CN113861149A - 一种基于香豆素和对溴苯甲酰肼的荧光探针及其制备方法 - Google Patents
一种基于香豆素和对溴苯甲酰肼的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对溴苯甲酰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和对溴苯甲酰肼的荧光探针及其制备方法。
背景技术
铜作为人体必需的一种微量元素在人体内发挥着重要作用,但当人体摄入过量铜离子后则会导致铜中毒,当人体内积累了大量的铜之后,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、癌症、帕金森、阿尔茨海默症等疾病。因此,开发一种能够快速检测铜离子的方法具有重要意义。
荧光探针由荧光探和识别基团组成,在环境化学、分析化学和生命科学领域具有重要应用。香豆素因其具有荧光强度高、溶解性与细胞渗透性好、易于合成与修饰、良好的荧光量子产率和好的光稳定性等特点被用于荧光团骨架。通过对香豆素母体进行修饰,衍生出不同的优良荧光团,以其为基础合成的荧光探针在检测重金属离子方面具有广泛应用。本申请涉及的化合物(HQ2)是7-(二乙胺基)-香豆素上醛基后与对溴苯甲酰肼反应生成的,在检测Cu2+时与之形成络合物,紫外吸收发生红移,而荧光迅速猝灭,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)香豆素和对溴苯甲酰肼有机的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,荧光迅速猝灭。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:
一种基于香豆素和对溴苯甲酰肼的荧光探针,特征在于其具体结构如下:
合成路线如下:
制备基于香豆素和对溴苯甲酰肼的荧光探针,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和对溴苯甲酰肼溶于溶剂,回流反应4-6h,冷却至室温,抽滤,干燥即得化合物HQ2,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和对溴苯甲酰肼的摩尔比为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)中对溴苯甲酰肼的用量为0.33g;
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(化合物1),将其与POCl3和DMF反应得到化合物2,再将化合物2与对溴苯甲酰肼反应得到化合物HQ2,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HQ2的核磁共振氢谱图;
(2)图2是化合物HQ2的质谱图;
(3)图3是化合物HQ2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和对溴苯甲酰肼0.33g溶于20ml无水乙醇中,混合均匀,在75℃下反应5h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。产率:92%。
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和对溴苯甲酰肼0.33g溶于20ml无水乙醇中,混合均匀,在75℃下反应5h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。产率:88%。
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和对溴苯甲酰肼0.32g溶于20ml无水乙醇中,混合均匀,在75℃下反应5h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。产率:90%。
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和对溴苯甲酰肼0.32g溶于15ml无水乙醇中,混合均匀,在75℃下反应4h,冷却至室温,抽滤,干燥即得化合物HQ2,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和对溴苯甲酰肼0.33g溶于25ml无水乙醇中,混合均匀,在75℃下反应6h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。产率:89%。
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和对溴苯甲酰肼0.215g溶于15ml无水乙醇中,混合均匀,在75℃下反应5h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。产率:87%。
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HQ2的结构式和核磁共振氢谱图分析得表1。该化合物共有10种氢。其中在1.14ppm附近出现的信号峰为质子1的信号峰,它的峰面积是6.20;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4.03;在6.59ppm出现信号峰为质子3的信号峰,它的峰面积是0.97;在6.78ppm附近出现的信号峰为质子4的信号峰,它的峰面积是1;在7.67出现的信号峰为质子5的信号峰,它的峰面积是0.96;在7.73ppm出现的信号峰为质子6的信号峰,它的峰面积是1.94;在7.91出现的信号峰为质子7的信号峰,它的峰面积是1.88;在8.39出现的信号峰为质子8的信号峰,它的峰面积是0.86;在8.50出现的信号峰为质子9的信号峰,它的峰面积是0.89;在11.96出现的信号峰为质子10的信号峰,它的峰面积是0.93。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C21H20BrN3O3,计算得其分子量为441.0688,测试得其分子量为442.0765([C21H20BrN3O3+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HQ2的1HNMR的化学位移和峰归属
取实施例1制备的化合物HQ2,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+后荧光猝灭,而加入其他离子荧光强度变化不大,而且不会发生荧光猝灭,此结果表明探针HQ2对Cu2+有很好的识别作用。
Claims (7)
3.制备如权利要求1所述的基于香豆素和对溴苯甲酰肼的荧光探针,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和对溴苯甲酰肼溶于溶剂,回流反应4-6h,冷却至室温,抽滤,干燥即得化合物HQ2,即最终产物。
4.如权利要求3所述的基于香豆素和对溴苯甲酰肼的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所述的基于香豆素和对溴苯甲酰肼的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所述的基于香豆素和对溴苯甲酰肼的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所述的基于香豆素和对溴苯甲酰肼的荧光探针的制备方法,其特征在于,步骤4)中化合物2和对溴苯甲酰肼的摩尔比为1:1~1:2,所用溶剂为无水乙醇。
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