CN107778196B - 一种芘衍生物及其合成方法和应用 - Google Patents

一种芘衍生物及其合成方法和应用 Download PDF

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CN107778196B
CN107778196B CN201711089648.0A CN201711089648A CN107778196B CN 107778196 B CN107778196 B CN 107778196B CN 201711089648 A CN201711089648 A CN 201711089648A CN 107778196 B CN107778196 B CN 107778196B
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于春伟
张军
傅琼瑶
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Abstract

本发明涉及铜离子的检测，具体的说是一种芘衍生物及其合成方法和应用。芘衍生物P如式一。本发明通过有效的合成手段得到的苯甲酰肼衍生物P，对铜离子表现出较好的选择性，在优化实验条件基础上，可以实现对铜离子的检测。

Description

一种芘衍生物及其合成方法和应用
技术领域
本发明涉及铜离子的检测，具体的说是一种芘衍生物及其合成方法和应用。
背景技术
在已报道的荧光分子探针中，多为同种识别机理实现特定目标物质的检测[1-3]。同一种探针，采用不同机理检测不同金属离子也有报道[4]。但是，同一种探针，不同机理识别同一种金属离子的报道较为少见。
芘衍生物具有优良的光学性质、合成简单，在金属离子荧光探针中有着广泛的应用。基于芘衍生物的荧光探针已被应用到汞离子、铅离子、铁离子、铬离子以及铜离子的检测中。但是基于一种探针，利用两种机理识别铜离子未见报道。
发明内容
本发明的目的是提供一种芘衍生物及其合成方法和应用。
为实现上述目的，本发明所采用的技术方案为：
一种芘衍生物，芘衍生物P如式一，
Figure BDA0001460891450000011
一种芘衍生物P的制备方法，将邻羟基苯甲酸乙酯与水合肼在无水乙醇中，75-80℃回流4-6h，冷却至室温后，析出固体在无水乙醇中， 75-80℃下与芘甲醛反应4-6h，冷却后将析出固体抽滤，得淡黄色固体式一纯品P，反应式为：
Figure BDA0001460891450000021
所述邻羟基苯甲酸乙酯与水合肼以摩尔比1︰3-5反应；
析出固体与芘甲醛以摩尔比1︰1-1.2反应。
一种芘衍生物P的应用，所述芘衍生物P在作为荧光探针中的应用。
所述芘衍生物P在作为荧光探针在检测铜离子中的应用。
本发明所具有的优点：
本发明通过有效的合成手段得到芘衍生物P，合成步骤简单，成本低，易于提纯、产率高(85％)。该化合物对铜离子具有好的选择性，通过在低浓度荧光猝灭、在高浓度荧光增强两种不同识别机理检测铜离子，在实际测试中检出限低。
附图说明
图1为本发明实施例提供的芘衍生物P的质谱图。
图2为本发明实施例提供的芘衍生物P的核磁谱图。
图3为本发明实施例提供的铜离子低浓度时与芘衍生物P的络合质谱图。
图4为本发明实施例提供的铜离子高浓度时与芘衍生物P的络合质谱图。
图5为本发明实施例提供的化合物P(10μM)与Cu2+(0—10.0μ M)在乙醇/水(v/v，7:3)中，pH6.8条件下的荧光滴定光谱。
具体实施方式
下面结合附图和实施例对本发明作进一步的解释说明。
实施例
芘衍生物P为式1所示的化合物。
芘衍生物P的制备：将1mM邻羟基苯甲酸乙酯与其5倍摩尔量的水合肼在30mL的无水乙醇中，75-80℃回流4h，冷却至室温后，析出固体过滤，固体再经无水乙醇洗涤，干燥后所得中间体化合物直接用于下一步。1mM中间体在无水乙醇中，75-80℃下与芘甲醛以摩尔比1︰1反应4h，冷却后将析出固体抽滤，依次用大量水和无水乙醇洗涤，干燥，得淡黄色固体纯品P，产率85％(参见图1和图2)。
由图1和2中可见分子离子峰和H的化学位移可知芘衍生物P的生成。
应用例
芘衍生物P对铜离子的光学识别
1)光学测定条件：在乙醇/水(7/3，v/v)介质中，用HEPES缓冲溶液控制体系pH为6.8。
2)实验方法：5mL比色管中，加入不同浓度的Cu2+标准溶液，而后加入50μL含上述作为探针分子的纯品P(1mM)的DMSO标准溶液，以乙醇/水(7/3，v/v，20mM HEPES，pH 6.8)稀释至刻度，摇匀。测试时，激发/发射狭缝＝10/10nm，激发波长为349nm(参见图5)。
由图5 Cu2+的荧光滴定谱图可见，P(10μM)的乙醇/水(7/3，v/v， 20mM HEPES，pH6.8)溶液，荧光很弱，说明体系中P自身无荧光；加入低浓度的Cu2+后，441nm处的荧光峰强度逐渐降低并红移，说明两个探针P与Cu2+以摩尔比2:1络合(MS:m/z 792.16[2P+Cu2++Cl-]+)(图3和图5)，形成激基缔合物，造成荧光猝灭；随着Cu2+浓度的增加，451nm处的荧光强度随之增强，该识别机理主要是分子内电子转移机理(MS:m/z 427.06 [P+Cu2++Cl-]+)(图4和图5)。
参考文献：
1.Y.T.Li and C.M.Yang,Chem.Commun.,2003,2884-2885.
2.L.Fabbrizzi,M.Licchelli,P.Pallavicini,A.Perotti,A.Taglietti and D.Sacchi,Chem.Eur.J.,1996,2,75-82.
3.M.N.Elizabeth,J.L.Stephen,J.Mater.Chem.,2005,15,2778-2783.
4.张灯青.化学进展,2009,21，715-723。

Claims (3)

1.一种芘衍生物的应用，其特征在于：芘衍生物P在作为荧光探针在非疾病诊断治疗中检测铜离子中的应用；
所述芘衍生物P如式一，
Figure DEST_PATH_IMAGE002
式一。
2.按权利要求1所述的芘衍生物的应用，其特征在于：所述芘衍生物P的制备方法为：
将邻羟基苯甲酸乙酯与水合肼在无水乙醇中，75-80 ℃回流4-6 h，冷却至室温后，析出固体在过量的无水乙醇中，75-80 ℃下与芘甲醛反应4-6h，冷却后将析出固体抽滤，得淡黄色固体式一纯品P。
3.按权利要求2所述的芘衍生物的应用，其特征在于：所述邻羟基苯甲酸乙酯与水合肼以摩尔比1︰3-5反应；
析出固体与芘甲醛以摩尔比1︰1-1.2反应。
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