CN115490680A - 基于苯并噻唑衍生物的香豆素类荧光探针及其制备方法和应用 - Google Patents
基于苯并噻唑衍生物的香豆素类荧光探针及其制备方法和应用 Download PDFInfo
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- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
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- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
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- 238000006862 quantum yield reaction Methods 0.000 description 1
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Abstract
本发明属于化学分析测试领域,具体涉及一种基于苯并噻唑衍生物的香豆素类荧光探针及其制备方法和应用。将7‑(二乙基氨基)香豆素‑3‑甲酸和2‑甲基苯并噻唑‑6‑胺溶于二氯甲烷中,加入缩合剂1‑羟基苯并三唑(HOBT)、1‑乙基‑(3‑二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)和三乙胺。常温搅拌,所得化合物通过柱层析法分离提纯,得到最终产物。本发明的香豆素类荧光探针在镉离子的参与下,在十二烷基硫酸钠(SDS)表面活性剂中,可特异性识别磷酸三丁酯(TBP)。
Description
技术领域
本发明属于化学分析测试领域,具体涉及一种基于苯并噻唑衍生物的香豆素类荧光探针及其制备方法和应用。
背景技术
磷酸三丁酯(tributyl phosphate,TBP)是一种有机磷酸酯,它是一种无色、有刺激性气味的液体。磷酸三丁酯(TBP)有着阻燃效果好、脂溶性高,热稳定性高的优点,是一种应用比较广泛的烷基有机磷系阻燃剂。研究发现,磷酸三丁酯(TBP)广泛存在于各种环境介质中,具有远距离输送特性,甚至在人迹稀少的北极海水中和高原冰川积雪中被检测出来。它作为一种典型的有机磷酸酯,有一定的毒性。研究表明,部分有机磷酸酯,有着不可逆地与神经突触乙酰胆碱酯酶结合的能力,会干扰神经冲动向生物系统的传递,并通过呼吸肌麻痹导致生物死亡。
目前,检测这些有机磷酸酯的分析技术有很多,例如电化学法、高效液相色谱法、核磁共振波谱(1H和31P NMR)等。但是,上述这些分析技术成本高、操作复杂。
发明内容
本发明提供了一种基于苯并噻唑衍生物的香豆素类荧光探针及其制备方法和应用。
荧光探针的结构式为:
基于苯并噻唑衍生物的香豆素类荧光探针的制备方法为:将2-甲基苯并噻唑-6-胺和7-(二乙基氨基)香豆素-3-甲酸溶于二氯甲烷溶剂中,加入缩合剂1-羟基苯并三唑(HOBT)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)和三乙胺,室温搅拌3-4小时,反应结束后,减压除去溶剂,通过柱层析法,得到黄色固体。
其中,2-甲基苯并噻唑-6-胺和7-(二乙基氨基)香豆素-3-甲酸的摩尔当量比为1:1。
缩合剂1-羟基苯并三唑(HOBT)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI),三乙胺摩尔当量比为1.2:1.2:2-2:2:3。
上述基于苯并噻唑衍生物的香豆素类荧光探针在Cd2+的参与下,在十二烷基硫酸钠(SDS)表面活性剂中可以特异性识别有机磷酸酯中的磷酸三丁酯(TBP)。
其中,Cd2+的浓度为10-20mM,十二烷基硫酸钠的浓度为3-4mM,荧光探针浓度为2mM,磷酸三丁酯浓度10μM-50mM
本发明的有益效果在于:本发明原料易得,合成方法较为简单,反应条件易于控制,反应完成后,通过简单的后处理即可得到纯品。在Cd2+的参与下,香豆素类荧光探针灵敏度高、选择性好,能够在在十二烷基硫酸钠(SDS)表面活性剂中可以特异性识别有机磷酸酯中的磷酸三丁酯(TBP)。
附图说明:
图1为实施例1制备的香豆素类荧光探针在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与不同离子(K+、Zn2+、Li+、Fe3+、Cd2+、Fe2+、Ag+、Co2+、Na+、Ca2+、Cu2+,浓度为10mM)作用后的荧光光谱图。
图2为实施例1制备的香豆素类荧光探针在Cd2+参与下在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与磷酸三丁酯(TBP)(浓度为10mM)作用后的荧光光谱图。
图3为实施例1制备的香豆素类荧光探针在Cd2+参与下,在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与不同有机磷酸酯(TMP、TEP、TBP、DCPP、DMECP、DMMCP、DCNP、DMMP,浓度为10mM)作用后的荧光光谱图。
图4为实施例1制备的基于苯并噻唑衍生物的香豆素荧光探针化合物的氢谱。
图5为实施例1制备的香豆素类荧光探针在Cd2+(20mM)参与下在十二烷基硫酸钠(SDS)表面活性剂(浓度为3mM)中与磷酸三丁酯(TBP)(浓度为10mM)作用后的荧光光谱图。
具体实施方式
下面结合具体的实施方式对本发明进行详细说明。
实施例1
将2-甲基苯并噻唑-6-胺(0.0385g,1mmol)和7-(二乙基氨基)香豆素-3-甲酸(0.06125g,1mmol),溶于二氯甲烷中,加入缩合剂1-羟基苯并三唑(HOBT)(0.038g,1.2mmol)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)(0.0538g,1.2mmol)和三乙胺(0.047g,2mmol)。室温搅拌3小时,反应结束后,减压除去溶剂,用二氯甲烷和甲醇的体系(DCM:MeOH=60:1)过柱子,得到黄色固体,得到0.0715g,产率为75%。
在该探针的结构中,由两部分组成:香豆素衍生物和苯并噻唑衍生物。香豆素衍生物具有斯托克斯位移大、量子产率高等优点。香豆素作为荧光基团,在香豆素的3号位上取代吸电子基(羧基),在7号位上取代给电子基团(氮二甲基),形成强荧光的推拉体系。靶点为苯并噻唑衍生物,苯并噻唑及其衍生物是重要的杂环化合物,有着光学功效好、有着刚性的共轭结构等优点。
具体应用方法为:香豆素类荧光探针对Cd2+的选择性识别。首先,在96孔板中分别加入2uL的离子溶液(每个孔中的离子分别为K+、Zn2+、Li+、Fe3+、Cd2+、Fe2+、Ag+、Co2+、Na+、Ca2 +、Cu2+,浓度为10mM,在孔中最终浓度为100μM)、其次加入196uL的十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM,在孔中最终浓度为40μM)和2uL的基于苯并噻唑衍生物的香豆素荧光探针(浓度为2mM,在孔中最终浓度为20μM),空白对照为不加离子的含有香豆素类化合物的溶液。先将每个孔的溶液混匀,并测出每个孔中溶液的荧光强度。结果表明,含Cd2+的溶液的荧光强度在475nm处显著增强;而该探针对于其他离子无特别明显的荧光变化,从而显示出在十二烷基硫酸钠(SDS)表面活性剂探针对于Cd2+的选择性识别作用。
香豆素类荧光探针对磷酸三丁酯(TBP)的选择性识别。向96孔板中先加入2uLCd2+(浓度为10mM,在孔中最终浓度为100μM),再加入194uL十二烷基硫酸钠(SDS)(浓度为4mM,在孔中最终浓度为40μM),再加2uL的基于噻唑衍生物的香豆素类荧光探针(浓度为2mM,在孔中最终浓度为20μM),将每个孔的溶液混匀,最后加入2uL有机磷酸酯(TMP、TEP、TBP、DCPP、DMECP、DMMCP、DCNP、DMMP)(浓度为10mM,在孔中最终浓度为100μM),再次混匀,并测出每孔中溶液的荧光强度。同时以不加有机磷酸酯的含Cd2+的香豆素荧光探针溶液作为空白对照。结果显示,含磷酸三丁酯(TBP)的探针在475nm处有明显的下降,而该探针对于其它有机磷酸酯无特别明显的荧光变化。从而显示出在十二烷基硫酸钠(SDS)表面活性剂中,在Cd2+参与下,香豆素荧光探针化合物对磷酸三丁酯(TBP)有选择性识别作用。
图1为实施例1制备的香豆素类荧光探针在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与不同离子(K+、Zn2+、Li+、Fe3+、Cd2+、Fe2+、Ag+、Co2+、Na+、Ca2+、Cu2+,浓度为10mM)作用后的荧光光谱图。图中显示,滴加不同离子溶液(浓度为10mM),探针的荧光强度变化情况。当加入镉离子(浓度为10mM)时,探针在475nm处的荧光强度发生了显著的升高;而该香豆素类荧光探针在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM),对于其他离子无特别明显的荧光变化,从而显示出在该体系中化合物对于Cd2+的选择性识别作用。
图2为实施例1制备的香豆素类荧光探针在Cd2+参与下在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与磷酸三丁酯(TBP)(浓度为10mM)作用后的荧光光谱图。图中显示,当加入磷酸三丁酯(TBP)后,探针在475nm处的荧光强度发生了下降。与未加有机磷酸酯的探针相比,荧光强度下降明显。与未加离子的探针相比,荧光强度略微升高。该探针在十二烷基硫酸钠(SDS)表面活性剂中,在Cd2+参与下,对于磷酸三丁酯(TBP)的选择性识别作用。
图3为实施例1制备的香豆素类荧光探针在Cd2+参与下,在十二烷基硫酸钠(SDS)表面活性剂(浓度为4mM)中与不同有机磷酸酯(TMP、TEP、TBP、DCPP、DMECP、DMMCP、DCNP、DMMP,浓度为10mM)作用后的荧光光谱图。图中显示,滴加不同有机磷酸酯,探针的荧光强度变化情况。图中显示,探针当加入磷酸三丁酯(TBP)后,探针的荧光强度在475nm处发生了显著的下降,而加入其它有机磷酸酯荧光强度无明显变化。从而显示出该探针在十二烷基硫酸钠(SDS)(浓度为4mM)表面活性剂中,在Cd2+参与下,对于磷酸三丁酯(TBP)的选择性识别作用。
图4为实施例1制备的基于苯并噻唑衍生物的香豆素荧光探针化合物的氢谱。1HNMR(400MHz,CDCl3)δ11.03(s,1H),8.74(s,1H),8.57(s,1H),7.85(d,J=8.7Hz,1H),7.51–7.39(m,2H),6.63(dd,J=9.0,2.2Hz,1H),6.48(d,J=2.0Hz,1H),3.41(s,4H),2.79(s,3H),1.22(s,6H).
向96孔板中先加入2uLCd2+(浓度为20mM,,在孔中最终浓度为200μM),再加入194uL十二烷基硫酸钠(SDS)(浓度为3mM,在孔中最终浓度为30μM),再加2uL的基于噻唑衍生物的香豆素类荧光探针(浓度为2mM,在孔中最终浓度为20μM),将每个孔的溶液混匀,最后加入2uL磷酸三丁酯(浓度为10mM,在孔中最终浓度为100μM),再次混匀,并测出每孔中溶液的荧光强度。同时以不加Cd2+的香豆素荧光探针溶液作为空白对照。结果表明,当加入磷酸三丁酯后,探针在475nm处的荧光强度发生了下降。与未加有机磷酸酯的探针相比,荧光强度略微下降。该探针在十二烷基硫酸钠(SDS)表面活性剂中,在Cd2+参与下,对于磷酸三丁酯(TBP)的特异性识别不明显。
图5为对比实施例1制备的香豆素类荧光探针在Cd2+(20mM)参与下在十二烷基硫酸钠(SDS)表面活性剂(浓度为3mM)中与磷酸三丁酯(TBP)(浓度为10mM)作用后的荧光光谱图。图中显示,当加入磷酸三丁酯(TBP)后,探针在475nm处的荧光强度发生了下降。与未加有机磷酸酯的探针相比,荧光强度略微下降。与未加离子的探针相比,荧光强度略微升高。该探针在十二烷基硫酸钠(SDS)(浓度为3mM)表面活性剂中,在Cd2+(20mM)参与下,对于磷酸三丁酯(TBP)的特异性识别不明显。
实施例2
将2-甲基苯并噻唑-6-胺(0.03g,1mmol)和7-(二乙基氨基)香豆素-3-甲酸(0.06125g,1mmol),溶于二氯甲烷中,加入缩合剂1-羟基苯并三唑(HOBT)(0.0522g,1.5mmol)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)(0.00369g,1.5mmol)和三乙胺(0.0552g,3mmol)。室温搅拌4小时,反应结束后,减压除去溶剂,用二氯甲烷和甲醇的体系(DCM:MeOH=60:1)过柱子,得到黄色固体,得到0.0438g,产率为59%。
实施例3
将2-甲基苯并噻唑-6-胺(0.03g,1mmol)和7-(二乙基氨基)香豆素-3-甲酸(0.06125g,1mmol),溶于二氯甲烷中,加入缩合剂1-羟基苯并三唑(HOBT)(0.0491g,2mmol)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)(0.0699g,2mmol)和三乙胺(0.0552g,3mmol)。室温搅拌4小时,反应结束后,减压除去溶剂,用二氯甲烷和甲醇的体系(DCM:MeOH=60:1)过柱子,得到黄色固体,得到0.0351g,产率为47.2%。
Claims (6)
2.一种如权利要求1所述的基于苯并噻唑衍生物的香豆素类荧光探针的制备方法,其特征在于,所述制备方法为:将2-甲基苯并噻唑-6-胺和7-(二乙基氨基)香豆素-3-甲酸溶于二氯甲烷中,加入缩合剂1-羟基苯并三唑(HOBT)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI)和三乙胺,室温搅拌3-4小时,反应结束后,减压除去溶剂,通过柱层析法,得到黄色固体。
3.如权利要求1基于苯并噻唑衍生物的香豆素类荧光探针的制备方法,其特征在于,所述2-甲基苯并噻唑-6-胺和7-(二乙基氨基)香豆素-3-甲酸的摩尔当量比为1:1。
4.如权利要求1基于苯并噻唑衍生物的香豆素类荧光探针的制备方法,其特征在于,所述缩合剂1-羟基苯并三唑(HOBT)、1-乙基-(3-二甲基氨基醛)碳酰二亚胺盐酸盐(EDCI),三乙胺摩尔当量比1.2:1.2:2-2:2:3。
5.一种如权利要求1所述的基于苯并噻唑衍生物的香豆素类荧光探针的应用,其特征在于,所述基于苯并噻唑衍生物的香豆素类荧光探针在Cd2+的参与下,在十二烷基硫酸钠(SDS)表面活性剂中可以特异性识别有机磷酸酯中的磷酸三丁酯(TBP)。
6.如权利要求5所述的基于苯并噻唑衍生物的香豆素类荧光探针的应用,其特征在于,所述Cd2+的浓度为10-20mM,十二烷基硫酸钠的浓度为3-4mM,荧光探针浓度为2mM,磷酸三丁酯浓度10μM-50mM。
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