CN106543125B - 基于香豆素对no2的荧光增强效应的荧光探针及其制备方法和应用 - Google Patents
基于香豆素对no2的荧光增强效应的荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于香豆素对NO2的荧光增强效应的荧光探针及其制备方法和应用。利用3‑N,N‑二甲胺基苯酚、三氯氧磷和无水DMF制备4‑N,N‑二甲胺基‑2‑羟基‑苯甲醛,然后利用4‑N,N‑二甲胺基‑2‑羟基‑苯甲醛和三苯基膦烯基乙酸乙酯制备7‑N,N‑二甲胺基‑香豆素,再将其与三氯氧磷和无水DMF反应制得7‑N,N‑二甲胺基‑8‑醛基香豆素,最后利用7‑N,N‑二甲胺基‑8‑醛基香豆素和盐酸羟胺、三乙胺反应得到探针7‑N,N‑二甲胺基‑8‑肟基香豆素,该探针可用于对NO2进行检测,探针与NO2发生检测作用后,荧光强度增强6.7倍。
Description
技术领域
本发明涉及二氧化氮检测技术领域,更具体地,本发明涉及一种基于香豆素对NO2的荧光增强效应的荧光探针及其制备方法和应用。
背景技术
二氧化氮(NO2)作为硝基脂肪族爆炸物的降解产物、空气环境中的大气污染物,发展针对NO2的新型检测方法对于维护公共安全、预防环境污染等具有十分重要的意义。荧光分析法具有灵敏度高、选择性好、操作简单等优点,是分析检测领域近年来的发展趋势之一,其中香豆素分子具有制备简单、Stokes 位移大、荧光亮度高等优点,在染料、传感和标记等分析检测领域具有很好的应用前景,目前国内外以香豆素分子为荧光团,发展了各式各样的荧光探针用于金属离子、自由基以及无机小分子的标记与检测,然而目前仍未见基于香豆素分子的荧光探针用于NO2的荧光增强检测应用。
发明内容
本发明针对二氧化氮气体的荧光检测,发展基于香豆素的荧光探针,利用香豆素荧光团的自有特性,实现对NO2高选择性的荧光增强检测。具体地,本发明针对NO2的荧光增强检测,以香豆素分子为荧光团,经过设计、制备得到荧光探针,考察其荧光性质,并将其用于NO2的荧光增强检测。为实现基于香豆素对 NO2的荧光增强检测,采用以香豆素为荧光团,肟基为NO2识别基团,通过化学合成方法将肟基构筑于香豆素分子的8位上得到新型荧光探针,并考察新型探针的自身光谱性质,主要包括吸收波长、发射波长、荧光量子产率等,评估新型探针对NO2的荧光增强响应行为,包括与NO2发生检测作用后紫外吸收光谱、荧光发射光谱以及荧光量子产率的变化,获得新型探针对NO2的荧光增强效果。
本发明的一种实施方式采用以下技术方案:
一种基于香豆素对NO2的荧光增强效应的荧光探针,该探针的结构如下:
上述基于香豆素对NO2的荧光增强效应的荧光探针的制备方法包括如下步骤:
(1)制备4-N,N-二甲胺基-2-羟基-苯甲醛
将3-N,N-二甲胺基苯酚溶于干燥的DMF中,并在室温下逐滴滴加至由三氯氧磷和无水DMF新制的Vilsmeier Haack试剂中,接着室温搅拌至少15min,然后升温至35~40℃反应至少15min,再升温至80~90℃反应30~40min,冷却至室温,将反应混合物快速倒入大量冰水中,所得溶液用Na2CO3中和,收集沉淀并经过滤、水洗、干燥后得到4-N,N-二甲胺基-2-羟基-苯甲醛;
(2)制备7-N,N-二甲胺基-香豆素
将4-N,N-二甲胺基-2-羟基-苯甲醛和三苯基膦烯基乙酸乙酯在氩气保护下加热至180~185℃反应1~1.5h,冷却至室温,粗产物经硅胶柱色谱分离纯化得到7-N,N-二甲胺基-香豆素;
(3)制备7-N,N-二甲胺基-8-醛基香豆素
将7-N,N-二甲胺基-香豆素溶于干燥的DMF中,并在室温下逐滴滴加至由三氯氧磷和无水DMF新制的Vilsmeier Haack试剂中,然后升温至50~55℃反应 3.5~4h,冷却至室温并搅拌过夜,接着将反应混合液倒入大量冰水中,静置后过滤,收集滤液,减压真空浓缩至有沉淀析出,再静置至少2天后过滤,收集沉淀物干燥,得到7-N,N-二甲胺基-8-醛基香豆素;
(4)制备7-N,N-二甲胺基-8-肟基香豆素
首先将7-N,N-二甲胺基-8-醛基香豆素溶于乙醇溶液中,接着将盐酸羟胺和三乙胺加入上述溶液中,加热至65~70℃反应3~3.5h,将适量的水加入反应液中,并用二氯甲烷萃取,有机层用无水硫酸钠干燥、过滤、旋干得到粗产物,以体积比乙酸乙酯:二氯甲烷=1:2为流动相经硅胶柱层析分离纯化得到7-N,N- 二甲胺基-8-肟基香豆素。
上述基于香豆素对NO2的荧光增强效应的荧光探针用于对NO2进行检测。
将获得的新型探针7-N,N-二甲胺基-8-肟基香豆素溶于乙腈溶液中,通过紫外吸收光谱仪考察其紫外吸收光谱范围和中心吸收波长,通过荧光分光光度计考察其荧光发射光谱范围和中心发射波长。以荧蒽为参比物质,借助紫外吸收和荧光发射获得新型探针的荧光量子产率。
将新型探针溶于乙腈溶液中,通入一定浓度的NO2,考察新型探针对NO2的检测时间;加入不同的活性小分子,考察新型探针对NO2的选择性响应;通入适量浓度NO2反应一定时间后,考察新型探针对NO2的荧光增强效果。
与现有技术相比,本发明通过分子设计、化学合成获得新型探针7-N,N-二甲胺基-8-肟基香豆素。新型探针紫外吸收光谱范围为275~425nm,中心吸收波长为361nm,新型探针荧光发射光谱范围为375~575nm,中心发射波长为440nm。新型探针与NO2发生检测作用后,荧光量子产率由0.0025增加至0.045,荧光强度增强6.7倍,新型探针从无荧光到发射出深蓝色荧光。
附图说明
图1为本发明新型探针的制备路线。
图2为本发明新型探针自身的紫外吸收光谱。
图3为本发明新型探针自身的荧光发射光谱。
图4为本发明新型探针对NO2的荧光响应行为图谱。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
7-N,N-二甲胺基-8-肟基香豆素的制备路线如图1所示。其中化合物1是7-N,N- 二甲胺基-8-肟基香豆素,化合物2是7-N,N-二甲胺基-8-醛基香豆素,化合物3是 7-N,N-二甲胺基-香豆素,化合物4是4-N,N-二甲胺基-2-羟基-苯甲醛,化合物5是 3-N,N-二甲胺基苯酚。
实施例1 4-N,N-二甲胺基-2-羟基-苯甲醛的制备
3-N,N-二甲胺基苯酚(10.5g,0.075mol)溶于20mL干燥的DMF中,并在室温下逐滴滴加至由三氯氧磷(8.2mL,0.09mol)和无水DMF(17mL,0.22mol) 新制的Vilsmeier Haack试剂中,接着室温搅拌20min,升温至40℃反应20min,再升温至80℃反应30min。冷却至室温,反应混合物快速倒入大量冰水中,上述溶液用NaHCO3中和,收集沉淀并经过滤、水洗、干燥后得到目标产物8.8g,产率65%。
实施例2 7-N,N-二甲胺基-香豆素的制备
4-N,N-二甲胺基-2-羟基-苯甲醛(5g,30mmol)和三苯基膦烯基乙酸乙酯 (12g,35mmol)在氩气保护下加热至180℃反应1h,冷却至室温,粗产物经硅胶柱色谱分离纯化得到目标产物5.5g,产率62%。
实施例3 7-N,N-二甲胺基-8-醛基香豆素的制备
7-N,N-二甲胺基-香豆素(0.75g,4.0mmol)溶于干燥的30mL的DMF中,并在室温下逐滴滴加至由三氯氧磷(1.8mL,20mmol)和无水DMF(4.0mL, 50mmol)新制的VilsmeierHaack试剂中,接着升温至55℃反应4h,冷却至室温并搅拌12h,接着将反应混合液倒入大量冰水中,静置后过滤,收集滤液,减压真空浓缩至有沉淀析出,再静置3天后过滤,收集沉淀物干燥,得到目标产物0.25 g,产率25%。
实施例4 7-N,N-二甲胺基-8-肟基香豆素的制备
首先7-N,N-二甲胺基-8-醛基香豆素(0.10g,0.46mol)溶于15mL乙醇溶液中,接着将盐酸羟胺(0.097g,1.39mmol)和三乙胺(0.19mL,1.39mmol) 加入上述溶液中,加热至65℃反应3h,将适量的水加入上述反应液中,并用二氯甲烷萃取,有机层用无水硫酸钠干燥、过滤、旋干得到粗产物,以乙酸乙酯/ 二氯甲烷(1/2)为流动相经硅胶柱层析分离纯化得到浅黄色目标产物85mg,产率85%。
实施例5 新型探针自身光谱性质
将新型探针7-N,N-二甲胺基-8-肟基香豆素(11.6mg)溶于DMSO溶液(5.0 mL)配制成1.0×10-2mol/L探针储备液,接着将探针储备液用乙腈稀释至1.0× 10-6mol/L探针测试液。将上述探针测试液置于紫外吸收光谱仪上在800~200nm 范围内扫描紫外吸收光谱,如图2所示,紫外吸收光谱范围为275~425nm,中心吸收波长为361nm。将上述探针测试液置于比色池中放于荧光分光光度计中以361nm为固定激发波长扫描荧光发射光谱,如图3所示,荧光发射光谱范围为 375~575nm,中心发射波长为440nm。
实施例6 新型探针对NO2的荧光检测行为
从二氧化氮标准气瓶(50ppm,4L)引出经配气系统稀释成一定浓度的NO2气体(20ppm)通入上述新型探针标准液中(1.0×10-6mol/L),分别反应1、3、 6、10、15min,接着在荧光分光光度计上考察其荧光强度,发现探针在10min 后对NO2的荧光增强达到平台期;新型探针标准液中(1.0×10-6mol/L)加入不同的潜在干扰物(H2S、SO2、NO、H2O2、NO2 -和NO3 -),上述干扰物的浓度为 NO2的100倍,反应10min,发现除了NO2外干扰物并没有引起探针荧光增强,表明新型探针对NO2具有高选择性响应。将上述探针标准液与20ppm的NO2反应10 min,于荧光分光光度计上在361nm激发下测试440nm的荧光强度,如图4所示,荧光增强6.7倍,表明新型探针对NO2发射出深蓝色的荧光增强响应,增强效果为6.7倍。
尽管这里参照本发明的解释性实施例对本发明进行了描述,但是,应该理解,本领域技术人员可以设计出很多其他的修改和实施方式,这些修改和实施方式将落在本申请公开的原则范围和精神之内。
Claims (3)
1.一种基于香豆素对NO2的荧光增强效应的荧光探针,其特征在于该探针的结构如下:
2.权利要求1所述的基于香豆素对NO2的荧光增强效应的荧光探针的制备方法,其特征在于包括如下步骤:
(1)制备4-N,N-二甲胺基-2-羟基-苯甲醛
将3-N,N-二甲胺基苯酚溶于干燥的DMF中,并在室温下逐滴滴加至由三氯氧磷和无水DMF新制的Vilsmeier Haack试剂中,接着室温搅拌至少15min,然后升温至35~40℃反应至少15min,再升温至80~90℃反应30~40min,冷却至室温,将反应混合物快速倒入大量冰水中,所得溶液用Na2CO3中和,收集沉淀并经过滤、水洗、干燥后得到4-N,N-二甲胺基-2-羟基-苯甲醛;
(2)制备7-N,N-二甲胺基-香豆素
将4-N,N-二甲胺基-2-羟基-苯甲醛和三苯基膦烯基乙酸乙酯在氩气保护下加热至180~185℃反应1~1.5h,冷却至室温,粗产物经硅胶柱色谱分离纯化得到7-N,N-二甲胺基-香豆素;
(3)制备7-N,N-二甲胺基-8-醛基香豆素
将7-N,N-二甲胺基-香豆素溶于干燥的DMF中,并在室温下逐滴滴加至由三氯氧磷和无水DMF新制的Vilsmeier Haack试剂中,然后升温至50~55℃反应3.5~4h,冷却至室温并搅拌过夜,接着将反应混合液倒入大量冰水中,静置后过滤,收集滤液,减压真空浓缩至有沉淀析出,再静置至少2天后过滤,收集沉淀物干燥,得到7-N,N-二甲胺基-8-醛基香豆素;(4)制备7-N,N-二甲胺基-8-肟基香豆素
首先将7-N,N-二甲胺基-8-醛基香豆素溶于乙醇溶液中,接着将盐酸羟胺和三乙胺加入上述溶液中,加热至65~70℃反应3~3.5h,将适量的水加入反应液中,并用二氯甲烷萃取,有机层用无水硫酸钠干燥、过滤、旋干得到粗产物,以体积比乙酸乙酯:二氯甲烷=1:2为流动相经硅胶柱层析分离纯化得到7-N,N-二甲胺基-8-肟基香豆素。
3.权利要求1所述的基于香豆素对NO2的荧光增强效应的荧光探针的应用,其特征在于该探针用于对NO2进行检测。
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