CN 201810178819A CN 108218863 A CN108218863 A CN 108218863A
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fluorescence
pyrazolo
pyridine
picolinic acid
phenylpyrazoles
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CN108218863B (zh
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葛燕青
吕花营
刘爱坤
段桂运
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Taishan Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—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
    • 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
    • C07D471/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

本发明公开了一种吡唑并[1,5‑a]吡啶羧酸类pH荧光探针，所述探针是2‑苯基吡唑并[1,5‑a]吡啶‑5‑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有较好的荧光选择性和较高的灵敏度，与现有探针相比，具有pH响应范围窄，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

一种吡唑并[1,5-a]吡啶羧酸类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2-苯基吡唑并[1,5-a]吡啶-5-羧酸及其应用。
背景技术
pH是细胞健康的一个重要指标, 其在细胞的增殖与凋亡、新陈代谢、细胞内吞作用、酶活性、离子运输、肌肉收缩、神经系统的信号传递、抗药性等过程中起着重要作用。人体内pH异常也会引起一些疾病,如:炎症、阿尔茨海默病、癌症等。因此，检测生物体内的pH值显得非常重要。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。
荧光探针因选择性好,灵敏度高,操作简单,成本低并且可以实现实时监测等优点,现广泛应用于细胞内pH值的测定。尽管已有多种pH荧光探针被报道,但是目前对于强酸性条件下细胞内pH的研究还不够深入。为此,开发新型的性能优异的酸性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、病理过程具有重要的意义。
吡唑并[1,5-a]吡啶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荧光探针新分子吡唑并[1,5-a]吡啶羧酸及其应用。
本发明的技术方案是：一种吡唑并[1,5-a]吡啶羧酸pH荧光探针，其化学结构式如式（1）所示：
本发明还包括吡唑并[1,5-a]吡啶羧酸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有较好的荧光选择性。
本发明还包括吡唑并[1,5-a]吡啶羧酸pH荧光探针的合成方法，在95%的乙醇溶液中，将2-苯基吡唑并[1,5-a]吡啶-5-羧酸乙酯与氢氧化钠按照物质的量比1:2投料，80度下回流反应2-5小时，得到2-苯基吡唑并[1,5-a]吡啶-5-羧酸。
配制吡唑并[1,5-a]吡啶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4.4变化至2.4的过程中，440 nm处荧光强度明显增强，如图1所示。因此，吡唑并[1,5-a]吡啶羧酸作为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25 mL圆底烧瓶中依次加入0.27g（1.00 mmol）2-苯基吡唑并[1,5-a]吡啶-5-羧酸乙酯，0.08g（2.00 mmol）氢氧化钠，10 mL95%的乙醇，80度下回流反应2-5小时，倒入100 mL水中，稀盐酸调pH至5-6，析出固体，抽滤，干燥得0.21g无色固体产品，产率88.2 %。
核磁共振氢谱，碳谱测定： 1H NMR (DMSO-d6, 400 MHz), δ 13.37 (s, 1H),8.78 (d, J = 8.0 Hz, 1H), 8.33 (s, 1H), 8.02 (m, 2H), 7.50 (t, J = 8.0 Hz,2H), 7.42 (m, 1H), 7.34 (s, 1H), 7.28 (dd, J = 8.0 Hz, 4.0 Hz, 1H). 13C NMR(DMSO-d6, 100 MHz), δ 166.48, 153.89, 140.74, 132.80, 129.38, 129.23, 129.16,126.57, 126.51, 120.93, 111.52, 97.39.
如图2，图3所示。
实施例2：
取2-苯基吡唑并[1,5-a]吡啶-5-羧酸0.0024g，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4.4变化至2.4的过程中，440 nm处荧光强度明显增强，如图1所示。

Claims (2)

1.一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针，其特征在于：它是2-苯基吡唑并[1,5-a]吡啶-5-羧酸，其化学结构式如式（1）所示：
式（1）化合物在二甲基亚砜的水溶液中对pH有较好的荧光选择性。
2.权利要求1所述2-苯基吡唑并[1,5-a]吡啶-5-羧酸的合成方法，其特征在于：在95%的乙醇溶液中，将2-苯基吡唑并[1,5-a]吡啶-5-羧酸乙酯与氢氧化钠按照物质的量比1:2投料，80度下回流反应2-5小时，得到2-苯基吡唑并[1,5-a]吡啶-5-羧酸。
CN201810178819.5A 2018-03-05 2018-03-05 一种吡唑并[1,5-a]吡啶羧酸类pH荧光探针及其应用 Expired - Fee Related CN108218863B (zh)

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CN109776531A (zh) * 2019-03-11 2019-05-21 张智涵 一种吡唑并吡啶醛类亚硫酸根离子荧光探针

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776531A (zh) * 2019-03-11 2019-05-21 张智涵 一种吡唑并吡啶醛类亚硫酸根离子荧光探针
CN109776531B (zh) * 2019-03-11 2021-06-15 张智涵 一种吡唑并吡啶醛类亚硫酸根离子荧光探针

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