CN110551499B - 一种检测铜离子的荧光探针及其合成方法 - Google Patents

一种检测铜离子的荧光探针及其合成方法 Download PDF

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CN110551499B
CN110551499B CN201910860207.9A CN201910860207A CN110551499B CN 110551499 B CN110551499 B CN 110551499B CN 201910860207 A CN201910860207 A CN 201910860207A CN 110551499 B CN110551499 B CN 110551499B
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郑开波
李梦
陈慧
王丽红
郑海峡
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Abstract

本发明公开了检测铜离子的荧光探针及其制备方法。本发明的检测铜离子荧光探针，其结构式如下：
Figure DDA0002199505710000011
本发明同时提供了该探针的制备方法。本发明提供的荧光探针本身在缓冲溶液中呈现蓝色荧光，可与铜离子与发生特异性反应，生成具有黄色荧光的产物，随着铜离子浓度的增大，黄色荧光信号又逐渐消失；从而实现对铜离子的特异性检测。探针对铜离子也具有很好的选择性。

Description

一种检测铜离子的荧光探针及其合成方法
技术领域
本发明公开了一种能够快速检测铜离子的荧光探针及其合成方法和应用，具体的说就是一种能通过不同发射波长检测铜离子的荧光探针，属于化学分析检测技术领域。
背景技术
正常情况下人体内，除了铁和锌，铜离子是第三种最丰富的必需微量元素，成人体内总铜含量一般是70～80毫克。
铜离子在各种生理过程发挥重要作用，然而，铜离子作为有毒的重金属元素，若水平异常时，可引起氧化应激和神经系统疾病，包括阿尔茨海默氏症、帕金森、门克斯和威尔逊等疾病。所以，对铜离子的检测引起人们的高度重视。
目前关于Cu2+荧光探针的研究中，大多是基于单波长荧光发射强度改变的荧光探针，比如荧光淬灭或荧光增强。这些基于单波长发射的荧光探针易受一些因素的影响，比如：光漂白、探针分子的浓度、周围的微环境和光照射下的稳定性等。而比率荧光探针能够克服上述因素的影响。比率荧光探针是通过记录两个荧光发射峰的比率来实现对金属离子的检测的，它有利于增加响应范围，减少环境因素的影响。根据探针和不同浓度的铜离子反应，本发明探针在铜离子低浓度时，呈比率荧光信号，在铜离子高浓度时，呈现“开-关”型的荧光信号，多重荧光信号检测效果报道较少，具有一定应用前景。
发明内容
本发明所述的一种能检测铜离子的荧光探针，分子式为C26H15N3O2S2，结构式如下所示：
Figure BDA0002199505690000011
本发明所述的一种能检测铜离子的荧光探针，通过如下方法实现：
Figure BDA0002199505690000021
本发明所述的能检测铜离子的比值型荧光探针，通过如下方法实现：
将化合物1、2-吡啶甲酸、EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐)、DMAP(4-二甲氨基吡啶)加至反应瓶中，同时加入干燥二氯甲烷作为溶剂，常温搅拌，TLC点板监测反应至原料反应完全，柱层析得到目标产物。化合物1、2-吡啶甲酸、EDC、DMAP的摩尔比为1：1-5：1-3：0.1-0.3。
本发明将所述的荧光分子探针化合物应用于检测铜离子上。
本发明的优点，探针的合成只需要一步就可以完成，且后处理过程简单。探针的选择性好，灵敏度高。显示出对铜离子有良好的选择性及对其它共存离子良好的抗干扰能力。
附图说明
图1是实施例1中探针的1HNMR图谱。
图2是实施例1中探针的13CNMR图谱。
图3是实施例1中探针的HRMS图谱。
图4为实施例5中检测0～7μM的不同浓度的铜离子溶液的荧光光谱。
图5为实施例5中检测8～30μM的不同浓度的铜离子溶液的荧光光谱。
图6是实施例6中探针检测铜离子的选择性荧光光谱。
具体实施方式
实施例1探针分子的合成
Figure BDA0002199505690000022
实施例1将76.1mg(0.21mmol)化合物1、EDC(79.8mg,0.42mmol)、DMAP(2.9mg,0.02mmol)加至反应瓶中，同时加入8ml干燥重蒸二氯甲烷作为溶剂，再加入2-吡啶甲酸(104.5mg,0.85mmol)反应0.5h后，TLC点板监测反应至原料反应完全，按PE:DC＝1:5-10的洗脱剂比例过柱得到目标产物，产率为25.1％。
实施例2将53mg(0.15mmol)化合物1、EDC(57mg,0.30mmol)、DMAP(2.8mg,0.023mmol)加至反应瓶中，同时加入8ml干燥重蒸二氯甲烷作为溶剂，再加入2-吡啶甲酸(38.2mg,0.31mmol)反应0.5h后，TLC点板监测反应至原料反应完全，按PE:DC＝1:5-10的洗脱剂比例过柱得到目标产物，产率为43.3％。
实施例3将36.5mg(0.10mmol)化合物1、EDC(38.3mg,0.20mmol)、DMAP(3.1mg,0.025mmol)加至反应瓶中，同时加入8ml干燥重蒸二氯甲烷作为溶剂，再加入2-吡啶甲酸(52mg,0.5mmol)反应0.5h后，TLC点板监测反应至原料反应完全，按PE:DC＝1:5-10的洗脱剂比例过柱得到目标产物，产率为32％。
实施例4将56.2mg(0.16mmol)化合物1、EDC(93.2mg,0.49mmol)、DMAP(2.1mg,0.017mmol)加至反应瓶中，同时加入8ml干燥重蒸二氯甲烷作为溶剂，再加入2-吡啶甲酸(42.8mg,0.35mmol)反应0.5h后，TLC点板监测反应至原料反应完全，按PE:DC＝1:5-10的洗脱剂比例过柱得到目标产物，产率为25.6％。
实施例5探针检测铜离子
取实施例1制备的荧光探针化合物，溶解到DMSO溶液中，配置成100μmol的探针母液，将二水合氯化铜溶解到去离子水中，配置成1mmol的铜离子母液。配置DMF：HEPES缓冲液(0.01mM，pH＝7.4)＝4：6的光谱溶液，每根试管3mL。从探针母液中取出30μL(1μM)加入到每根试管当中，取不同体积的铜离子母液于前述盛有3mL光谱溶液和探针的试管中。反应20分钟后，采用350nm的激发波，用荧光光谱仪测试探针与不同浓度(0、1、2、3、4、5、6、7μM)的铜离子溶液的荧光光谱变化。荧光光谱变化情况如图4所示；用荧光光谱仪测试探针与不同浓度(8、9、10、11、12、13、14、15、16、17、18、19、20、22、24、26、28、30μM)的铜离子溶液的荧光光谱变化。如图4显示中随着加入(0～7μM)不同浓度的铜离子溶液后，在513nm处荧光发射逐渐增强；如图5显示加入(8～30μM)不同浓度的铜离子溶液后，在513nm处荧光发射逐渐减弱。
实施例6探针对铜离子的选择性检测
取实施例1制备的荧光探针化合物，溶解到DMSO溶液中，配置成100μmol的探针母液，将二水合氯化铜溶解到去离子水中，配置成1mmol的铜离子母液。配置DMF：HEPES缓冲液(0.01mM，pH＝7.4)＝4：6的光谱溶液，每根试管3mL。从探针母液中取出30μL(1μM)加入到每根试管当中，取相同浓度的不同离子母液于前述盛有3mL光谱溶液和探针的试管中。反应20分钟后，采用350nm的激发波，用荧光光谱仪测试探针与相同浓度的不同离子母液即(blank、Cu2+、K+、Na+、Ca2+、Mg2+、Hg2+、Fe3+、Fe2+、Ni2+、Co2+、Cd2+、Cr2+、Al3+、Pb2+)的荧光光谱变化情况如图6所示。结果显示，随着加入相同浓度的不同离子母液后，只有铜离子对探针有较高的响应性。

Claims (3)

1.一种荧光探针在检测铜离子上的应用，其特征在于，其分子式为：C26H15N3O2S2；其结构式如下：
Figure FDA0003653401050000011
2.根据权利要求1所述应用的荧光探针的合成方法，其特征在于，
步骤如下：
Figure FDA0003653401050000012
将化合物1、2-吡啶甲酸、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、4-二甲氨基吡啶加至反应瓶中，同时加入干燥二氯甲烷作为溶剂，常温搅拌，TLC点板监测反应至原料反应完全，柱层析得到目标产物。
3.根据权利要求2所述的荧光探针的合成方法，其特征在于：化合物1、2-吡啶甲酸、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、4-二甲氨基吡啶的摩尔比为1：1-5：1-3：0.1-0.3。
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