CN110669350B - 一种哌啶基bodipy类红光荧光染料及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种哌啶基BODIPY类红光荧光染料及制备方法和应用,该荧光染料通过1,3,5,7‑四甲基‑8‑(2,4,6‑三甲基苯基)氟硼二吡咯化合物与对氟苯甲醛的缩合反应制备。该染料能用于检测溶液pH值,对pH的检测范围在1‑7。且该染料具有较好的细胞渗透性,能用于细胞内荧光成像。可作为性能优异的红光染料,在荧光成像、生物荧光分析、荧光传感器、荧光标记等领域具有广泛应用。
Description
技术领域
本发明涉及荧光化合物及其制备方法和应用领域,具体涉及一种哌啶基BODIPY类红光荧光染料及其制备方法和应用。
背景技术
BODIPY(氟硼二吡咯)类荧光物质是一类新兴的染料,具有斯托克斯位移较小、稳定性好、对酸碱不敏感、荧光量子产率较高、荧光激发和发射峰较窄,在许多有机溶剂中的溶解性较高等优点。通常的BODIPY衍生物吸收和发射波长大部分均在500nm左右,限制了其应用范围。发展高效便捷的有机合成方法对BODIPY进行结构修饰,制备吸收和发射波长位于红光或近红外区域的BODIPY类荧光化合物是近期的研究热点。
经过修饰的BODIPY衍生物被广泛应用在离子探针、分子探针、荧光标记、分析化学、生物分析检测、环境科学等领域。pH值是一个重要的参数,在环境分析、化学反应过程控制、生物医学等方面中,pH值的测定具有十分重要的意义。物质的物化性质及其在水溶液中的反应性能、生命体系中的许多生理过程都与其所处环境的pH值密切相关。目前,pH测定方法主要有指示剂法、pH试纸法、玻璃电极法、光学传感器法等。近年来,利用荧光分子各种荧光参数(如荧光强度、荧光寿命、荧光的波长等)的变化来监测pH的变化,已引起人们的广泛兴趣。相比于其他pH测定方法,基于光学信号变化而建立的pH探针测定方法由于具有灵敏度高、选择性好、反应时间短的优点而得到广泛的关注。
细胞作为重要的生命单元,在生命体的生长等方面有重要的作用,细胞的组织架构的变化与疾病的表型有密切的关系。因此,对细胞荧光成像及靶向定位细胞等研究,有着重要的意义。这不仅可以使人们深入了解基因组信息,还可以为病理学家提供早期诊断和预测病变信息。然而目前可以特异性定位到细胞的荧光染料存在种类少、价格昂贵、可修饰性差等诸多问题。所以细胞染料的研究作为前沿领域的热点和难点,长期备受研究人员的关注。鉴于细胞荧光成像在细胞定位、细胞靶向载药和肿瘤细胞光动力杀伤等领域的重要的意义,因此合成新型的具有荧光性质的有机染料分子在细胞的荧光成像领域有很高的科研价值和应用价值。
发明内容
发明目的:针对现有技术中存在的不足,本发明的目的是提供一种哌啶BODIPY类红光荧光染料及其制备方法和应用。
技术方案:为了实现上述发明目的,本发明采用的技术方案为:
本发明的一种哌啶基BODIPY类红光荧光染料及其制备方法和应用,其特征在于该荧光探针具有如下结构式(I):
一种含哌啶基BODIPY类近红光荧光染料的制备方法,步骤如下:
1)在配备有Dean-stark装置的圆底烧瓶中加入1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯、对氟苯甲醛和对甲苯磺酸,然后溶解于25~30mL甲苯和2~4mL哌啶中,反应混合物加热到120~130℃回流,反应时间16~18小时。其中,1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯与对氟苯甲醛的摩尔比为1∶0.8~1.0。
2)将反应混合物冷至室温,二氯甲烷萃取、水洗,有机层干燥,减压蒸馏除去有机溶剂,残留物经硅胶柱层析分离,洗脱剂为二氯甲烷-石油醚,得到黑绿色固体产物。
具体化学反应式如下:
上述步骤(1)中,加入的1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯体积物质的量与甲苯的体积比为1mmol∶15~20mL。
上述步骤(1)中,1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯与对甲苯磺酸摩尔比为2∶0.8~1。
上述步骤(2)中,硅胶柱层析分离洗脱剂为石油醚∶二氯甲烷=3∶7。
上述的哌啶基BODIPY类红光荧光染料(I)作为荧光探针在pH值检测方面的应用。
上述的哌啶基BODIPY类红光荧光染料(I)作为长波长的红光染料在肿瘤细胞成像方面的应用。
本发明的有益效果
本发明具有以下优点:本发明的哌啶基BODIPY类红光荧光染料(I)的结构、合成、荧光性质及应用在现有技术中未见报道,其性能优异,在二氯甲烷等纯有机溶剂中发射红色荧光,最大发射波长为671nm;且随pH值减小,其发射波长蓝移,荧光增强,可作为pH荧光探针;还能作为有机荧光染料用于肿瘤细胞荧光成像;本发明的哌啶基BODIPY类红光荧光染料在活细胞成像、荧光传感器、生物荧光分析、荧光标记等领域具有极为重要的应用前景。
附图说明
图1为哌啶基BODIPY类红光荧光染料(I)在二氯甲烷中(浓度为1×10-5mol/L)的荧光光谱图;
图2为不同pH值下,哌啶基BODIPY类红光荧光染料(I)(浓度为1×10-5mol/L)的荧光光谱图;
图3为哌啶基BODIPY类红光荧光染料(I)与肝癌细胞HepG2共同孵化后的激光共聚焦荧光显微照片;
图4为哌啶基BODIPY类红光荧光染料(I)的电喷雾高分辨质谱图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明,但本发明并不限于以下实施例。实施例1哌啶基BODIPY类红光荧光染料(I)的制备
在无水条件下,在三颈圆底烧瓶中加入1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯(2mmol,732mg),对氟苯甲醛(2.0mmol,248mg),对甲苯磺酸(0.87mmol,150mg),用甲苯30ml和哌啶2ml进行溶解。加热至125℃回流,反应16小时。冷至室温,用饱和食盐水洗2次,用二氯甲烷萃取3次,旋干溶剂后得到粗产品。使用硅胶层析柱进行分离,洗脱剂为二氯甲烷∶石油醚=7∶3,得黑绿色固体化化合物(I),产率31%。化合物(I)核磁共振氢谱:1H-NMR(600MHz,CDCl3,ppm):δ7.53-7.48(m,4H),7.19(d,J=16.2Hz,1H),6.95(s,2H),6.88(d,J=8.7Hz,2H),6.58(s,1H),5.96(s,1H),3.27(t,J=10.8Hz,3H),2.59(s,3H),2.34(s,3H),2.11(s,6H),1.72-1.68(m,4H),1.64-1.54(m,2H),1.43(s,3H),1.39(s,3H).HRMS(ESI):[M+H]+,C34H39BF2N3 calculated:538.3205;found:538.3215.
哌啶基BODIPY类红光荧光染料(I)的合成路线如下:
实施例2哌啶基BODIPY类红光荧光染料(I)的制备
与实施例1基本一样,所不同的在于,本实施例中的1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯与对氟苯甲醛按摩尔比为1∶0.8反应;反应温度控制在130℃。
实施例3哌啶基BODIPY类红光荧光染料(I)的制备
与实施例1基本一样,所不同的在于,本实施例中的1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯与对氟苯甲醛、对甲苯磺酸按摩尔比为1∶0.8∶1反应;反应温度控制在125℃。
实施例4哌啶基BODIPY类红光荧光染料(I)溶液荧光
将哌啶基BODIPY类红光荧光染料(I)溶于二氯甲烷中,配置成浓度为1×10-5mol/L二氯甲烷溶液,测定其荧光发射光谱。图1为本发明实施例1制备的荧光染料(I)溶液荧光光谱。
实施例5哌啶基BODIPY类红光荧光染料(I)检测pH=1~7酸性溶液
准确称取1.0mg化合物I,溶于1.41ml二氯甲烷中,得探针母液,溶液浓度为1×10- 3mol/L。将三氟乙酸溶于二氯甲烷中配制不同pH的溶液,准确吸取一定量探针母液分别加入到上述溶液中,使哌啶基BODIPY类红光荧光染料(I)的最终浓度为1×10-5mol/L。通过荧光分光光度计测定不同pH值哌啶基BODIPY类红光荧光染料(I)溶液的荧光发射强度(图2)。从图2可以清楚看出,随着pH的降低,其发射波长蓝移,荧光探针的荧光强度开始逐渐增强。
实施例6哌啶基BODIPY类红光荧光染料(I)用于肿瘤细胞荧光成像
将哌啶基BODIPY类红光荧光染料(I)与肝癌细胞HepG2共同孵化后在双通道共聚焦荧光显微镜下观察HepG2细胞成像照片。图3为HepG2细胞与荧光染料(I)共同孵化后的激光共聚焦荧光成像照片。在HepG2细胞中加入荧光染料(I)共同孵化后,荧光染料进入HepG2细胞内部清晰成像。哌啶基BODIPY类红光荧光染料(I)可用于肿瘤细胞成像。
Claims (5)
2.根据权利要求1所述的应用,其特征在于:采用荧光法,哌啶基BODIPY类红光荧光染料在溶液中对pH有荧光强度效应,能用于溶液中pH检测分析,检测范围在pH=1~7。
4.根据权利要求3所述的应用,其特征在于:甲苯与1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯体积物质的量比为15~20mL:1mmol。
5.根据权利要求3所述的应用,其特征在于:1,3,5,7-四甲基-8-(2,4,6-三甲基苯基)氟硼二吡咯与对甲苯磺酸摩尔比为2:0.8~1。
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