CN111533725B - 一种深红外比率型快速响应二氧化硫的荧光探针 - Google Patents

一种深红外比率型快速响应二氧化硫的荧光探针 Download PDF

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CN111533725B
CN111533725B CN202010473168.XA CN202010473168A CN111533725B CN 111533725 B CN111533725 B CN 111533725B CN 202010473168 A CN202010473168 A CN 202010473168A CN 111533725 B CN111533725 B CN 111533725B
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sulfur dioxide
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吕正亮
孙鑫
蒋绪川
范春华
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Abstract

本发明公开了一种检测二氧化硫的荧光探针，属于分析化学技术领域。该探针由制备的新型香豆素染料和4‑二乙氨基水杨醛在浓硫酸中90℃下制备而得。本发明所述荧光探针的制备原料易得，合成方法简单，对二氧化硫具有高选择性、高灵敏性、低检测限等优点。本发明所述荧光探针可应用于细胞中的二氧化硫的检测。

Description

一种深红外比率型快速响应二氧化硫的荧光探针
技术领域
本发明提供了一种检测二氧化硫的荧光探针，属于荧光探针技术领域。
技术背景
二氧化硫(SO2)是一种重要的化工原料，广泛应用于各种各样的行业，例如纸浆制造、金属加工和食品防腐剂。同时又是环境的主要污染物之一，在生物体中以HSO3 –的形式存在，可通过含硫氨基酸的氧化或磺胺基丙酮酸的分解而产生。越来越多的研究表明，SO2作为抗氧化剂在对抗ROS，调节氧化还原状态方面具有积极作用。同时二氧化硫还是一种重要的内源性气体递质，在许多生理活动中起着至关重要的作用，如血管舒张、肌肉放松、信号传导。细胞内水平异常与某些疾病密切相关，如心血管疾病，呼吸系统疾病，神经系统疾病，甚至癌症。因此，发展准确有效的检测环境和生物体中二氧化硫的方法是特别值得关注的。
目前，如高效液相色谱法、质谱法、气相色谱法及电化学方法等等都可以用于二氧化硫。然而这些方法具有操作步骤复杂、所用仪器昂贵、响应时间长等缺点。与此相反，荧光探针具有的高灵敏度、操作简单、检测时间短、低成本，以及能够实现对细胞和活体的实时可视化示踪的优点恰恰能够弥补传统检测方法的不足。因此，开发出能够用于检测生物体内二氧化硫的荧光探针有助于环境或者医学等相关领域的推进。
发明内容
本发明所述的一种检测二氧化硫的荧光探针，其特征在于，所述荧光探针的化学结构式1所示：
上述检测二氧化硫的荧光探针以如下方法制备：
将0.2克化合物Cou-Acetyl与0.18克4-二乙氨基水杨醛溶解于2.9毫升浓硫酸中，上述体系在90摄氏度下搅拌回流8小时，反应结束后冷却至室温，滴加2.9毫升高氯酸，加入50毫升冰水，抽滤并用冰水洗涤，将得到的抽滤物经柱层析纯化，得到蓝紫色固体产物1，收率为80%。
本发明所述的荧光探针可用于水溶液中的二氧化硫的检测。
进一步优选的，所述荧光探针用于在pH=7.4的乙醇与HEPES的体积比为1：9的混合液中的二氧化硫的快速检测，检测限为 0.075微摩尔/升。
本发明所述荧光探针用于在pH=7.4的乙醇与HEPES的体积比为1：9的混合液中对二氧化硫具有快速响应性能。本发明通过实验验证，所述荧光探针在pH=7.4的乙醇与HEPES的体积比为1：9的混合液中以654nm波长的光源作为激发光，其溶液发出690nm的红色荧光，随着亚硫酸氢钠的加入，溶液以470nm的光激发时，溶液在610nm处发出强烈的橙色荧光。其荧光强度值可在1分钟内达到最大值。因此，本探针可对二氧化硫在1分钟实现快速检测。其它阴、阳离子，巯基氨基酸等生物活性物质的加入对荧光没有影响。因此，本发明的荧光探针化合物对二氧化硫具有很高的选择性。
本发明的荧光探针化合物在pH=7.4的乙醇与HEPES的体积比为1：9的混合液中，亚硫酸氢钠的浓度与两个波长下荧光强度的比值呈线性关系，因此，可以比率性定量测定溶液中二氧化硫的含量。
本发明所述荧光探针可用于细胞内二氧化硫的检测。具体检测方法为：在37℃下Hela细胞在10微摩尔/升的探针1的溶液中培养30分钟，细胞呈现红色荧光。在37℃下Hela细胞先在10微摩尔/升的探针1的溶液中培养30分钟后，用PBS洗涤三次，再用47.5微摩尔/升的亚硫酸氢钠溶液孵育30分钟，细胞发出强烈的橙色荧光。实验表明，本发明所述荧光探针能够用于细胞内二氧化硫的检测，在生物医学等方面具有潜在的应用价值。
本发明的有益效果：
本发明所涉及的一种检测二氧化硫的荧光探针，具有以下优势：1、该探针能快速与二氧化硫发生反应，具有较强的荧光发射；2、该探针在检测二氧化硫过程中具有较高的选择性；3、该探针可用于环境中定量或者活细胞内定性检测二氧化硫的有效工具。
附图说明
图1是化合物1的结构示意图。
图2是化合物1的1H NMR谱图。
图3是化合物1的选择性荧光光谱图。
图4是470nm激发下化合物1随亚硫酸氢钠浓度变化的荧光光谱图。
图5是654nm激发下化合物1随亚硫酸氢钠浓度变化的荧光光谱图。
图6是在470nm激光激发下的化合物1与亚硫酸氢钠的细胞成像图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明，但不限于此。实施例中的各种原料均来自于市场购买。
实施例1 探针的合成
将0.2克化合物Cou-Acetyl与0.18克4-二乙氨基水杨醛溶解于2.9毫升浓硫酸中，上述体系在90摄氏度下搅拌回流8小时，反应结束后冷却至室温，滴加2.9毫升高氯酸，加入50毫升冰水，抽滤并用冰水洗涤，将得到的抽滤物经柱层析纯化，得到蓝紫色固体探针1，收率为80%。图2为该探针的核磁图。
实施例2 探针的选择性分析
在含有10微摩尔/升的探针1的EtOH与HEPES的体积比为1：9的混合液中一次性添加到浓度为200微摩尔/升的亚硫酸氢钠溶液，检测溶液荧光的变化。结果如图3，当激发光波长为470nm时，探针对NaHSO3在610nm出有强烈的橙色荧光，而且探针对其他阴、阳离子、巯基氨基酸没有明显响应。说明探针对二氧化硫具有优异的选择性。
实施例3 探针对二氧化硫浓度变化响应分析
将不同浓度的亚硫酸氢钠溶液加入含有10微摩尔/升的探针1的EtOH与HEPES的体积比为1：9的混合液中，分别用470nm、654nm激发，探针1在610nm、690nm处的荧光强度的比值随亚硫酸氢钠量的增加呈规律性变化。如图4和5，说明探针可以在两个波长的光激发下比率型灵敏响应亚硫酸氢钠浓度的变化。
实施例4 探针在活细胞中检测二氧化硫
将10 μM的探针加入到Hela细胞的培养液中，然后在37℃下培养30分钟，然后再加入47.51微摩尔/升亚硫酸氢钠水溶液培养30分钟，洗涤后成像，细胞发出强烈的橙色荧光，结果如图6。实验表明，探针能够对细胞中的二氧化硫的可视化检测。

Claims (1)

1.一种深红外比率型快速响应二氧化硫的荧光探针，其特征在于，所述荧光探针的化学结构式如下所示
Figure DEST_PATH_IMAGE001
。
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