CN106632138B - 一种识别肼的小分子荧光探针及其应用 - Google Patents
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Abstract
本发明公开了一种识别肼的小分子荧光探针及其应用,属于有机小分子荧光探针技术领域。该荧光探针的分子式为C20H12N2OS,结构式如下:该探针的合成只需要一步就可以完成,且后处理过程相对简单;本发明实现了N2H4分子探针的选择性快速检测,并且选择性好,抗其它分子干扰能力强,可以应用于水环境和生物体系中N2H4的传感检测,在生物分子检测领域具有广阔的应用前景。
Description
技术领域
本发明涉及一种快速识别肼的小分子荧光探针及其应用,属于有机小分子荧光探针领域。
背景技术
肼是一种非常重要的化学试剂,在化学领域广泛的用于催化剂、乳化剂、医药中间体、纺织染料、摄影化学品等方面。同时,肼作为一种高能燃料推进剂在导弹、卫星和火箭推进系统中发挥着非常重要作用。但是,肼也是一种毒性较大的物质,可以通过呼吸和皮肤接触进入人体,对人体的肝、肾、肺及神经系统造成重大伤害。因此,一般的饮用水中的含量不可超过10ppb。因此,发展一种可以在生物体和环境中方便快捷检测肼的方法非常重要。
目前检测肼的常用方法有电化学法、流量检测和化学发光法,其中荧光光谱分析法有着操作简单、灵敏度高、选择性好、生物相容性好等优势。但是都存在着波长短、无法检测气态肼、无法实现细胞成像等缺点。鉴于此,开发双光子荧光探针可以实现长波长激发,从而检测细胞中的肼,并且可以通过肼试纸的制备实现环境和气体肼的检测。而这一问题一直是目前亟待解决的课题。因此,通过利用萘荧光平台,发展具有新型识别位点的双光子肼荧光探针,具有非常重要的科学意义。
发明内容
针对目前有机小分子荧光探针在N2H4的检测中所面临的问题,本发明通过分子设计,合成出一种具有选择性高的N2H4荧光探针。
本发明采用以下技术方案:
一种识别肼的小分子荧光探针,该探针分子的分子式为:C20H12N2OS,它的结构式如下:
所述荧光探针的制备方法如下:
将100.0mg化合物1与58.9mg化合物2在氮气氛围下加至反应瓶中,然后将46.8mg哌啶和5.0mL乙醇/乙腈按体积比1:1组成的混合溶液一次性加至上述反应器中,于氮气氛围下在加热回流5h后,点板检测反应至原料消失,二氯甲烷萃取,无水Na2SO4干燥,减压旋干溶剂得粗产品,并用硅胶柱进行分离得到目标探针化合物,简记为NS-N2H4;
所述化合物1结构式如下:
所述化合物2结构式如下:
上述的识别肼的小分子荧光探针的应用,该荧光探针可以应用于水环境和生物体系中N2H4的传感检测;所述的传感检测包含荧光检测、细胞成像以及环境中肼的检测。
本发明的优点:(1)探针的合成只需要一步就可以完成,且后处理过程相对简单;(2)本发明实现了N2H4分子探针的选择性快速检测,并且选择性好,抗其它分子干扰能力强。基于其特异性和显著的颜色变化,该试剂可作为显示水溶液中和生物细胞内N2H4分子存在的专一性指示剂,可进行实时定性的目视比色法检测。故而,本发明是一种简单,快速,灵敏的N2H4分子特异性检测试剂,在生物分子检测领域具有广阔的应用前景。其性能将在实施例中结合附图给予详细说明。
附图说明
图1是实施例1中探针NS-N2H4的1H NMR图谱。
图2是探针NS-N2H4随N2H4的加入荧光强度的变化情况。
图3是探针NS-N2H4随时间变化荧光强度变化情况。
图4是探针NS-N2H4选择性柱状图数据,1:none;2:Al3+;3:Ca2+;4:Co2+;5:Cu+;6:Cu2 +;7:Mg2+;8:Zn2+;9:S2-;10:SO3 2-;11:Cys;12:Cl-;13:N2H4。
图5是探针NS-N2H4应用于细胞中N2H4的荧光成像图,其中a)将20μM探针DMF溶液加入到育有HeLa细胞的培养液中在二氧化碳培养箱中培养0.5h,明场成像,可以看到细胞大致的轮廓;b)将a)用蓝光进行激发得到成像图;c)将a)和b)图成像叠加;d)将20μM探针DMF溶液加入到育有HeLa细胞的培养液中在二氧化碳培养箱中培养0.5h,加入N2H4后,明场成像,可以看到细胞大致的轮廓;e)将d)用蓝光进行激发得到成像图;f)将d)和e)图成像叠加。
图6是探针NS-N2H4在不同N2H4浓度下紫外灯试纸条的颜色变化情况图。
具体实施方式
下面结合实施例和附图对本发明做进一步说明,但本发明不受下述实施例的限制,实施例中化合物的号码对于上述方案中化合物的号码。
实施例1
探针化合物NS-N2H4的合成
将化合物1(0.5mmol,100.0mg)与化合物2(1.1equiv,58.9mg)在氮气氛围下加至反应瓶中,然后将哌啶(1.1equiv 46.8mg)和乙醇/乙腈(v/v=1/1,5.0mL)一次性加至上述反应器中,于氮气氛围下在加热回流5h后,点板检测反应至原料消失,使用二氯甲烷萃取,无水Na2SO4干燥,减压旋干溶剂得粗产品,并用硅胶柱进行分离得到探针化合物NS-N2H4,硅胶颗粒大小为200-300目,产率为63%。1H-NMR(400MHz,DMSO-d6)δ10.4(s,1H),8.49(d,J=12.4Hz,2H),8.22-8.19(m,2H),8.09(d,J=8.0Hz,1H),7.90(dd,J=14.4,7.6Hz,2H),7.60(t,J=8.0Hz,3H),7.52(t,J=7.2Hz,1H),7.23-7.16(m,2H).该探针的1H NMR图谱见图1。
实施例2
探针化合物NS-N2H4荧光探针随N2H4加入当量的增加荧光谱图的变化
取实施例1制备的探针NS-N2H4溶于N,N-二甲基甲酰胺(DMF)中,制成1mmol/L储备液。从储备液中取出30μL加入到5mL的离心管当中,加入不同当量(0-100equiv)的N2H4标准溶液,用PBS缓冲溶液(0.1mol/L,pH=7.5)与DMSO体积比为2:1的溶液稀释至3mL,以360nm为激发光,测量其荧光性质。荧光光谱如图2所示。由图2可见,随着N2H4加入当量的增加荧光逐渐增强。
实施例3
探针NS-N2H4对随时间变化的荧光谱图的变化
从实施例2中荧光探针储备液中取出30μL加入到5mL的离心管当中,加入N2H4(20equiv)标准溶液,用DMSO/PBS(1:2,v/v)稀释至3mL(10μM),测量其荧光性质。荧光光谱如图3所示。由图3可见,加入探针NS-N2H4后,直接加入N2H4,随时间的增加荧光强度迅速达到最大,实现了N2H4的检测。
实施例4
化合物NS-N2H4荧光探针对不同离子的选择性
从实施例2中荧光探针储备液中取出30μL加入到5mL的离心管当中,分别加入等摩尔量的竞争分子标准溶液,其中一个加入等摩尔量的N2H4标准溶液,20min后检测溶液的荧光发射光谱变化,由图4可以发现,其他干扰离子对化合物NS-N2H4的荧光几乎没有影响,而N2H4溶液的加入使化合物NS-N2H4的荧光显著增强。
实施例5
NS-N2H4荧光探针对细胞中N2H4荧光成像
我们将本发明探针应用于HeLa细胞中N2H4的检测进行荧光成像应用。结果如图5所示,具体操作步骤如下:a)将20μM探针DMF溶液加入到育有HeLa细胞的培养液中在二氧化碳培养箱中培养0.5h,明场成像,可以看到细胞大致的轮廓;b)将a)用蓝光进行激发观得到成像图;c)将a)和b)图成像叠加;d)将20μM探针DMF溶液加入到育有HeLa细胞的培养液中在二氧化碳培养箱中培养0.5h,加入N2H4后,明场成像,可以看到细胞大致的轮廓;e)将d)用蓝光进行激发观得到成像图;f)将d)和e)图成像叠加。说明此荧光探针实现细胞中N2H4的检测。
实施例6
本发明的探针作为气态肼试纸条测试
用1mmol/mL的NS-N2H4溶液浸泡硅胶板,烘干制成条状,然后放置于不同浓度肼的容量瓶的瓶口,10min后置于紫外灯下拍照。随肼浓度增大,紫外灯下显示硅胶板由红色变成蓝色,详见图6。
Claims (1)
1.一种识别肼的小分子荧光探针,其特征在于,探针分子的分子式为:
C20H12N2OS,它的结构式如下:
所述荧光探针的制备方法如下:
将100.0mg化合物1与58.9mg化合物2在氮气氛围下加至反应瓶中,然后将46.8mg哌啶和5.0mL乙醇/乙腈按体积比1:1组成的混合溶液一次性加至上述反应器中,于氮气氛围下在加热回流5h后,点板检测反应至原料消失,二氯甲烷萃取,无水Na2SO4干燥,减压旋干溶剂得粗产品,并用硅胶柱进行分离得到目标探针化合物;
所述化合物1结构式如下:
所述化合物2结构式如下:
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