CN108219776B - 一种增强型荧光探针、制备方法及在检测甲醛上的应用 - Google Patents
一种增强型荧光探针、制备方法及在检测甲醛上的应用 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种开关型甲醛荧光探针的制备方法及在检测环境中甲醛含量应用,属于环境分析化学及生物检测领域。
背景技术
甲醛,分子式为HCHO,是最简单的醛类物质。是一种无色具有特殊的刺激气味的气体,对人眼、鼻等有刺激作用,对人体有致敏、致畸和致癌等毒性,是一种公认的致癌和致崎物质。室内空气、大气环境和食品污染中的甲醛会导致中毒,造成头晕、头痛或恶心、呕吐,严重的会引起记忆力减退,甚至死亡。正常情况下,机体内有完整的代谢机制,一般可通过酶促反应将甲醛降解转化为CO2、甲酸和水,若过量的甲醛在机体内积累会使组织细胞内活性氧增多,诱发脂质过氧化反应、损伤线粒体膜,使细胞的抗氧化应激能力下降。通过非酶促反应与一些重要的生物大分子形成不可逆的共价交联复合物,导致强烈的细胞毒性、基因毒性、致突变、致癌等。因此,在环境和生物系统内实现对甲醛的高灵敏度、高选择性的实时检测是非常必要的。
目前,甲醛的检测分析方法主要包括分光光度法,色谱法,极谱法,电位法,传感器法等,但是这些方法往往需要特定的仪器设备、操作复杂,测试条件严格。由于荧光探针具有简单方便、特异选择性高、实时检测等优点而备受关注。目前仅有少量用于检测甲醛的荧光探针被报导,而多数存在着检测选择性、灵敏性差的问题。因此,发展具有特异选择性、高灵敏度新型荧光探针,是目前探针研究领域的前沿和热点。
发明内容
本发明的目的在于提供一种具有特异选择性、高灵敏度的甲醛荧光探针,并进一步提供了该探针的制备方法和应用。
本发明所述的甲醛荧光探针,其分子式为:C24H21N3O3S;其结构式如下:
所述的甲醛荧光探针的合成路线如下:
包括如下步骤:将化合物1在冰浴条件下溶解于溶剂中,再向其中加入对硝基苯甲醛和氰基硼氢化钠和乙酸,撤掉冰浴,常温下搅拌,氮气保护。其中化合物1和对硝基苯甲醛、氰基硼氢化钠、乙酸的摩尔比为1:1~10:1~10:1~20。
本发明将所述的甲醛荧光探针,是一种开-关型荧光探针。
本发明将所述的甲醛荧光探针在检测溶液中甲醛的应用。
本发明将所述的甲醛荧光探针在检测空气中甲醛的应用。
附图说明
图1是实施例1中探针TP的1HNMR图谱。
图2是实施例1中探针TP的13CNMR图谱。
图3是实施例4中探针TP随不同量甲醛的加入,荧光谱图的变化情况。
图4是实施例5中探针TP在不同混合溶液中荧光谱图的变化情况。
图5是实施例6中探针TP在空气环境下检测甲醛的荧光变化图。
具体实施方式
实施例1:
将330.1mg化合物1(1.1mM)在冰浴条件下溶解于18ml THF中,再向其中加入831.1mg对硝基苯甲醛(5.5mM)和345.6氰基硼氢化钠(5.5mM)和660mg乙酸(11.0mM),撤掉冰浴,常温下搅拌,氮气保护。反应10h以上。反应完后,将反应液通过减压旋转蒸发仪除去溶剂得到粗产品,并用硅胶(200-300目)层析柱,以体积比为12:1的乙酸乙酯与石油醚为洗脱剂进行纯化,得到180.1mg白色固体(产率为37.4%)。
实施例2
将100.4mg化合物1(0.34mM)在冰浴条件下溶解于8ml THF中,再向其中加入256.9mg对硝基苯甲醛(1.70mM)和128.2mg氰基硼氢化钠(2.04mM)和360.3mg乙酸(6.0mM),撤掉冰浴,常温下搅拌,氮气保护。反应10h以上。反应完后,将反应液通过减压旋转蒸发仪除去溶剂得到粗产品,并用硅胶(200-300目)层析柱,以体积比为12:1的乙酸乙酯与石油醚为洗脱剂进行纯化,得到29.5mg白色固体(产率为20.1%)。
实施例3
将175.5mg化合物1(0.59mM)在冰浴条件下溶解于14ml THF中,再向其中加入624.5mg对硝基苯甲醛(4.13mM)和259.5mg氰基硼氢化钠(4.13mM)和474.4mg乙酸(7.9mM),撤掉冰浴,常温下搅拌,氮气保护。反应10h以上。反应完后,将反应液通过减压旋转蒸发仪除去溶剂得到粗产品,并用硅胶(200-300目)层析柱,以体积比为12:1的乙酸乙酯与石油醚为洗脱剂进行纯化,得到74.1mg白色固体(产率为29.1%)。
实施例4:探针TP随不同量甲醛的加入荧光谱图的变化情况;
取实施例1制备的探针TP溶于DMSO中,配制成浓度为0.5mmol/L探针母液(探针TP的浓度为0.5mmol/L);将质量分数为37%的甲醛溶液加入蒸馏水,配制成甲醛浓度为200mmol/L的甲醛母液。配置乙腈:磷酸二氢钾水溶液(浓度10mmol/L,pH=7.4)=3:7的缓冲液300ml,按3mL/根试管平均分配。向试管中加入30μl探针母液,分别加入不同浓度(0、0.3、0.8、1.0、1.5、2.0、2.5、3.0、3.5、4.0、4.5、5.0、5.5、6.0、7.0、8.0、9.0、10mM)的甲醛,反应3h后,测定探针的荧光变化。由图可见,随着甲醛浓度的增加,荧光探针TP在542nm处产生一个新的发射带并且其荧光峰值逐渐增强。
实施例5:探针TP在不同混合溶液中荧光谱图的变化情况;
取实施例1制备的探针TP溶于DMSO中,配制成浓度为0.5mmol/L探针母液(探针TP的浓度为0.5mmol/L);将质量分数为37%的甲醛溶液加入蒸馏水,配制成甲醛浓度为200mmol/L的甲醛母液。配置DMF:磷酸二氢钾水溶液(浓度10mmol/L,pH=7.4)=3:7的缓冲液6ml,按3mL/根试管平均分配成两根。向每根试管中加入30μl探针母液,分别加入0、10mM的甲醛,反应3h后,测定探针的荧光变化。由图可见,荧光探针TP在542nm处产生一个新的发射带并且其荧光峰值逐渐增强。
实施例6:探针TP在空气环境下检测甲醛的荧光变化图;
取实施例1制备的探针TP溶于DMSO中,配制成浓度为0.5mmol/L探针母液(探针TP的浓度为0.5mmol/L);稀释成20μmol/L的探针母液。分别取37%的甲醛溶液和蒸馏水各10ml于锥形瓶中。将滤纸剪成小纸条放置于锥形瓶瓶口,密闭瓶口,37℃水浴加热半小时,观察纸条荧光颜色的变化。由图可见,纸条颜色由无色变为黄色。
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CN112521383A (zh) * | 2020-12-11 | 2021-03-19 | 三峡大学 | 苯并噻唑衍生物及作为荧光染料上的应用 |
CN113004200B (zh) * | 2021-02-03 | 2022-02-18 | 台州学院 | 基于萘酰亚胺衍生物的甲醛浓度和pH值双响应型探针及其制备和应用 |
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