CN103601679A - 一种以吡唑啉为母体的还原型谷胱甘肽荧光探针 - Google Patents

一种以吡唑啉为母体的还原型谷胱甘肽荧光探针 Download PDF

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CN103601679A
CN103601679A CN201310648786.3A CN201310648786A CN103601679A CN 103601679 A CN103601679 A CN 103601679A CN 201310648786 A CN201310648786 A CN 201310648786A CN 103601679 A CN103601679 A CN 103601679A
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赵宝祥
苗俊英
王胜清
吴清华
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Abstract

本发明公开了一种以吡唑啉为母体的还原型谷胱甘肽荧光探针，所述探针是2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯。本发明的探针可以选择性的与还原型谷胱甘肽作用，具有荧光增强效应，可通过荧光光度法进行分析和实现对还原型谷胱甘肽的微量检测，灵敏度高，适于广泛推广。

Description

一种以吡唑啉为母体的还原型谷胱甘肽荧光探针
技术领域
本发明涉及一种荧光探针，尤其涉及一种以吡唑啉为母体的还原型谷胱甘肽荧光探针。
背景技术
吡唑啉衍生物具有较大摩尔消光系数和较高量子产率，常常修饰后用于荧光探针，并用作标记生物分子。近几年，利用荧光增强效应检测活体细胞中还原型谷胱甘肽的研究得到不断发展。
谷胱甘肽是细胞内最多的非蛋白巯基，在维持细胞生理功能中起着重要作用，包括细胞内的氧化还原反应，异物代谢，细胞内的信号传导与基因调控。更具体地说，谷胱甘肽是细胞内最多的小分子生物硫醇（1-10mM），并且还原型谷胱甘肽与氧化型谷胱甘肽之间存在着一个氧化还原平衡。研究发现，还原型谷胱甘肽在细胞的生长，和维持细胞正常功能的氧化还原平衡中起着关键的作用。此外，人体中谷胱甘肽浓度异常与癌症、阿尔茨海默氏症和心血管等疾病有关。因此，生物和环境样品中生物分子硫醇的检测始终吸引着科学家们极大的兴趣。已授权的专利【CN200710065564.3】、【CN200810020777.9】和【CN201010558433.0】中可以实现选择生物体中的活性硫醇，但是缺乏对还原型谷胱甘肽的专一性。经检索，利用合成的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯作为还原型谷胱甘肽荧光探针的应用还未见报道。
发明内容
针对现有技术的不足，本发明要解决的问题是提供一种以吡唑啉为母体的还原型谷胱甘肽荧光探针。
本发明所述的以吡唑啉为母体的还原型谷胱甘肽荧光探针，其特征在于：所述探针是2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯，其结构式如式（I）所示：
Figure BDA0000430029170000011
上述2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯由如下方法制得：
将1-(2-羟基苯基)-3-苯基丙-2-烯-1-酮与苯肼反应得到2-(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯酚，然后与丙烯酸酰氯反应得到2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯。
上述2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯作为还原型谷胱甘肽探针的应用。
本发明所述的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯可以与还原型谷胱甘肽发生迈克尔加成反应生成具有荧光性质的吡唑啉谷胱甘肽产物。
配制2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的PBS/乙醇缓冲液（20mMPBS，pH=7.4，3:7，体积比）的溶液，分别定量加入微升级的Cys,Hcy,GSH,Arg,Asp,Glu,Gly,His,Lys,Ser,Thr,Trp,Tyr,Val，KNO3,Ca(NO3)2,NaNO3,Mg(NO3)2,Zn(NO3)2,Fe(NO3)3,过氧化氢和葡萄糖的水溶液。通过荧光分光光度法测试对不同氨基酸、人体常见金属离子、还原型谷胱甘肽、双氧水和葡萄糖的选择性和响应能力。结果显示2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物对还原型谷胱甘肽具有很好的选择性，加入还原型谷胱甘肽前后对照显示具有很强强荧光增强效应。见图1。
本发明设计合成的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯可以与还原型谷胱甘肽发生加成反应生成具有荧光性质的物质，从而可以专一性的选择还原型谷胱甘肽，把还原型谷胱甘肽与半胱氨酸、同型半胱氨酸进行区分。明显提高了其作为荧光探针检测活体细胞中还原型谷胱甘肽高选择性和高灵敏度，实现对还原型谷胱甘肽的微量检测。
本发明提供的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯能使膜渗透性增强，而且低毒抗荧光漂白。
附图说明
图1为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的PBS/乙醇缓冲液（20mMPBS，pH=7.4，3:7，体积比）的溶液加入不同的氨基酸、常见金属离子、双氧水、葡萄糖和还原型谷胱甘肽的荧光发射图谱。
图2为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的核磁共振氢谱。
图3为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的核磁共振碳谱。
图4为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯与还原型谷胱甘肽加成产物的核磁共振氢谱。
图5为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯与还原型谷胱甘肽加成产物的核磁共振碳谱。
图6为2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯在HeLa细胞内荧光显微成像图
其中：A组是在37℃条件下，HeLa细胞在3.0μM的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的细胞培养液中培养0.5小时的图像；B组是先把HeLa细胞在100mM的N-乙基马来酰亚胺中浸泡8小时，然后再在3.0μM的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯的细胞培养液中培养0.5小时的图像。
具体实施方式
实施例1
由1-(2-羟基苯基)-3-苯基丙-2-烯-1-酮合成2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯再与还原型谷胱甘肽反应生成吡唑啉谷胱甘肽衍生物的反应过程如下式所示：
Figure BDA0000430029170000031
将查尔酮(0.224g,1.0mmol)（1），0.162g苯肼（2）（1.5mmol），氢氧化钠(0.12g,3.0mmol)，加入15mL无水乙醇中，加热至回流，继续反应四小时左右，反应完全后降温，残留物中加入100mL水，调节pH值到5，水相继续用二氯甲烷萃取三次，合并有机相，无水硫酸镁干燥，石油醚：二氯甲烷=5:1为洗脱剂，柱层析的淡黄色固体（3）0.144g，熔点：167-168℃收率：45.8%。
核磁共振氢谱测定：1H NMR(300MHz,CDCl3):δ3.25(dd,1H,J=7.5,17.1Hz,4-Htrans),3.95(dd,1H,J=12.3,17.1Hz,4-Hcis),5.22(dd,1H,J=7.5,12.3Hz,5-H of pyrazoline),6.81-6.90(m,2H,Ar-H),6.96(dd,2H,J=1.2,9.0Hz,Ar-H),7.04-7.13(m,2H,Ar-H),7.16-7.20(m,2H,Ar-H),7.22-7.31(m,2H,Ar-H),7.32-7.38(m,4H,Ar-H),10.78(s,1H,OH)。
核磁共振碳谱测定：13C-NMR(75MHz,CDCl3):157.3,149.7,144.1,141.9,130.5,129.3,129.1,127.9,127.2,125.9,119.9,119.4,116.7,116.4,113.4,63.4,44.0。
把吡唑啉衍生物3(1.0mmol)和三乙胺(2.0mmol)溶于5mL的二氯甲烷中，在冰水浴条件下加入丙烯酰氯(1.3mmol)，反应体系缓慢升温至室温然后搅拌4小时。停止反应后加入二氯甲烷50mL，饱和食盐水洗涤三次，无水硫酸镁干燥，二氯甲烷：石油醚=1:1柱层析得淡黄色固体（L）219mg,熔点：113-114℃收率：59.5%。
核磁共振氢谱测定：1H NMR(300MHz,CDCl3):δ3.15(dd,1H,J=6.9,16.8Hz,4-Htrans),3.84(dd,1H,J=12.3,16.8Hz,4-Hcis),5.21(dd,1H,J=6.9,12.3Hz,5-H of pyrazoline),6.05(dd,1H,J=1.2,10.5Hz,-CH=CH2),6.43(dd,1H,J=10.5,17.1Hz,-CH=CH2),6.64(dd,1H,J=1.2,17.1Hz,-CH=CH2),6.76(t,1H,J=7.2Hz,Ar-H),6.98(d,2H,J=7.8Hz,Ar-H),7.09-7.15(m,3H,Ar-H),7.19-7.39(m,7H,Ar-H),7.60(dd,1H,J=1.8,7.8Hz,Ar-H)。
核磁共振碳谱测定：13C-NMR(75MHz,CDCl3):164.6,147.7,144.4,143.5,142.3,132.7,129.2,129.1,128.8,128.7,128.3,127.6,126.3,125.9,125.7,123.7,119.3,113.7,63.7,45.2;HRMS:calcd for[M+H]+C24H21N2O2:369.1603;found:369.1569。
在乙醇与pH=7.4的PBS缓冲溶液中加入(1.8mmol)的还原型谷胱甘肽与(0.3mmol)的配体L，然后室温搅拌12小时，减压蒸馏除去部分乙醇，抽滤，洗涤，得白色固体100mg,熔点：167-170℃收率：14.8%。
核磁共振氢谱测定：1H NMR(300MHz,DMSO-d6):δ1.87-1.94(m,2H),2.27-2.41(m,2H),2.65-2.73(m,1H),2.84(t,1H,J=6.3Hz),2.92-2.98(m,3H),3.08(dd,2H,J=6.0,17.4Hz),3.27-3.31(m,1H),3.62(s,2H),3.96(dd,1H,J=12.3,17.4Hz),5.45(dd,1H,J=6.0,12.0Hz),6.73(t,1H,J=7.5Hz),6.93(d,2H,J=8.1Hz),7.13-7.44(m,11H),7.69(d,1H,J=7.5Hz),8.50(s,2H)。
核磁共振碳谱测定：13C-NMR(75MHz,DMSO-d6):172.5,171.4,170.8,170.7,170.6,147.9,144.7,144.4,142.6,133.2,129.9,129.4,129.3,127.9,126.7,126.3,125.7,124.3,113.6,62.9,53.7,53.1,45.1,42.3,35.0,33.8,32.2,27.5,26.7;HRMS:calcd for[M+H]+C34H38N5O8S:676.2441;found:676.2272。
实施例2
用微量注射器分别向盛有10mL配好的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物的PBS/乙醇缓冲液（20mM PBS，pH=7.4，3:7，体积比）的溶液中加入10当量Cys,Hcy,GSH,Arg,Asp,Glu,Gly,His,Lys,Ser,Thr,Trp,Tyr,Val，KNO3,Ca(NO3)2,NaNO3,Mg(NO3)2,Zn(NO3)2,Fe(NO3)3,过氧化氢和葡萄糖的水溶液，作用12小时候，进行荧光分光光度法测试，显示2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物对还原型谷胱甘肽具有很好的选择性，加入还原型谷胱甘肽前后对照显示具有很强强荧光增强效应。
结果见图1。
实施例3
细胞内荧光成像测试：
实验分为对照组A和B两组，对照组A：在37℃条件下，HeLa细胞在加入3.0μM的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物的细胞培养液中培养0.5小时；对照组B：HeLa细胞在含有100mM N-乙基马来酰亚胺细胞培养液中浸泡8小时，PBS缓冲溶液洗涤三次后，再在加入3.0μM的2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物的细胞培养液中培养0.5小时。
荧光成像显示2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯衍生物较好地渗透进细胞内。对照组A细胞内显较强荧光。对照组B不显荧光。见图6。

Claims (1)

1.一种以吡唑啉为母体的还原型谷胱甘肽荧光探针，其特征在于：所述探针是2–(1,5-二苯基-4,5-二氢-1H-吡唑-3-基)苯基丙烯酸酯，其结构式如式（I）所示：
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CN106537124A (zh) * 2014-05-14 2017-03-22 新加坡科技研究局 丙烯酸的检测

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