CN113861148A - 一种基于香豆素的淬灭型荧光探针及其制备方法 - Google Patents
一种基于香豆素的淬灭型荧光探针及其制备方法 Download PDFInfo
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Abstract
本申请属于荧光探针领域,具体涉及一种基于香豆素和4‑联苯基羧酸肼的荧光探针及其制备方法。该荧光探针在检测Cu2+时能与之形成络合物,紫外吸收发生红移,荧光迅速猝灭,检测Cu2+后,溶液颜色由黄色变为棕色,肉眼观察明显;并且该荧光探针具有选择性好,抗干扰能力强,快速响应等特点,是一种优良的Cu2+特异性检测试剂,可以应用于材料领域或传感器领域。
Description
技术领域
本申请属于荧光探针领域,具体涉及一种基于香豆素的淬灭型荧光探针及其制备方法。
背景技术
铜是人体必需的微量元素,在机体内的生化功能主要是催化作用。铜是构成含铜酶与铜结合蛋白的成分,能够维持正常造血功能,参与铁的代谢和红细胞生成。铜在维护中枢神经系统的健康和中枢神经系统中的一些遗传性和偶发性神经紊乱的发病中有着重要作用,并且对免疫功能、激素分泌等也有一定影响。而人体摄入过量铜离子后则会导致铜中毒,当人体内残存了大量的铜之后,极易对身体内的脏器造成负担,特别是肝和胆,当这两种器官出现问题后,维持人体内的新陈代谢就会出现紊乱,会引发一系列的健康问题,如肝硬化和癌症等疾病。近年来,有研究表明,铜离子的过量累积会导致帕金森和阿尔茨海默症。因此,开发一种能够快速检测铜离子的方法具有重要意义。
酰肼类化合物在接近生物体内环境的条件下,有着较高的活性,可以和生物体内许多微量元素进行反应,但由于酰肼结构中-NH2基团的存在,这类化合物对生物体有一定的毒害作用。酰腙类化合物是酰肼类化合物改性后得到的一类Schiff碱化合物,酰腙类化合物具有优良的配位能力,能够和多种金属离子形成稳定的配合物。本申请涉及的化合物(HQ1)是7-(二乙胺基)-香豆素上醛基后与4-联苯基羧酸肼反应生成的,在检测Cu2+时与之形成配合物,紫外吸收发生红移,而荧光迅速淬灭,该化合物的合成及应用于荧光材料还未见相关报道,本申请把7-(二乙胺基)香豆素和4-联苯基羧酸肼有机结合起来制成的探针对Cu2+具有很好的特异性选择,同时具有快速响应的特点,pH范围广,颜色发生变化由黄色变为棕色肉眼就可以检测到Cu2+,具有很高的实际应用价值。
发明内容:
为了克服现有仪器昂贵且操作复杂的技术缺陷,本申请提供了一种新的探测Cu2+的荧光探针。该荧光探针为香豆素酰腙类化合物,该化合物的荧光性能较强,加入Cu2+后能与之快速络合,紫外吸收发生红移,荧光迅速淬灭。因此,是一种理想的检测Cu2+的荧光探针。另外,该合成工艺具有操作简单、产率高、成本低等优点。具体技术方案如下:
一种基于香豆素的淬灭型荧光探针,特征在于,其具体结构如下:
合成路线如下:
制备基于香豆素的淬灭型荧光探针,其特征在于,制备方法如下:
1)称取4-(二乙氨基)水杨醛、丙二酸二乙酯和哌啶溶于溶剂,加入2-3滴冰乙酸;4-(二乙氨基)水杨醛、丙二酸二乙酯的摩尔比为1:1~1:3;
2)将上述溶液于室温下搅拌8-15分钟后,加热至75-90℃,回流,反应20-25h后,冷却至室温,加入浓盐酸、冰乙酸,加热至75-90℃继续反应5-8h。冷却到室温,用NaOH水溶液调节PH,过滤,水洗,干燥得化合物1;
3)称取DMF、POCl3和步骤2)得到的化合物1,回流反应6h,冷却到室温调节PH,水洗,干燥,柱色谱分离,干燥,即得化合物2;
4)称取步骤3)得到的化合物2和4-联苯基羧酸肼溶于溶剂,回流反应1-2h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。
步骤1)中4-(二乙氨基)水杨醛、丙二酸二乙酯的摩尔比为1:1~1:3;哌啶与丙二酸二乙酯的摩尔比为1:1~1:3,加入2滴冰乙酸,反应用的溶剂为无水乙醇。
步骤2)中浓盐酸与冰醋酸的体积比为1:1~1:2,NaOH溶液的浓度为30-40%,PH需要调到5-7。
步骤3)中DMF与POCl3的摩尔比为1:1,需要把PH调到5-7。
步骤4)中化合物2和4-联苯基羧酸肼的摩尔比为1:1~1:2,所用溶剂为无水乙醇。
优选的,步骤1)中4—(二乙氨基)水杨醛与丙二酸二乙酯的摩尔比为1:2;
优选的,步骤1)中哌啶的用量为1ml,冰乙酸的用量为2滴;
优选的,步骤1)中的溶剂为无水乙醇;
优选的,步骤2)中浓盐酸的用量为20ml,冰醋酸的用量为20ml;
优选的,步骤2)中NaOH溶液的浓度为30%,pH调节到5;
优选的,步骤3)中DMF的用量为6.5ml,POCl3的用量为6.5ml;
优选的,步骤3)中NaOH溶液的浓度为30%,pH调节到5.2;
优选的,步骤4)中4-联苯基羧酸肼的用量为0.32g;
优选的,步骤4)中所述溶剂为无水乙醇,反应温度为75℃。
本发明将4-(二乙氨基)水杨醛与丙二酸二乙酯反应,制备得7-(二乙氨基)香豆素,将其与POCl3和DMF反应得到化合物2,再将化合物2与4-联苯基羧酸肼反应得到化合物HQ1,即最终产物。经测试,该化合物具有对Cu2+良好的选择性,本发明的新化合物可以作为荧光探针应用于金属离子检测领域。
附图说明:
(1)图1是化合物HQ1的核磁共振氢谱图;
(2)图2是化合物HQ1的质谱图;
(3)图3是化合物HQ1对金属离子铜选择性的荧光谱图(横坐标为发射波长,纵坐标为荧光强度)。
具体实施方式:
为了更好的理解本发明的技术方案,以下通过具体的实施例作进一步详细叙述。
实施例1
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,100℃下反应6h。冷却至室温,用30%NaOH溶液调节PH至5,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至5.2,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.32g溶于15ml无水乙醇中,混合均匀,在75℃下反应1h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:94%。
实施例2
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,90℃下反应7h。冷却至室温,用30%NaOH溶液调节PH至5,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至5.2,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.32g溶于15ml无水乙醇中,混合均匀,在75℃下反应1h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:85%。
实施例3
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,110℃下反应6h。冷却至室温,用30%NaOH溶液调节PH至5,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至5.2,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.32g溶于15ml无水乙醇中,混合均匀,在75℃下反应1h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:84%。
实施例4
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,100℃下反应6h。冷却至室温,用30%NaOH溶液调节PH至6,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至6,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.32g溶于20ml无水乙醇中,混合均匀,在75℃下反应1h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:87%。
实施例5
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,100℃下反应6h。冷却至室温,用30%NaOH溶液调节PH至7,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至7,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.32g溶于20ml无水乙醇中,混合均匀,在60℃下反应2h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:80%。
实施例6
称取4-(二乙氨基)水杨醛1.93g、丙二酸二乙酯3ml,哌啶1ml,溶于60ml的无水乙醇中,加入2滴冰乙酸,室温下预溶解,油浴加热,回流,温度升至85℃,恒温下反应24h,冷却至室温,旋蒸除去溶剂。向旋好的溶液中加入20ml浓盐酸,20ml冰乙酸,100℃下反应6h。冷却至室温,用30%NaOH溶液调节PH至5,搅拌1h,过滤,水洗3次,干燥,的粗产物。粗产物经柱层析分离提纯后得7-(二乙氨基)香豆素,即化合物1。
称取2.25g化合物1,用15mlDMF溶解,将6.5ml POCl3加入到6.5ml DMF中,混合均匀,用滴液漏斗将POCl3和DMF混合液滴加到DMF溶解的化合物1中,在冷井中进行,温度为0℃,滴加时间为30min。滴加完成后,放进油浴锅中加热,在60℃下回流反应24h,冷却至室温,倒入100ml冰水中,用30%NaOH调节PH至5.2,过滤,水洗三次,柱层析分离,干燥后得化合物2。
称取0.245g化合物2和4-联苯基羧酸肼0.212g溶于15ml无水乙醇中,混合均匀,在75℃下反应1h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。产率:82%。
最终产品化合物核磁氢谱(附图1)及质谱分析(附图2):
通过对化合物HQ1的结构式和核磁共振氢谱图分析得表1。该化合物共有13种氢。其中在1.16ppm附近出现的信号峰为质子1的信号峰,它的峰面积是5.52;在3.48ppm附近出现的信号峰为质子2的信号峰,它的峰面积是3.99;在6.61ppm出现信号峰为质子3的信号峰,它的峰面积是1.28;在6.8ppm附近出现的信号峰为质子4的信号峰,它的峰面积是1.16;在7.4出现的信号峰为质子5的信号峰,它的峰面积是1.2;在7.68ppm出现的信号峰为质子6的信号峰,它的峰面积是1.13;在7.52出现的信号峰为质子7的信号峰,它的峰面积是2.27;在7.79-7.73出现的信号峰为质子8的信号峰,它的峰面积是2.40;在7.84出现的信号峰为质子9的信号峰,它的峰面积是2.07;在8.04出现的信号峰为质子10的信号峰,它的峰面积是2.03;在8.41出现的信号峰为质子11的信号峰,它的峰面积是1.09;在8.54和11.96出现的信号峰为质子12和13的信号峰,它的峰面积分别是0.98,1。由此可以看出,化合物核磁共振氢谱图很好的符合了化合物的结构。
化合物结构C27H25N3O3,计算得其分子量为439.1896,测试得其分子量为440.1971([C27H25N3O3+H]+)。由此可以得出,化合物质谱图符合预期分子量。
表1化合物HQ1的1HNMR的化学位移和峰归属
取实施例1制备的化合物HQ1,利用二甲基亚砜:水(1/1,v/v)溶解、稀释,配置成1.0×10-5mol/L的样品溶液。利用F-7000荧光分光光度计测定化合物的荧光激发波长,并测定化合物的荧光光谱。向溶液中分别加入等当量的不同金属离子Cu2+,Ag+,Al3+,Ba2+,Cd2+,Cr3+,Fe2+,Fe3+,Hg2+,K+,Na+,Pb2+,Sr2+,Zn2+,测定在各金属离子存在下,荧光探针的荧光发射光谱(如附图3所示),探针发射强烈的荧光,加入Cu2+后荧光淬灭,而加入其他离子荧光强度变化不大,而且不会发生荧光淬灭,此结果表明探针HQ1对Cu2+有很好的识别作用。
Claims (7)
3.制备如权利要求1所述的基于香豆素的淬灭型荧光探针,其特征在于,制备方法如下:
1)称取4-(二乙氨基)水杨醛、丙二酸二乙酯和哌啶溶于溶剂,加入2-3滴冰乙酸;4-(二乙氨基)水杨醛、丙二酸二乙酯的摩尔比为1:1~1:3;
2)将上述溶液于室温下搅拌8-15分钟后,加热至75-90℃,回流,反应20-25h后,冷却至室温,加入浓盐酸、冰乙酸,加热至75-90℃继续反应5-8h。冷却到室温,用NaOH水溶液调节PH,过滤,水洗,干燥得化合物1;
3)称取DMF、POCl3和步骤2)得到的化合物1,回流反应6h,冷却到室温调节PH,水洗,干燥,柱色谱分离,干燥,即得化合物2;
4)称取步骤3)得到的化合物2和4-联苯基羧酸肼溶于溶剂,回流反应1-2h,冷却至室温,抽滤,干燥即得化合物HQ1,即最终产物。
4.如权利要求3所述的基于香豆素的淬灭型荧光探针的制备方法,其特征在于,步骤1)4-(二乙氨基)水杨醛、丙二酸二乙酯的摩尔比为1:1~1:3;哌啶与丙二酸二乙酯的摩尔比为1:1~1:3,加入2滴冰乙酸,反应用的溶剂为无水乙醇。
5.如权利要求3所述的基于香豆素的淬灭型荧光探针的制备方法,其特征在于,步骤2)中浓盐酸与冰醋酸的体积比为1:1~1:2,NaOH溶液的浓度为30-40%,PH需要调到5-7。
6.如权利要求3所述的基于香豆素的淬灭型荧光探针的制备方法,其特征在于,步骤3)中DMF与POCl3的摩尔比为1:1,需要把PH调到5-7。
7.如权利要求3所述的基于香豆素的淬灭型荧光探针的制备方法,其特征在于,步骤4)中化合物2和4-联苯基羧酸肼的摩尔比为1:1~1:2,所用溶剂为无水乙醇。
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