CN111793371A - 一种3，5位不对称修饰bodipy类近红外荧光染料及其制备方法 - Google Patents
一种3，5位不对称修饰bodipy类近红外荧光染料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种3，5位不对称修饰BODIPY类近红外荧光染料及其制备方法，采用BODIPY衍生物与含3‑甲基对氟苯甲醛及哌啶为原料在对甲苯磺酸和哌啶催化作用下发生Knoevenagel缩合反应合成。该制备方法可以通过一步反应合成一种3，5位不对称修饰BODIPY类近红外荧光染料，其中哌啶既是催化剂，又是反应物。该类荧光染料最大电子吸收光谱红移至639nm，荧光发射波长达到678nm，并具有高的摩尔消光系数和良好的溶解性等优异的光物理性能，且该染料具有很好的细胞渗透性，能用于细胞内荧光成像。可作为近红外荧光染料应用于近红外荧光成像、荧光标记或者光电材料等领域。
Description
技术领域
本发明属于有机化合物合成、功能性荧光染料和精细化工技术领域，具体涉及一种3，5位不对称修饰BODIPY类近红外荧光染料及其制备方法。
背景技术
氟硼二吡咯甲川类(Boron-dipyrromethene，简称BODIPY)染料作为有机荧光染料以其优越的光物理性质和易于修饰的化学结构备受科学界的青睐。与传统荧光染料相比，如荧光素和罗丹明等，BODIPY类化合物具有较高摩尔吸光系数、荧光量子产率和荧光寿命；荧光信号对溶剂极性和pH不敏感；在可见光区域有强吸收；较好的光热稳定性等性质。因此，BODIPY类化合物在光动力疗法、离子识别、pH荧光探针、细胞成像与示踪、蛋白质与DNA标记及新型染料敏化太阳能电池等领域有很大的应用价值。
近年来，对BODIPY染料的研究倾向于合成长波长的近红外荧光染料，主要是由于近红外光在传播过程中受到的干扰小、对物质透过性好，特别是在近红外光谱区，生物分子自身的吸收和荧光最小，可以避免生物体散射光以及自荧光对检测结果造成的偏差，散射干扰也大为减少，且对组织细胞渗透性强。因此，近红外荧光染料在生物检测领域具有无与伦比的优势，不仅可避免背景干扰而获得较高的分析灵敏度，而且还可以降低对生物体的损伤。BODIPY分子母核3，5位的甲基具有一定的化学活性，可与芳香醛发生Knoevenagel缩合反应，因此引入不同类型的苯乙烯基，与BODIPY主体形成较大的苯基共轭体系可使化合物的电子吸收和发射波长发生明显红移。因此，可利用苯乙烯基对BODIPY-3，5位的修饰制备近红外BODIPY类衍生物。
通过Knoevenagel缩合一步反应合成一种3，5位不对称修饰BODIPY类近红外荧光染料，避免了大多数近红外氟硼二吡咯类染料合成步骤多、难度大等问题。另外，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近红外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3，5位不对称修饰BODIPY类近红外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3，5位不对称修饰BODIPY类近红外荧光染料及其制备方法，其特征在于该近红外荧光染料具有如下结构式(I)：
一种3，5位不对称修饰BODIPY类近红外荧光染料及其制备方法，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、3-甲基对氟苯甲醛和对甲苯磺酸，然后溶解于20～25mL甲苯和1.5～2mL哌啶中，反应混合物加热到110～120℃回流，反应时间4～7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3-甲基对氟苯甲醛的摩尔比为1∶1.8～2.0。
2)将反应混合物冷至室温，二氯甲烷萃取、水洗，有机层用无水硫酸钠干燥，减压蒸馏除去有机溶剂，残留物经硅胶柱层析分离，洗脱剂为体积比为6∶4的二氯甲烷-石油醚混合溶液，得到蓝绿色固体产物。
具体化学反应式如下：
上述步骤(1)中，BODIPY衍生物与3-甲基对氟苯甲醛的摩尔比为1∶1.8～2.0。
上述步骤(1)中，加入的甲苯和哌啶的用量分别是25mL和2mL。
上述步骤(1)中，催化剂为对甲苯磺酸和哌啶，且哌啶还作为反应物。
上述步骤(2)中，硅胶柱层析分离洗脱剂为二氯甲烷∶石油醚＝6∶4。
上述的3，5位不对称修饰BODIPY类近红外荧光染料(I)作为近红外荧光染料在肿瘤细胞成像方面的应用。
本发明的有益效果
与现有技术相比，本发明的一种3，5位不对称修饰BODIPY类近红外荧光染料及其制备方法具有的优点有：(1)制备方法简便易行，只需一步反应就可得3，5位不对称修饰的近红外BODIPY类衍生物，避免了不对称BODIPY类近红外染料合成步骤多、难度大等问题；(2)其中哌啶既是催化剂，也是反应物；(3)最大发射波长为671nm(4)能作为有机荧光染料用于肿瘤细胞荧光成像；本发明的3，5位不对称修饰BODIPY类近红外荧光染料在荧光标记、荧光传感器和生物成像等领域具有及为重要的应用前景。
附图说明
图1是3，5位不对称修饰BODIPY类近红外荧光染料(I)的紫外-可见吸收光谱图；
图2是3，5位不对称修饰BODIPY类近红外荧光染料(I)的荧光发射光谱图；
图3是3，5位不对称修饰BODIPY类近红外荧光染料(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，5位不对称修饰BODIPY类近红外荧光染料(I)的电喷雾高分辨质谱图。
具体实施方式
下面结合具体附图对本发明做进一步的说明。
用1H-NMR、UV-Vis谱表征并证实近红外BODIPY类荧光染料的结构。检测所用仪器为：Bruker ARX400型核磁共振仪(TMS为内标，氘代氯仿为溶剂)，岛津UV-3100型紫外-可见分光光度计(扫描范围300～900nm，光路狭缝2nm)，荧光光谱用美国Amico Bowman Series2 Luminescence Spectrometer测试。
实施例1 3，5位不对称修饰BODIPY类近红外荧光染料(I)的制备
在无水条件下，干燥的圆底烧瓶中配备有Dean-Stark装置，将1，3，5，7-四甲基8-(2，4，6-三甲苯)-BODIPY(366mg，1mmol)，3-甲基对氟苯甲醛(276mg，2mmol)和对甲苯磺酸(176mg)溶于25mL甲苯和2mL哌啶，加热至115℃回流，反应6小时。冷至室温，用二氯甲烷萃取，水洗，合并有机层，减压蒸除有机溶剂，残余物经硅胶柱层析分离提纯，洗脱剂为二氯甲烷-石油醚(V/V＝6∶4)，得到蓝绿色固体化合物(I)(33mg，5％)。1H NMR：(600MHz，CDCl3)δ7.63(dd，J＝16.17，11.08Hz，2H)，7.47(s，2H)，7.43-7.37(m，2H)，7.22(d，J＝16.22Hz，1H)，7.16(d，J＝16.20Hz，1H)，7.02(t，J＝8.88Hz，1H)，6.99(d，J＝8.4Hz，1H)，6.96(s，2H)，6.62(s，1H)，6.59(s，1H)，2.94-2.85(m，4H)，2.37-2.32(m，9H)，2.13(s，6H)，1.76-1.70(m，4H)，1.62-1.58(m，2H)，1.45(d，J＝2.4Hz，6H)
UV-vis：343nm，589nm，639nm(图1)；Emission Wavelength：678nm(图2)。
实施例2 3，5位不对称修饰BODIPY类近红外荧光染料(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3-甲基对氟苯甲醛按摩尔比为1∶1.8反应；反应温度控制在110℃，反应时间7小时。
实施例3 3，5位不对称修饰BODIPY类近红外荧光染料(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3-甲基对氟苯甲醛、对甲苯磺酸按摩尔比为1∶1.8∶1反应；反应温度控制在120℃，反应时间为4小时。
实施例4 3，5位不对称修饰BODIPY类近红外荧光染料(I)溶液紫外-可见吸收光谱
将3，5位不对称修饰BODIPY类近红外荧光染料(I)溶于二氯甲烷中，配置成浓度为1×10-5mol/L二氯甲烷溶液，测定其紫外-可见吸收光谱。图1为本发明实施例1制备的荧光染料(I)溶液紫外-可见吸收光谱。
实施例5 3，5位不对称修饰BODIPY类近红外荧光染料(I)溶液荧光
将3，5位不对称修饰BODIPY类近红外荧光染料(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2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6 3，5位不对称修饰BODIPY类近红外荧光染料(I)用于肿瘤细胞荧光成像
将3，5位不对称修饰BODIPY类近红外荧光染料(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)共同孵化后的激共光聚焦荧光成像照片。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。3，5位不对称修饰BODIPY类近红外荧光染料(I)可用于肿瘤细胞成像。
Claims (6)
1.一种3，5位不对称修饰BODIPY类近红外荧光染料，其特征在于，其结构式如下：
2.权利要求1所述的3，5位不对称修饰BODIPY类近红外荧光染料(I)的制备方法，其特征在于，由如下步骤实现：在无水条件下，将1，3，5，7-四甲基-8-(2，4，6-三甲基苯基)氟硼二吡咯与3-甲基对氟苯甲醛按摩尔比1∶1.8～2.0加入到干燥甲苯中，再加入对甲苯磺酸和哌啶，搅拌并加热，温度控制在110～120℃，反应时间4～7小时，结束反应，经萃取、干燥、硅胶层析柱进行分离提纯，得到3，5位不对称修饰BODIPY类近红外荧光染料(I)，该过程的反应式如下：
3.根据权利要求2所述的一种3，5位不对称修饰BODIPY类近红外荧光染料的制备方法，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20～25mL∶1mmol。
4.根据权利要求2所述的一种3，5位不对称修饰BODIPY类近红外荧光染料的制备方法，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3-甲基对氟苯甲醛摩尔比为1∶1.8～2.0。
5.根据权利要求2所述的一种3，5位不对称修饰BODIPY类近红外荧光染料，其特征在于，哌啶既是催化剂，又是反应物，哌啶与甲苯的体积比为2∶25。
6.权利要求1所述的3，5位不对称修饰BODIPY类近红外荧光染料(I)作为近红外荧光染料在肿瘤细胞成像方面的应用。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461722A (zh) * | 2021-08-06 | 2021-10-01 | 南京林业大学 | 一种具有aie效应的双bodipy类近红外荧光染料及其制备方法 |
| CN113501836A (zh) * | 2021-07-28 | 2021-10-15 | 南京林业大学 | 一种星型bodipy近红外荧光染料及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650610A (zh) * | 2015-01-28 | 2015-05-27 | 天津理工大学 | 一种不对称近红外bodipy荧光染料及其制备和应用 |
| CN106928262A (zh) * | 2017-03-16 | 2017-07-07 | 南京林业大学 | 一种近红外三聚茚基共轭双bodipy类荧光染料及其制备方法 |
| CN109020999A (zh) * | 2018-06-21 | 2018-12-18 | 南京林业大学 | 一种含哌啶基氟硼二吡咯类近红外pH荧光探针的制备及应用 |
| CN109233325A (zh) * | 2018-09-03 | 2019-01-18 | 南京大学 | 一类不对称苯并氟硼二吡咯荧光染料及其制法 |
| CN110669350A (zh) * | 2019-11-04 | 2020-01-10 | 南京林业大学 | 一种哌啶基bodipy类红光荧光染料及其制备方法和应用 |
| CN110709540A (zh) * | 2017-05-02 | 2020-01-17 | 犯罪科学技术公司 | 4-硼-3a,4a-二氮杂-s-茚烯在生产荧光纤维中的用途 |
-
2020
- 2020-07-24 CN CN202010727921.3A patent/CN111793371B/zh not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650610A (zh) * | 2015-01-28 | 2015-05-27 | 天津理工大学 | 一种不对称近红外bodipy荧光染料及其制备和应用 |
| CN106928262A (zh) * | 2017-03-16 | 2017-07-07 | 南京林业大学 | 一种近红外三聚茚基共轭双bodipy类荧光染料及其制备方法 |
| CN110709540A (zh) * | 2017-05-02 | 2020-01-17 | 犯罪科学技术公司 | 4-硼-3a,4a-二氮杂-s-茚烯在生产荧光纤维中的用途 |
| CN109020999A (zh) * | 2018-06-21 | 2018-12-18 | 南京林业大学 | 一种含哌啶基氟硼二吡咯类近红外pH荧光探针的制备及应用 |
| CN109233325A (zh) * | 2018-09-03 | 2019-01-18 | 南京大学 | 一类不对称苯并氟硼二吡咯荧光染料及其制法 |
| CN110669350A (zh) * | 2019-11-04 | 2020-01-10 | 南京林业大学 | 一种哌啶基bodipy类红光荧光染料及其制备方法和应用 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113501836A (zh) * | 2021-07-28 | 2021-10-15 | 南京林业大学 | 一种星型bodipy近红外荧光染料及其制备方法 |
| CN113461722A (zh) * | 2021-08-06 | 2021-10-01 | 南京林业大学 | 一种具有aie效应的双bodipy类近红外荧光染料及其制备方法 |
| CN113461722B (zh) * | 2021-08-06 | 2022-04-19 | 南京林业大学 | 一种具有aie效应的双bodipy类近红外荧光染料及其制备方法 |
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