CN110128455A - 一种冰片酯基苯乙炔基BODIPY类pH荧光探针的制备方法 - Google Patents
一种冰片酯基苯乙炔基BODIPY类pH荧光探针的制备方法 Download PDFInfo
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Abstract
本发明公开了一种冰片酯基苯乙炔基BODIPY类pH荧光探针及其制备方法,其化学结构如(I)所示,该荧光探针以2,6‑二碘代BODIPY衍生物为起始原料,与2‑甲氧基4‑(N,N‑二乙基胺基)苯甲醛发生Knoevenagel缩合反应得到中间体,再与冰片酯基苯乙炔通过Sonogashira偶联制得。该化合物制备方法简单、反应条件温和、操作简便,且在中性至酸性pH范围(pH=5.52‑7.0)表现出较高的灵敏度。该探针在结合H+前后颜色变化明显,可通过溶液的颜色变化定性判断环境的pH值,具有巨大的应用前景。
Description
技术领域
本发明属于有机合成技术领域,涉及一种冰片酯基苯乙炔基BODIPY类pH荧光探针的制备方法。
背景技术
氟硼二吡咯(BODIPY)是近年来出现的一种新型荧光染料,以其优越的光物理化学性质和多样化的应用得到科学界广泛的关注,在荧光分析、环境监测、肿瘤诊断等领域有着广泛的应用。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。除此之外,BODIPY分子具有一定的化学活性,易于进行修饰。基于此,我们可以通过对BODIPY主体进行一定的化学修饰,改变其光学特性,以达到不同的应用目的。因此,合成结构新颖的BODIPY类有机荧光染料具有非常重要的意义。
冰片,一种天然的单萜类化合物,它具有许多良好的药理活性和功能,如镇痛、抗菌、抗炎等,在中医中有着举足轻重的地位。冰片具有多个手性中心,因其独特的空间构型,冰片可用作手性来源,用其对一些功能有机分子进行化学修饰可提高功能分子生物活性及细胞渗透性。
pH值的精确测量对环境分析、化学反应过程控制、生物医学研究具有十分重要的意义。相比于其他pH值的测定方法,使用光谱法进行pH检测具有灵敏度高、选择性好等优点。而pH荧光探针是荧光光谱随着环境pH值的变化而产生规律性变化的探针,由于荧光探针的高选择性、高灵敏度、快速响应等特点,因此可以对pH值进行实时监测。近年来,利用荧光探针和高分辨的荧光显微技术研究分子或离子在空间和时间上的变化,在分子化学、生物化学及药物化学等学科得到广泛的应用。
基于BODIPY类化合物的优点,本发明中对BODIPY母体结构进行修饰,分别在3位引入共轭的2-甲氧基-4-(N,N-二乙基胺基)苯乙烯基和在2,6位引入共轭的冰片酯基苯乙炔基,设计合成了一种pH响应的BODIPY类荧光探针。该探针在氢离子作用下吸收光谱和荧光发生蓝移,强度和颜色也发生显著变化。因此,该探针可以对氢离子具有荧光识别和裸眼显色的用途。
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冰片酯基苯乙炔基BODIPY类pH荧光探针。
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:
本发明涉及的一种冰片酯基苯乙炔基BODIPY类pH荧光探针的结构如下:
本发明涉及的一种冰片酯基苯乙炔基BODIPY类pH荧光探针的合成路线为:
本发明涉及的一种冰片酯基苯乙炔基BODIPY类pH荧光探针的制备过程包括以下步骤:
步骤1:在无水条件下,在配备有Dean-Stark装置的圆底烧瓶中加入式(II)所示的2,6-二碘代BODIPY衍生物、式(III)所示的2-甲氧基-4-(N,N-二乙基胺基)苯甲醛和对甲苯磺酸,然后溶于甲苯,并加入适量哌啶,混合物加热到140℃回流反应14-16h,反应结束后减压除去有机溶剂,残余物经硅胶柱层析分离提纯得到式(IV)所示的芳环乙烯基修饰的二碘代BODIPY衍生物;
步骤2:在氩气保护下,将式(IV)2,6-二碘代BODIPY衍生物、式(V)所示冰片酯基苯乙炔、CuI溶于干燥四氢呋喃与三乙胺,迅速加入四(三苯基膦)钯,缓慢升温至60℃反应过夜,反应结束后减压除去有机溶剂,残余物经硅胶柱层析分离提纯得到式(I)所示的冰片酯基苯乙炔基BODIPY类荧光探针分子。
上述反应步骤1中,式(II)所示的2,6-二碘代BODIPY衍生物与式(III)所示的2-甲氧基-4-(N,N-二乙基胺基)苯甲醛物质的量之比为1∶1.2;
上述反应步骤1中,加入的甲苯与哌啶的体积分别为20mL和3mL。
上述反应步骤2中,催化剂四(三苯基膦)钯、碘化亚铜用量与芳环苯乙基修饰的二碘代BODIPY衍生物(IV)的物质的量之比为1∶1∶10。
与现有技术相比,本发明中冰片基苯乙炔BODIPY类pH荧光探针的制备方法所具有的优点有:(1)本发明的用作pH探针的冰片酯基苯乙炔基BODIPY类化合物制备工艺简单、反应条件温和、分离方法简便;(2)本发明提供了一种较大光谱移动的pH荧光探针,本发明在pH5.52-7.0溶液中发生质子化反应,其紫外-可见吸收和荧光强度产生相应变化。溶液颜色由绿色变为紫红色。(3)本发明化合物在不同pH值时溶液颜色变化非常明显,颜色由绿色变为紫红色,可通过溶液的颜色变化定性判断环境的pH值,是一种较好的可视化pH荧光探针,并具有操作简单、灵敏度高、响应快等优点。
附图说明
图1为不同pH值下,探针I(浓度为1×10-5mol/L)的紫外-可见吸收光谱图;
图2为不同pH值下,探针I(浓度为1×10-5mol/L)的荧光发射光谱图;
图3为将探针加入到pH=7~5.52溶液中,日光灯照射下拍摄的图像;
图4为探针I的核磁共振氢谱;
具体实施方式
下面结合具体实例对本发明作进一步地解释,具体实施事例并不对本发明作任何限定。
实施例1
将化合物II(1.00mmol)和化合物III(1.20mmol)加入到配备有分水器的50mL圆底烧瓶中,依次加入对甲苯磺酸(2.70mmol)、甲苯(20mL)和哌啶(3mL),加热至140℃回流14-16h,冷却到室温。用饱和食盐水洗涤,二氯甲烷萃取,有机相用无水硫酸钠干燥,减压蒸馏除去溶剂,得到粗产物。通过硅胶层析柱分离,洗脱剂为二氯甲烷-石油醚(v∶v=1∶1)得到化合物IV(产率:26%)。1H-NMR(CDCl3,600MHz,ppm)δ8.63(d,J=16.6Hz,1H),7.64-7.59(m,2H),7.15(d,J=8.6Hz,2H),7.02(d,J=8.6Hz,2H),6.34(d,J=8.4Hz,1H),6.13(d,J=2.4Hz,1H),3.91(s,3H),3.89(s,3H),3.42(d,J=7.2Hz,4H),2.65(s,3H),1.49(s,3H),1.41(s,3H),1.21(t,J=7.1Hz,6H).Esi-MS:calculated for C32H34BF2I2N3O2:796.2857;found:796.0802(M+).
实施例2
在Ar气保护条件下,在50mL圆底烧瓶中,化合物IV(0.10mmol)、化合物V(0.25mmol)、CuI(0.01mmol)溶于15mL四氢呋喃和3mL三乙胺。加入Pd(PPh3)4(0.01mmol)。60℃加热体系回流过夜,反应结束后用饱和食盐水洗涤,二氯甲烷萃取,无水硫酸钠干燥,旋蒸除去有机溶剂得到粗产物,再经硅胶柱层析分离,洗脱剂为二氯甲烷-石油醚(v∶v=2∶1),得化合物I(产率:25%)。1H-NMR(CDCl3,600MHz,ppm)δ8.89(d,J=9.6Hz,1H),8.02-7.99(m,4H),7.73(d,J=8.9Hz,1H),7.61(d,J=8.4Hz,3H),7.51(d,J=8.4Hz,2H),7.22(d,J=8.4Hz,2H),7.05(d,J=8.4Hz,2H),6.35(t,J=8.3Hz,1H),6.12(s,1H),5.12(d,J=9.0Hz,1H),3.91(s,3H),3.74(s,3H),3.42(m,4H),2.76(s,3H),2.50-2.45(m,2H),2.14-2.09(m,2H),1.84-1.80(m,2H),1.75(d,J=3.6Hz,2H),1.65(s,3H),1.59(s,3H),1.46-1.40(m,3H),1.24-1.22(m,6H),1.13(d,J=13.8Hz,3H),0.97(d,J=2.6Hz,6H),0.92(t,J=2.8Hz,12H).Esi-MS:calculated for C70H76BF2N3O6:1103.58;found:1104.20(M+).
实施例3
探针在不同pH溶液中的吸收光谱:分别配置含有实施例2中探针的不同pH值(pH为5.52、5.57、5.62、5.68、5.74、5.82、5.92、6.05、6.22、6.52、7.0)的溶液,探针的浓度为1.0×10-5mol/L。测定各个不同pH值溶液的紫外吸收光谱,结果如附图1所示。
实施例4
探针在不同pH溶液中的吸收光谱:分别配置含有实施例2中探针的不同pH值(pH为5.52、5.57、5.62、5.68、5.74、5.82、5.92、6.05、6.22、6.52、7.0)的溶液,探针的浓度为1.0×10-5mol/L。测定各个不同pH值溶液的荧光发射光谱,结果如附图2所示。
实施例5
探针对不同pH溶液的裸眼显色识别:配置含有实施例2中探针的pH值分别为5.52、5.74、5.92、6.05、6.22、6.52、7.0的缓冲溶液,探针的浓度为1.0×10-5mol/L。肉眼观察不同pH值溶液的颜色并用相机拍照,结果如附图3所示。
Claims (8)
1.一种冰片酯基苯乙炔基BODIPY类pH荧光探针,其特征在于,其化学结构如(I)所示:
。
2.一种如专利要求1所述的式(I)所示的一种冰片酯基苯乙炔基BODIPY类pH荧光探针的制备方法,其特征在于,所述的制备方法为:2,6-二碘代BODIPY衍生物与2-甲氧基-4-(N,N-二乙基胺基)苯甲醛在钯催化剂作用下得到芳环乙烯基修饰的二碘代BODIPY衍生物;然后与冰片酯基苯乙炔发生Sonogashira偶联反应得到如式(I)所示的冰片酯基苯乙炔基BODIPY类pH荧光探针。
3.如专利要求2所述的制备方法,其特征在于,所述制备方法包括以下步骤:
步骤1:在无水条件下,在配备有Dean-Stark装置的圆底烧瓶中加入2,6-二碘代BODIPY衍生物、2-甲氧基-4-(N,N-二乙基胺基)苯甲醛和对甲苯磺酸,然后用甲苯溶解,并加入少量哌啶,混合物加热到140℃回流反应14-16h。减压除去有机溶剂,残余物经硅胶柱层析分离提纯得到芳环乙烯基修饰的二碘代BODIPY衍生物。
步骤2:在氩气保护下,将芳环乙烯基修饰的二碘代BODIPY衍生物、冰片酯基苯乙炔、CuI溶于干燥四氢呋喃与三乙胺中,迅速加入四(三苯基膦)钯,缓慢升温至60℃反应过夜,反应结束后减压除去有机溶剂,残余物经硅胶柱层析分离提纯得到冰片酯基苯乙炔基BODIPY衍生物。
4.根据权利要求3所述的制备方法,其特征在所述步骤1中,二碘代BODIPY衍生物与2-甲氧基-4-(N,N-二乙基胺基)苯甲醛的物质的量之比为1∶1.2。
5.根据权利要求3所述的制备方法,其特征在所述步骤2中,芳环乙烯基修饰的二碘代BODIPY衍生物与冰片酯基苯乙炔的物质的量之比为1∶2.5。
6.一种如权利要求1所述荧光探针的用途,其特征在于,采用紫外可见吸收和荧光法,荧光分子探针在溶液中对pH有吸收强度和荧光强度效应,用于溶液中pH检测分析。
7.一种如权利要求1所述pH荧光探针的用途,其特征在于:适用于酸性环境,且在pH=5.52-7.0时效果明显。
8.一种如权利要求1所述的pH荧光探针的应用,其特征在于:直接通过肉眼观察溶液颜色的变化便可快速检测出pH值。
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