CN110305039A - 一种新型的荧光增强型探针在检测硫化氢中的应用 - Google Patents

一种新型的荧光增强型探针在检测硫化氢中的应用 Download PDF

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CN110305039A
CN110305039A CN201810255421.7A CN201810255421A CN110305039A CN 110305039 A CN110305039 A CN 110305039A CN 201810255421 A CN201810255421 A CN 201810255421A CN 110305039 A CN110305039 A CN 110305039A
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孙治刚
李志娜
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Abstract

一种含硝基的荧光增强探针，中文名为(3,4‑二甲氧基‑苯基)‑(2‑硝基‑苯亚甲基)‑胺，它具有如下结构式式。实验证明，含硝基的荧光增强探针对硫化氢具有很好的选择性，可以定量检测水溶液中的硫化氢。本发明公开了(3,4‑二甲氧基‑苯基)‑(2‑硝基‑苯亚甲基)‑胺的制法。

Description

一种新型的荧光增强型探针在检测硫化氢中的应用
技术领域
本发明涉及含希夫碱结构和硝基基团的荧光增强型探针的制备与在检测硫化氢中的应用。
背景技术
硫化氢是继一氧化碳和一氧化氮之后，第三种可在生命体内发挥生理作用的内源性气体信号分子。据报道，在自然界中，硫化氢主要由有机物腐败而产生。人为产生硫化氢的主要来源是炼焦厂、牛皮纸浆厂、人造丝厂和炼油厂。人体内也能产生硫化氢，正常水平的硫化氢参与一系列生理调节过程，还能对抗人体内的活性氧和活性氮物种。然而一旦体内硫化氢浓度失常，可能引起唐氏综合征、高血压和肝硬化等疾病。由于硫化氢有刺激性，能引起眼结膜炎，进入血液后部分与血红蛋白结合，生成硫化血红蛋白而使人出现中毒症状，因而在污水处理厂和城市下水道曾发生工人硫化氢中毒死亡事件。
荧光小分子探针因为具有高灵敏性、简单操作性以及高选择性而被应用于检测重金属离子以及一些能与其发生作用的酶。硝基类荧光化合物由于可以提供可被硫化氢还原的硝基而被应用检测硫化氢，因此可将它们开发成为检测硫化氢的探针。
本发明基于希夫碱类荧光化合物的荧光性质，对其引入硝基进行修饰，合成出一个含硝基的荧光探针，并对其进行检测硫化氢的活性测试。
发明内容
本发明涉及一种含硝基的希夫碱类衍生物的制备与在检测硫化氢中的应用。
本发明的技术方案如下：
一种含硝基的希夫碱类衍生物，中文名为(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺，其化学结构式如下：
(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的合成方法，其特征是它由下列步骤组成：
步骤1在含有一定体积无机溶剂的反应容器中依次加入化合物1、2-硝基苯甲醛，在适当条件下搅拌,溶解。在一定的温度下反应一段时间(TLC监测反应)，在反应结束后，通过萃取获得粗产品，粗产品再采用适当有机溶剂经过柱层析提纯获得目标化合物2。
上述制法中所述层析，是采用200-300目柱层析硅胶柱，洗脱液为一定比例的无水乙酸乙酯和石油醚。
本发明的含硝基的荧光增强探针在液体中检测硫化氢具有较好的效果。
附图说明
图1、本发明所列(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的荧光活性图。
图2、本发明所列(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的对于S2+响应的线性图。
图3、本发明所列(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的选择性(0代表空白对照组)。
具体实施方式
通过以下实施例进一步详细说明本发明，但本发明的范围并不受这些实施例的任何限制。
实施例一：(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的制备
称取3,4-二甲氧基苯胺1.0mmol，2-硝基苯甲醛1.0mmol溶解在30mL的无水乙醇中，室温下搅拌1.5h。反应毕，收集溶液后减压蒸除溶剂，经柱层析 [200-300目硅胶柱，洗脱剂为一定比例(1:5)的无水乙酸乙酯和石油醚]，得到目标产物。产物为棕色粉末状固体。产率73％。Mp:122-124℃.1H NMR(400MHz, DMSO)δ8.89(s,1H),8.12(dd,J＝30.3,7.3Hz,2H),7.79(dd,J＝35.8,7.0Hz,2H), 7.10–6.81(m,3H),3.80(d,J＝8.8Hz,6H).HRMS(MSESI+):Calc.for[M+Na]+ 309.0846,found:309.0732.
实施例二：(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的体外荧光活性研究
1.实验材料和方法
1.1药品与试剂
利用荧光仪来测定(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的荧光活性研究。
(1)PBS缓冲液的配制：135mM NaCl,4.7mM KCl,10mM Na2HPO4,2mM NaH2PHO4,pH7.4。
(2)实验药液的配制：将测试样品用少量的乙腈溶解配成储备液，一般按实验最高浓度的10倍配制储备液。
(3)硫化钠溶液的配制：将硫化钠用少量的去离子水溶解配制成储备液。
(4)加药：将0.5μL测试药液按照最终浓度分别加入到各个1.5mL离心管中。实验分为药物试验组(加入浓度梯度的硫化钠)、对照组(只加测试药，不加硫化钠)。将加药后的离心管室温静置一段时间。
(5)荧光活性的测定：在静置了一段时间后，将离心管中的反应液用移液器转移到比色皿中，激发波长选择310nm,发射波长选择330nm-500nm,狭缝选择5nm。
2.实验结果
(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的荧光活性结果见图1。
结果表明：只加探针的时候发射峰在390nm的强度很低,加入浓度梯度的硫化钠之后，发射峰的强度明显增大。证明探针与硫化钠发生了作用。
根据这个实验，我们利用在390nm处的F/F0得到了线性图。
(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的对于S2+响应的线性研究结果见图2。
结果表明：当硫化钠浓度在0-8μM时，具有很好的线性关系。本探针可以用于定量检测硫化氢。
实施例三：(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的选择性研究
1.实验材料和方法
1.1药品与试剂
利用荧光仪来测定(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的选择性活性研究。
(1)PBS缓冲液的配制：135mM NaCl,4.7mM KCl,10mM Na2HPO4,2mM NaH2PHO4,pH7.4。
(2)实验药液的配制：将测试样品用少量的乙腈溶解配成储备液，一般按实验最高浓度的10倍配制储备液。
(3)待测化合物溶液的配制：将硫化钠，硫酸钠,谷胱甘肽,硫代硫酸钠,硫氰酸钾,溴化钠，氟化钠，氯化钠，碘化钠，硝酸钠，亚硝酸钠，磷酸二氢钠，磷酸氢二钠，亚硫酸氢钠，过氧化氢，抗坏血酸,用少量的去离子水溶解配制成储备液。
(4)加药：将0.5μL探针测试药液按照最终浓度分别加入到各个1.5ml离心管中。硫化钠与谷胱甘肽终浓度为50μM,其余待测化合物溶液浓度为100μM。将加药后的离心管室温静置一段时间。
(5)荧光活性的测定：在静置了一段时间后，将离心管中的反应液用移液器转移到比色皿中，激发波长选择310nm,发射波长选择330nm-500nm,电压狭缝选择5nm。
2.实验结果
(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的选择性(0代表空白对照组)结果见图3。
结果表明：只加探针的时候F/F0值在1.0左右，加入50μM的Na2S之后， F/F0值在7.0左右，加入其他待测化合物的时候F/F0值都在1.0左右。证明探针对于硫化氢有很好的选择性。

Claims (4)

1.一类含硝基的荧光增强型探针，中文名为(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的制备，其特征是它具有以下结构式：
2.一种权利要求1中所述的含硝基的荧光增强型探针的制法，其特征是它由以下步骤组成：
称取3,4-二甲氧基苯胺1.0mmol，2-硝基苯甲醛1.0mmol溶解在30mL的无水乙醇中，室温下搅拌1.5h。反应毕，收集溶液后减压蒸除溶剂，经柱层析，得到本发明的含硝基的荧光增强型探针。
3.根据权利要求2所述制法，其步骤2中所述层析，是采用200-300目硅胶柱，洗脱剂为一定比例(1:5)的无水乙酸乙酯和石油醚。
4.权利要求1所述的(3,4-二甲氧基-苯基)-(2-硝基-苯亚甲基)-胺的制备与在检测硫化氢的应用。
CN201810255421.7A 2018-03-27 2018-03-27 一种新型的荧光增强型探针在检测硫化氢中的应用 Pending CN110305039A (zh)

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Citations (6)

* Cited by examiner, † Cited by third party
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US4198349A (en) * 1977-10-06 1980-04-15 William H. Rorer, Inc. Benzylideneaniline derivatives
CN105038765A (zh) * 2015-06-16 2015-11-11 渤海大学 一种具有aiee性质高选择性氰离子荧光探针的制备方法及其应用
CN105884713A (zh) * 2016-04-26 2016-08-24 济南大学 一种荧光增强型硫化氢分子荧光探针及其制备方法和应用
CN106117080A (zh) * 2016-06-16 2016-11-16 渤海大学 一种在纯水溶液中快速检测铝离子的荧光探针的制备方法及其应用
CN106496065A (zh) * 2016-10-31 2017-03-15 重庆理工大学 一种邻苯二胺席夫碱衍生物及其制备方法与应用
CN107216270A (zh) * 2017-07-24 2017-09-29 南京微瑞莱电子科技有限公司 一种检测硫化氢高选择性反应型荧光探针的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198349A (en) * 1977-10-06 1980-04-15 William H. Rorer, Inc. Benzylideneaniline derivatives
CN105038765A (zh) * 2015-06-16 2015-11-11 渤海大学 一种具有aiee性质高选择性氰离子荧光探针的制备方法及其应用
CN105884713A (zh) * 2016-04-26 2016-08-24 济南大学 一种荧光增强型硫化氢分子荧光探针及其制备方法和应用
CN106117080A (zh) * 2016-06-16 2016-11-16 渤海大学 一种在纯水溶液中快速检测铝离子的荧光探针的制备方法及其应用
CN106496065A (zh) * 2016-10-31 2017-03-15 重庆理工大学 一种邻苯二胺席夫碱衍生物及其制备方法与应用
CN107216270A (zh) * 2017-07-24 2017-09-29 南京微瑞莱电子科技有限公司 一种检测硫化氢高选择性反应型荧光探针的应用

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