CN106518855B - 一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针及其应用 - Google Patents

一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针及其应用 Download PDF

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CN106518855B
CN106518855B CN201610976291.7A CN201610976291A CN106518855B CN 106518855 B CN106518855 B CN 106518855B CN 201610976291 A CN201610976291 A CN 201610976291A CN 106518855 B CN106518855 B CN 106518855B
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赵宝祥
苗俊英
李东鹏
王朝阳
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Abstract

本发明公开了一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针，所述荧光探针是由黄酮醇荧光团与半川菁荧光团通过非共轭连接而成，命名为L‑HF1，其化学结构式如式(I)所示。本发明还公开了所述荧光探针在检测液体或细胞中的二氧化硫衍生物的应用。实验证实本发明的探针可以选择性的与二氧化硫衍生物作用，使测试体系由红色变为无色，使得检测肉眼可辨，并且荧光由红色变为绿色，这些现象可以通过紫外吸收仪及荧光分光光度计进行分析。同时，本发明公开的该荧光探针可实现对微量二氧化硫衍生物的高灵敏度检测，具有重要的应用价值。

Description

一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光 探针及其应用
技术领域
本发明涉及一种半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针，尤其涉及一种能检测肝癌细胞内源性二氧化硫衍生物的荧光探针及其应用；属于有机小分子荧光探针技术领域。
背景技术
黄酮醇是具有ESIPT(激发态分子内质子转移)现象的、具有较高的荧光量子产率的荧光结构，是很重要的绿色荧光染料，经过修饰后用于发光材料、化学传感器以及标记生物分子。近几年利用荧光变化检测活体细胞中的二氧化硫衍生物研究得到不断发展。
细胞可以利用半胱氨酸等底物及细胞内酶的作用下产生二氧化硫衍生物——亚硫酸盐及亚硫酸氢盐，可参与细胞内多种生理过程，比如改变心率、降低血压及参与炎症反应等。但是体内二氧化硫衍生物含量过高会引起一系列不良反应，对人体健康造成危害。同时，二氧化硫是非常有害的空气污染物。所以对它的准确检测及控制具有重要的意义。
发明内容
本发明要解决的问题是提供一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针，且该探针具有高选择性和高灵敏度从而具有实际应用价值。
本发明所述的以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针，其特征在于：所述荧光探针简称是L-HF1，其化学结构式如式(I)所示：
上述荧光探针化合物L-HF1由如下方法制得：
邻羟基苯乙酮与对羧基苯甲醛经二步反应关环得到黄酮醇荧光团，然后通过酰胺键的构建引入芳香醛基，进而与吲哚盐缩合得到化合物L-HF1。
实验证实：本发明所述的二氧化硫衍生物比例荧光探针L-HF1可以与半川菁荧光团中的烯键发生Michael加成反应，从而阻断半川菁荧光团的共轭，使得其红色荧光减弱直至消失，而黄酮醇荧光团的特征绿色荧光由于荧光共振能量转移的阻断而得以重现，同时半川菁的特征紫外吸收峰消失，从而达到检测的效果，见图1。
本发明所述以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针在检测液体或细胞中的二氧化硫衍生物的应用。
其中：所述液体或细胞优选是PBS/DMF缓冲体系、L-02细胞、HepG2细胞或Hela细胞。
具体的，配制L-HF1在PBS/DMF缓冲体系(pH＝7.4，DMF体积分数25％)中的溶液，分别定量加入微升级的阴离子(F-,Cl-,Br-,I-,HCO3 -,NO3 -,NO2 -,N3 -,AcO-,H2PO4 -,ClO-,ClO3 -,SO4 2-,HSO4 -,HS-,SCN-,S2O3 2-,HSO3 -及SO3 2-)和各种氨基酸分子(glutamate，histidine，lysine，tryptophan，valine，arginine，sarcosine，aspartic acid，cysteine，homocysteine，glutathione)的水溶液。通过荧光分光光度法测试对不同氨基酸、人体常见阴离子的选择性和响应能力，结果见图2、图3。
往活HeLa细胞或L-02细胞中加入探针L-HF1，然后用亚硫酸氢钠培育细胞，对照加入亚硫酸氢钠前后细胞内荧光显微成像变化，结果见图4、图5。
本发明所述以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针在检测肝癌细胞内源性二氧化硫衍生物中的应用。
往活HepG2细胞中加入探针L-HF1，然后加入硫代硫酸钠及GSH以刺激该类细胞产生内生的亚硫酸氢盐，采集刺激前后细胞内荧光显微成像变化，结果见图6。
本发明设计合成的L-HF1，可以与二氧化硫衍生物发生亲核加成反应，从而使溶液荧光由红色变为绿色，肉眼可分辨，且具有很好的选择性与专一性，同时具有极高的灵敏度，实现了对二氧化硫衍生物的微量高灵敏度检测，具有重要的应用价值。
附图说明
图1：为探针L-HF1的PBS/DMF缓冲体系(pH＝7.4，DMF体积分数25％，5μM)中加入不同10当量的亚硫酸氢钠的荧光图谱及紫外吸收图谱随时间的变化。其中：a为荧光图谱，b为紫外吸收图谱。
图2：为探针L-HF1的PBS/DMF缓冲体系(pH＝7.4，DMF体积分数25％，5μM)中加入不同种类的阴离子的荧光发射图谱。其中：a为荧光曲线图谱，b为对应的比例荧光柱状图谱。
图3：为探针L-HF1的PBS/DMF缓冲体系(pH＝7.4，DMF体积分数25％，5μM)中加入不同种类的氨基酸的荧光发射图谱。其中：其中：a为荧光曲线图谱，b为对应的比例荧光柱状图谱。
图4：为探针L-HF1在活HeLa细胞内荧光显微成像图。HeLa细胞是在37℃条件下，于加入5μM的探针L-HF1的细胞培养液中培养1小时，然后用不同浓度的亚硫酸氢钠细胞培养液培育0.5小时。其中：a为细胞成像效果图，b为对应的比例荧光信号统计数据柱状图。
图5：为探针L-HF1在活L-02细胞内荧光显微成像图。L-02细胞是在37℃条件下，于加入5μM的探针L-HF1的细胞培养液中培养1小时，然后用不同浓度的亚硫酸氢钠细胞培养液培育0.5小时，或用硫代硫酸钠和GSH培育0.5小时。其中：a为细胞成像效果图，b为对应的比例荧光信号统计数据柱状图。
图6：为探针L-HF1在活HepG2细胞内荧光显微成像图。HepG2细胞是在37℃条件下，于加入5μM的探针L-HF1的细胞培养液中培养1小时，然后用硫代硫酸钠和GSH培育0.5小时。HepG2细胞是在37℃条件下，于加入5μM的探针L-HF1的细胞培养液中培养1小时，然后用TNBS(2,4,6-trinitrobenzenesulphonate)培育细胞0.5小时，再用硫代硫酸钠及GSH培育细胞0.5小时。其中：a为细胞成像效果图，b为对应的比例荧光信号统计数据柱状图。
具体实施方式
实施例1本发明所述以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针的制备
邻羟基苯乙酮与对羧基苯甲醛经二步反应关环得到黄酮醇荧光团，然后通过酰胺键的构建引入芳香醛基，进而与吲哚盐缩合得到化合物L-HF1。
上述反应过程反应式如下：
将化合物1(1mmol)，化合物2(1mmol)，DMAP(0.1mmol)和EDC(1mmol)加入到30mL二氯甲烷中，室温反应8小时后，用卤水洗涤有机相，无水硫酸钠干燥，抽滤，液相旋干，硅胶柱柱层析(二氯甲烷：乙酸乙酯＝1:1)，得化合物3，产率82％，熔点：238-239℃。
红外测定(KBr,cm-1):3270,3000,2918,2850,2809,2724,1731,1664,1633,1603,1568,1483,1421,1288,1227,1159,1006,753。
核磁共振氢谱测定：1H NMR(300MHz,CDCl3):δ9.83(s,1H),8.36(d,J＝8.7Hz,2H),8.27(dd,J＝8.1,1.5Hz,1H),7.80(d,J＝8.7Hz,2H),7.75-7.72(m,1H),7.64-7.61(m,3H),7.45(t,J＝7.8Hz,1H),7.12(s,1H),6.97(d,J＝8.7Hz,2H),3.97-3.49(m,8H)。
核磁共振碳谱测定：13C NMR(75MHz,CDCl3):δ190.4,173.5,169.7,155.4,154.5,143.5,138.9,136.4,134.0,132.7,131.8,128.0,127.9,127.4,125.5,124.7,120.6,118.3,114.1。
高分辨质谱：m/z calculated for C27H23N2O5 +455.1607,found 455.1602。
把化合物3(0.5mmol)和4(0.6mmol)溶在20mL无水乙醇中，加热至回流。TLC跟踪反应至化合物3消失。旋蒸出去乙醇，硅胶柱层析(CH2Cl2:MeOH＝30:1到15:1)得红色固体，即本发明的荧光探针L-HF1，产率：79％。
红外测定(KBr,cm-1):3014,2919,2850,1729,1611,1571,1522,1466,1384,1297,1237,1190,1115,1004。
核磁共振氢谱测定：1H NMR(400MHz，CDCl3)8.37(d,J＝8.4Hz,2H),8.27(d,(d,J＝7.6Hz,1H),8.24(d,J＝7.2Hz,2H),8.09(d,J＝15.6Hz,1H),7.75-7.63(m,5H),7.53-7.45(m,5H),7.14(s,1H),6.99(d,J＝6.8Hz,2H)。
核磁共振碳谱测定：13C NMR(CDCl3,100MHz)δ180.3,173.5,169.7,155.3,154.7,154.5,143.6,142.2,141.6,138.9,136.2,134.9,134.0,132.7,129.3,128.5,127.9,127.5,125.3,124.7,124.1,122.4,120.5,118.4,114.1,113.5,107.2,51.45,46.84,35.79,27.43。
高分辨质谱：m/z calculated for C39H36N3O4 +610.2706,found 610.2702。
实施例2
用微量注射器向10mL配好的探针L-HF1的PBS/DMF缓冲液(pH＝7.4，DMF体积分数为25％，5μM)中，分别定量加入最终浓度为50μM的各种阴离子(F-,Cl-,Br-,I-,HCO3 -,NO3 -,NO2 -,N3 -,AcO-,H2PO4 -,ClO-,ClO3 -,SO4 2-,HSO4 -,HS-,SCN-,S2O3 2-,HSO3 -及SO3 2-)和最终浓度为1mM的各种氨基酸分子(glutamate，histidine，lysine，tryptophan，valine，arginine，sarcosine，aspartic acid，cysteine，homocysteine，glutathione)，作用5分钟后进行荧光分光光度法测试，显示探针对亚硫酸钠与亚硫酸氢钠有很好的选择性，加入亚硫酸钠与亚硫酸氢钠前后对照显示具有明显的荧光发射变化。见图1，2，3。
实施例3
细胞内荧光成像测试：
HeLa细胞：在37℃条件下，HeLa细胞在加入5μM的L-HF1的细胞培养液中培养1小时；再在加入不同浓度的亚硫酸氢钠的细胞培养液中培养0.5小时。荧光成像显示探针L-HF1可渗透进细胞，且随亚硫酸氢钠浓度的增大绿色荧光与红色荧光的强度之比逐渐增大。见图4。
L-02细胞：在37℃条件下，L-02细胞在加入5μM的L-HF1的细胞培养液中培养1小时，再在加入不同浓度的亚硫酸氢钠的细胞培养液中培养0.5小时。荧光成像显示探针L-HF1可渗透进细胞，且随亚硫酸氢钠浓度的增大绿色荧光与红色荧光的强度之比逐渐增大。往活L-02细胞中加入5μM的探针L-HF1，然后用硫代硫酸钠及GSH培育细胞，荧光成像显示加入硫代硫酸钠及GSH前后细胞内荧光显微成像变化，见图5。
HepG2细胞：在37℃条件下，HepG2细胞在加入5μM的L-HF1的细胞培养液中培养1小时，然后用硫代硫酸钠及GSH培育细胞，荧光成像显示加入硫代硫酸钠及GSH前后细胞内荧光显微成像发生变化。在37℃条件下，HepG2细胞在加入5μM的L-HF1的细胞培养液中培养1小时，然后用TNBS(2,4,6-trinitrobenzenesulphonate)培育细胞0.5小时，再用硫代硫酸钠及GSH培育细胞，荧光成像显示此情形下荧光显微成像未见明显变化，见图6。

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1.一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针，其特征在于：所述荧光探针是由黄酮醇荧光团与半川菁荧光团通过非共轭连接而成，命名为L-HF1，其化学结构式如式(I)所示：
2.权利要求1所述以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针在检测液体中的二氧化硫衍生物的应用。
CN201610976291.7A 2016-11-07 2016-11-07 一种以半川菁及黄酮醇为荧光团的二氧化硫衍生物比例荧光探针及其应用 Expired - Fee Related CN106518855B (zh)

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