CN110790781A - 一类红光发射且具有大Stokes位移的不对称氟硼染料 - Google Patents
一类红光发射且具有大Stokes位移的不对称氟硼染料 Download PDFInfo
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Abstract
本发明涉及一类具有红光发射和大Stokes位移的不对称氟硼染料，属于荧光染料范围。其分子结构如下：
该染料分子具有红光发射、大Stokes位移以及高量子效率，并且可以用于生物成像。
Description
本发明涉及一类基于不对称氟硼(BF2)骨架的荧光染料，包括其制备、光物理性质研究及在生物成像领域的应用，属于荧光染料领域。
背景技术
荧光染料的研究工作受到了很多学者的青睐，2008年，诺贝尔化学奖颁给了日裔美国科学家下村修(Osamu Shimomura)、美国科学家马丁·查尔菲(Martin Chalfie),以及美国华裔科学家钱永健，以表彰他们发现和研究绿色荧光蛋白方面做出的贡献。早在1845年，Herschel发现奎宁水溶液在光照射下发出蓝色荧光，随后Stokes对奎宁进行了系统的研究，并把这种光称为荧光。之后，更多的合成及天然的荧光染料被发掘出来并得到了广泛的应用，如生物分子标记、疾病诊断、OLED和各种添加剂等。由于BODIPY/BF2染料具有优良的光学及化学性能，一直以来受到科研工作者们的关注。BODIPY/BF2具有大的摩尔消光系数(通常＞80000M-1cm-1)、发射光谱窄、荧光量子产率高等优点。同时BODIPY/BF2具有稳定的氧化还原电位，且不受光、溶剂或者温度的影响。尤其重要的是，BODIPY/BF2染料的结构赋予了其良好的化学可修饰性，许多类型的反应都可以发生，比如2，6-号位可以发生亲电取代反应，3,5-、4-和8-号位可以发生亲核取代反应，在钯催化下可以在除了4-号位发生Suzuki和Sonogashira偶联反应。然而，传统BODIPY/BF2荧光染料的Stokes位移比较小，检测过程中，样品的吸收光谱和发射光谱有交叉重叠，这就造成了检测过程中的信号相互干扰，从而导致检测误差，并且严重影响检测的灵敏度。同时，传统的BODIPY/BF2染料发射波长较短，也不利于生物应用。因此，为了拓展BODIPY/BF2染料在荧光探针、环境研究、生物传感和生物成像领域的应用，对染料性能的改进势在必行。
发明内容
本发明目的在于提供一类红光发射且具有大Stokes位移的不对称氟硼染料，其结构式如下：
合成路线如下：
具体合成方法如下：
第一步：称取2,4-二乙基-1,2,3,4-四氢喹喔啉水杨醛1(234mg，1mMol)和2-氰甲基苯并咪唑2(172mg，1.1mMol)溶于5mL无水乙醇，搅拌溶解，加入15μL的哌啶，升温至80℃，氩气保护回流反应，TLC监测反应，2小时反应完全，溶液由黄绿色变成深红色。
第二步：在上述反应体系中再加入10mL无水乙醇稀释反应体系，加入5mg对甲苯磺酸和对R基苯胺(214mg，2mMol)，继续氩气保护下回流反应，TLC监测，15小时反应完全。减压旋干溶剂，得深红色油状物，柱层析分离，洗脱剂二氯甲烷：乙醇＝100:1(v:v)，得红色固体4a-f，不需纯化直接用于下一步反应。
第三步：将上述得到的化合物4a/4b/4c/4d/4f溶于20mL 1,2-二氯乙烷，加入100μL的N,N-二异丙基乙胺，室温搅拌均匀，加入100μL的三氟化硼乙醚，80℃氩气保护回流反应，溶液由暗红色迅速变成亮红色，TLC监测反应，2小时后反应完全。停止反应，冷却到室温，加入20mL二氯甲烷稀释上述反应体系，然后倒入到100mL饱和碳酸氢钠溶液中猝灭反应，二氯甲烷萃取(30mL×3)，合并有机相，无水硫酸钠干燥2小时，减压旋干溶剂，得深红色油状物，柱层析纯化两次，洗脱剂为二氯甲烷：乙醇＝100:0→50:1(v:v)，得暗红色固体。
本发明的染料测试方法如下，将荧光染料THQ-BF2-R分别用色谱级二氯甲烷、乙醇、乙腈和二甲亚砜配成浓度为1.0×10-5mol/L的溶液。室温(25℃)下进行测试其吸收、发射波长，以及量子效率。具体实施方法在实施实例中详细介绍。
本发明的荧光染料以2,4-二乙基-1,2,3,4-四氢喹喔啉作为强供电子基团，以N^B^N作为吸电子基团，有效增强了分子的ICT效应。
本发明的荧光染料具有红光发射，发射波长大于600nm，在极性溶剂可达650nm以上。
本发明的荧光染料具有大Stokes位移，在极性溶剂中Stokes位移可达120nm，远大于传统氟硼染料(BODIPY/BF2)。
本发明的荧光染料具有高荧光量子效率，最高可达80％。
本发明的荧光染料可用于活细胞和斑马鱼成像。
附图说明
图1为本发明的荧光染料THQ-BF2-CH3在氘代氯仿中核磁共振氢谱，横坐标化学位移，纵坐标为强度。
图2为本发明的荧光染料THQ-BF2-CH3在氘代氯仿中核磁共振碳谱，横坐标化学位移，纵坐标为强度。
图3为本发明的荧光染料THQ-BF2-CH3的高分辨质谱，横坐标为分子量，纵坐标为强度。
图4为本发明的荧光染料THQ-BF2-CH3在不同溶剂中(二氯甲烷、乙醇、乙腈和二甲亚砜)的归一化吸收光谱，横坐标为波长，纵坐标为相对强度。
图5为本发明的荧光染料THQ-BF2-CH3在不同溶剂中(二氯甲烷、乙醇、乙腈和二甲亚砜)的归一化发射光谱，横坐标为波长，纵坐标为相对强度。
图6为本发明的荧光染料THQ-BF2-CH3在不同溶剂中(二氯甲烷、乙醇、乙腈和二甲亚砜)的吸收、发射、Stokes位移、荧光量子产率。
图7为本发明的荧光染料THQ-BF2-CH3在HeLa细胞中的成像情况。
图8为本发明的荧光染料THQ-BF2-CH3在斑马鱼中的成像情况。
具体实施实例
实施例1：染料4a的合成：称取2,4-二乙基-1,2,3,4-四氢喹喔啉水杨醛1(234mg，1mMol)和2-氰甲基苯并咪唑2(172mg，1.1mMol)溶于5mL无水乙醇，搅拌溶解，加入15μL的哌啶，升温至80℃，氩气保护回流反应，TLC监测反应，2小时反应完全，溶液由黄绿色变成深红色。再加入10mL无水乙醇稀释反应体系，加入5mg对甲苯磺酸和对甲苯胺(214mg，2mMol)，继续氩气保护下回流反应，TLC监测，15小时反应完全。减压旋干溶剂，得深红色油状物，柱层析分离，洗脱剂二氯甲烷：乙醇＝100:1(v:v)，得红色固体，不需纯化直接用于下一步反应。
实施例2：染料THQ-BF2-CH3的合成：将上述得到的化合物质4a溶于20mL 1,2-二氯乙烷，加入100μL的N,N-二异丙基乙胺，室温搅拌均匀，加入100μL的三氟化硼乙醚，80℃氩气保护回流反应，溶液由暗红色迅速变成亮红色，TLC监测反应，2小时后反应完全。停止反应，冷却到室温，加入20mL二氯甲烷稀释上述反应体系，然后倒入到100mL饱和碳酸氢钠溶液中猝灭反应，二氯甲烷萃取(30mL×3)，合并有机相，无水硫酸钠干燥2小时，减压旋干溶剂，得深红色油状物，柱层析纯化两次，洗脱剂为二氯甲烷：乙醇＝100:0→50:1(v:v)，得暗红色固体31.5mg，产率6.16％。1H NMR(400MHz,CDCl3)δ9.12(s,1H),7.81(dd,J＝10.7,4.3Hz,2H),7.41(d,J＝8.6Hz,2H),7.38(d,J＝8.5Hz,2H),7.35-7.29(m,2H),6.65(s,1H),6.25(s,1H),3.63-3.53(m,2H),3.42(q,J＝7.1Hz,4H),3.34-3.25(m,2H),2.50(s,3H),1.32-1.11(m,5H).13C NMR(100MHz,CDCl3)δ142.95,141.76,138.23,133.88,130.70,126.64,126.42,121.25,117.78,114.66,110.29,98.93,81.42,81.10,80.78,53.49,53.28,53.07,52.85,52.64,52.43,52.21,51.25,50.16,49.37,47.99,25.04,14.55,13.50.HRMS(ESI)m/z[C29H29BF2N5O+H]+calcd.:512.2433,found:512.2549.
实施案例3：本发明荧光染料光物理性质研究：染料THQ-BF2-CH3的紫外吸收和荧光发射光谱性能分别是在色谱级二氯甲烷、乙醇、乙腈和二甲亚砜中进行的。将荧光染料分别配成浓度为1.0×10-5mol/L的溶液，测定其紫外吸收和荧光发射。
实施案例4：本发明荧光染料THQ-BF2-CH3细胞成像研究：将HeLa细胞在37℃，5％CO2的湿润细胞培养箱中培养，培养基为含有10％的胎牛血清和1％盘尼西林的DMEM培养液。将消化的细胞接种至玻璃培养皿中，培养24小时待细胞贴壁后进行荧光成像。激光共聚焦显微镜成像：将处理好的细胞与染料THQ-BF2-CH3在37℃培养15分钟，PBS缓冲溶液漂洗细胞后进行激光共聚焦成像。收集红色荧光通道，λex＝488nm，λem＝610±15nm。
Claims (1)
1.一类红光发射且具有大Stokes位移的不对称氟硼染料，其结构为：
其中R为-H,-CH3,OCH3,-OH,-Br,-I,-Cl,-CN。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
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