CN108658838A - 一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法 - Google Patents
一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法 Download PDFInfo
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Abstract
本发明公开了一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法。本发明提供的甲醛荧光探针能通过肉眼观察探针溶液的颜色变化或者通过探针溶液的荧光强度变化判断溶液中是否含有甲醛。若有甲醛存在,在自然光下,探针溶液的颜色会由蓝色变为绿色且探针溶液的荧光强度会降低。本发明提供的甲醛荧光探针能抗H2O、乙醛、丙醛、丙酮醛、乙酸的干扰,特异性地检测甲醛,检测准确性高。在检测过程中使用方便,具有潜在的实际应用价值。
Description
技术领域
本发明属于甲醛检测技术领域,特别涉及一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法。
技术背景
甲醛是最简单的醛类化合物且应用广泛。甲醛广泛应用于化工产品中,特别是表面活性剂、涂料、橡胶、防腐剂等。甲醛也存在于食物中如蔬菜、水果、肉类和海鲜等。由于甲醛具有高度的毒性和挥发性,所以甲醛在人类健康方面引起了极大关注。人体暴露于高浓度甲醛的环境下会导致打喷嚏、咳嗽、恶心甚至死亡。据报道,甲醛对人体具有急性,慢性(非癌症)和潜在的致癌作用。因此,早期对甲醛的敏感检测对确保人体健康具有重要的意义。
目前检测甲醛的方法多种多样,包括高效液相色谱(HPLC)、气相色谱(GC)、辐射测定和质谱等。然而,这些传统的分析方法受到昂贵的分析仪器、样品准备程序复杂、分析时间长、分析结果易受干扰且无法实时检测等限制。近年来,基于荧光染料的检测技术由于具有高选择性、敏感性和操作简单等优点成为一种新的检测方法。因此,开发一种高敏感性及特异性的甲醛荧光探针,具有潜在的实际应用价值。
发明内容
本发明的目的在于提供一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法,探针对甲醛分子的选择性好,在其它干扰分析物存在下也能很好地对甲醛分子进行检测,且合成过程简便易操作,成本较低。
本发明的目的由以下实验方案实现:
一种基于七甲川吲哚菁的甲醛荧光探针,其特征在于,化学结构式如(I)所示:
其中,
中的任意一种。
一种基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,包括如下步骤:
1)将1,1,2-三甲基-1H-苯并[e]吲哚化合物或吲哚化合物和烷基化试剂加入三口烧瓶中,并加入乙腈或三氯甲烷使其完全溶解;溶液在氮气气氛下回流反应5-20小时,反应完全后冷却至室温,减压除去溶剂,用乙醚洗涤2-5次,干燥后得到季铵化的吲哚啉衍生物1;
2)将N,N-二甲基甲酰胺和二氯甲烷加入三口烧瓶中,并在-10-0℃下冷却0.5-2小时;然后加入三氯氧磷和二氯甲烷的混合溶剂;继续将环己酮滴加到三口烧瓶中,溶液在氮气气氛下回流反应2-5小时,反应完全后冷却至室温,倒入冰,静置过夜;将混合液过滤,收集固体并干燥,得到黄色固体化合物2;
3)将季铵化的吲哚啉衍生物1和化合物2加入三口烧瓶中,并加入溶剂正丁醇和甲苯使其完全溶解;溶液在氮气气氛下加热至90-110℃,反应1-5小时后冷却至室温;随后将反应液用乙醚沉淀,并用柱层析法纯化产物,得到七甲川吲哚菁衍生物3;
4)将七甲川吲哚菁衍生物3和哌嗪加入三口烧瓶中,并加入溶剂N,N-二甲基甲酰胺使其完全溶解;溶液在氮气气氛下加热至25-100℃,反应5-20小时后冷却至室温,减压除去溶剂,用柱层析法纯化产物,得到七甲川吲哚菁衍生物4;
5)将七甲川吲哚菁衍生物4、碘化钠、碳酸钾和2-溴乙胺氢溴酸盐加入三口烧瓶中,并加入甲醇使其全部溶解;溶液在氮气气氛下回流反应5-20小时,反应完全后冷却至室温,减压除去溶剂,用柱层析法纯化产物,即得到基于七甲川吲哚菁的甲醛荧光探针。
优选的,步骤1)中1,1,2-三甲基-1H-苯并[e]吲哚化合物或吲哚化合物和烷基化试剂的摩尔比在1:1-1:5之间。
优选的,步骤2)中,N,N-二甲基甲酰胺和二氯甲烷的摩尔比在1:1-1:5之间;三氯氧磷和二氯甲烷的摩尔比在1:1-1:5之间。
优选的,步骤3)中,季铵化的吲哚啉衍生物1和化合物2的摩尔比在1:1-1:5之间,溶剂体积比为正丁醇:甲苯=7:3。
优选的,步骤4)中,七甲川吲哚菁衍生物3和哌嗪的摩尔比在1:1-1:10之间。
优选的,步骤5)中,七甲川吲哚菁衍生物4、碘化钠、碳酸钾和2-溴乙胺氢溴酸盐的摩尔比在1:0.1:0.1:1-1:1:1:5之间。
优选的,所述制备方法得到的基于七甲川吲哚菁的甲醛荧光探针的特征在于:1HNMR(400MHz,DMSO)δ8.19(d,J=8.5Hz,2H),8.09–7.97(m,4H),7.76(d,J=13.3Hz,4H),7.67(d,J=8.8Hz,2H),7.61(t,J=7.6Hz,2H),7.45(t,J=7.5Hz,2H),5.97(d,J=13.5Hz,2H),3.78(s,4H),3.65(s,6H),3.10(s,2H),2.78(d,J=15.8Hz,6H),2.55(s,4H),1.92(s,12H),1.83–1.74(m,2H).13C NMR(101MHz,DMSO)δ171.04,141.41,140.55,132.03,131.14,130.47,130.40,128.19,127.96,124.43,123.96,122.32,111.60,96.35,54.85,54.59,49.78,49.37,43.46,41.85,36.33,31.52,28.42,24.90,22.02。
一种基于七甲川吲哚菁的甲醛荧光探针的使用方法:将上述基于七甲川吲哚菁的甲醛荧光探针用于甲醛的检测。
优选的,将上述基于七甲川吲哚菁的甲醛荧光探针的浓度为1×10-6-1×10-4mol/L的甲醇溶液用于甲醛的检测,然后加入待测液混合均匀,最后进行荧光发射测定或者直接观察溶液颜色的变化;若有甲醛存在,探针溶液的荧光强度降低且探针溶液的颜色由蓝色变为绿色。
本发明具有如下有益效果:
本发明设计合成的甲醛荧光探针,对甲醛分子具有裸眼可分辨的检测效果;对甲醛分子响应快,在甲醛分子存在的条件下1分钟内就能使吸收光谱红移;对甲醛分子的选择性好,在其它干扰分析物存在下也能很好地对甲醛分子进行检测,能抗H2O、乙醛、丙醛、丙酮醛、乙酸的干扰,特异性地检测待测样品中的甲醛;合成过程简便易操作,成本较低。
附图说明
图1为实施例1中探针HCy1的反应流程图。
图2为实施例1中探针HCy1的1H NMR图。
图3为实施例1中探针HCy1的13C NMR图。
图4为实施例1中探针HCy1的质谱。
图5为实施例2中探针HCy1溶液加入不同浓度甲醛的紫外吸收谱图。
图6为实施例2中探针HCy1溶液加入不同浓度甲醛的荧光谱图。
图7为实施例2中探针HCy1溶液加入甲醛后的表观颜色对照图。
图8为实施例3中探针HCy1对不同干扰分析物的吸收谱图。
图9为实施例3中探针HCy1对不同干扰分析物的选择性图谱;图中,1,空白;2,甲醛;3,水;4,乙醛;5,丙醛;6,丙酮醛;7,乙酸。
图10为实施例4中探针HCy1的荧光强度与甲醛浓度的线性关系图。
图11为实施例1中探针HCy1识别甲醛的机理。
具体实施方式
为使本领域的技术人员更好地理解本发明的技术方案,下面结合附图对本发明提供的一种基于七甲川吲哚菁的甲醛荧光探针及其制备方法和使用方法进行详细描述,所述的七甲川吲哚菁衍生物以探针HCy1为例。以下实施例仅用于说明本发明而非用于限制本发明的范围。
下述实施例中均采用常规实验方法,如有特殊情况会予以说明。下述实施例中均采用商业购买的材料、试剂等,如有特殊情况会予以说明。
实施例1:探针HCy1的制备
1)将1,1,2-三甲基-1H-苯并[e]吲哚(1.19g,5mmol)和碘甲烷(1.08g,5mmol)(摩尔比在1:3)加入三口烧瓶中,并加入溶剂乙腈使其完全溶解。溶液在氮气气氛下回流反应10小时,反应完全后冷却至室温,减压除去溶剂,残余物用乙醚洗涤3次,干燥后得到白色粉末状化合物1(1.7g),产率为85%。
1H NMR(400MHz,DMSO)δ8.38(d,J=8.3Hz,1H),8.34–8.28(m,1H),8.23(d,J=8.1Hz,1H),8.11(d,J=8.9Hz,1H),7.80(s,1H),7.73(s,1H),4.10(s,3H),2.88(s,3H),1.76(s,6H)。
2)将N,N-二甲基甲酰胺(DMF)(40mL,0.5mmol)和二氯甲烷(40mL)(摩尔比在1:3)加入三口烧瓶中,并在0℃下冷却0.5小时。然后加入三氯氧磷(37mL)和二氯甲烷(35mL)的混合溶剂,继续将环己酮(10g,0.1mol)滴加到三口烧瓶中。溶液在氮气气氛下回流反应3小时,反应完全后冷却至室温,倒入300g冰,静置过夜。将混合液过滤,收集固体并干燥,得到黄色固体状化合物2(9g),产率为52%。
3)将化合物1(386mg,1.1mmol)和化合物2(172mg,1.1mmol)(摩尔比在1:1)加入三口烧瓶中,并加入溶剂体积比为正丁醇:甲苯=7:3的溶剂使其完全溶解。溶液在氮气气氛下加热至105℃,回流反应3小时,反应完全后冷却至室温,再用乙醚沉淀,并用柱层析法纯化产物,得到金色粉末状化合物3(368mg),产率为47%。
1H NMR(400MHz,CDCl3)δ8.48(d,J=14.2Hz,2H),8.16(d,J=8.5Hz,2H),7.98(dd,J=8.4,3.0Hz,4H),7.64(t,J=7.7Hz,2H),7.50(dd,J=11.7,7.1Hz,4H),6.34(s,2H),3.92(s,6H),2.84(t,J=6.0Hz,4H),2.06(s,14H)。
4)将化合物3(60mg,0.1mmol)和哌嗪(43mg,0.4mmol)(摩尔比在1:4)加入三口烧瓶中,并加入溶剂DMF使其完全溶解。溶液在氮气气氛下加热至80℃,反应3小时,反应完全后冷却至室温,减压除去溶剂,用柱层析法纯化产物,得到金黄色粉末状化合物4(62mg),产率为99%。
1H NMR(400MHz,CDCl3)δ8.27(d,J=8.4Hz,2H),7.95(dd,J=16.6,11.4Hz,6H),7.65(t,J=7.7Hz,2H),7.46(t,J=7.3Hz,2H),7.37(d,J=8.8Hz,2H),5.88(s,2H),4.11(s,4H),3.77(s,6H),3.54(s,4H),3.19(s,1H),2.95(d,J=29.1Hz,2H),2.57(t,J=6.2Hz,4H),2.07(s,12H)。
5)将化合物4(30mg,0.04mmol)、碘化钠(1.5mg,0.01mmol)、碳酸钾(1.5mg,0.01mmol)和2-溴乙胺氢溴酸盐(33mg,0.16mmol)(摩尔比在4:1:1:16)加入三口烧瓶中,并加入甲醇使其全部溶解。溶液在氮气气氛下回流反应6小时,反应完全后冷却至室温,减压除去溶剂,用柱层析法纯化产物,最终得到紫色粉末状化合物HCy1(13mg),产率为35%。
1H NMR(400MHz,DMSO)δ8.19(d,J=8.5Hz,2H),8.09–7.97(m,4H),7.76(d,J=13.3Hz,4H),7.67(d,J=8.8Hz,2H),7.61(t,J=7.6Hz,2H),7.45(t,J=7.5Hz,2H),5.97(d,J=13.5Hz,2H),3.78(s,4H),3.65(s,6H),3.10(s,2H),2.78(d,J=15.8Hz,6H),2.55(s,4H),1.92(s,12H),1.83–1.74(m,2H).13C NMR(101MHz,DMSO)δ171.04,141.41,140.55,132.03,131.14,130.47,130.40,128.19,127.96,124.43,123.96,122.32,111.60,96.35,54.85,54.59,49.78,49.37,43.46,41.85,36.33,31.52,28.42,24.90,22.02。
实施例2:不同浓度甲醛对探针HCy1的吸收和荧光滴定实验
取上述所合成的探针HCy1溶于甲醇溶液中,配制成浓度为1mmol/L的探针母液;将甲醛水溶液稀释成浓度为0.1mmol/L的甲醛母液。取12份体积为10μL的探针母液,分别加入1mL的甲醇溶液和不同浓度的甲醛,用甲醇溶液定容至2mL,配制成探针浓度为10μmol/L以及甲醛浓度分别为0、0.1、0.15、0.2、0.25、0.3、0.35、0.4、0.45、0.5、1、2mmol/L的测试溶液。分别用紫外光谱仪和荧光光谱仪测试探针HCy1随不同浓度甲醛的加入,其吸收和荧光谱图的变化。如图6所示,随着甲醛浓度的升高,探针在718nm处的吸收强度逐渐降低,同时在804nm处的吸收强度逐渐增强。如图7所示,随着甲醛浓度的升高,探针在816nm处的荧光强度逐渐降低。
实施例3:探针HCy1对不同干扰分析物的选择性研究
从上述取出5等份10μL的探针母液,向其中分别加入甲醛、H2O、乙醛、丙醛和丙酮醛溶液,用甲醇溶液稀释至2mL。配成探针浓度为10μmol/L,干扰分析物的浓度为0.1mmol/L的测试溶液,5分钟后测试溶液的吸收光谱的变化。如图8所示,只有加入甲醛的测试液在718nm处的吸收强度逐渐降低,同时在804nm处的吸收强度逐渐增强。为了更加直观地观察荧光探针HCy1与各种分析物反应之后紫外可见光谱的变化,将紫外可见光谱红移的波长以柱状图的形式呈现出来,如图9所示。
实施例4:探针HCy1的检测极限
根据图6的荧光光谱图,将荧光探针HCy1(10μmol/L)与甲醛反应后的荧光强度与甲醛浓度(0-0.35mmol/L)作图,发现探针的荧光强度与甲醛在一定浓度范围内呈现良好的线性关系,如图10所示。经线性拟合得到方程为y=-31844.54X+1.3465E6,线性相关系数为R2=0.9636。检测限用下式:D1=3σ/k(D1为检测下限,σ为截距标准差,k为斜率)可计算出检测限为1.32μM。
最后,上述实施例中仅列出的甲醛荧光探针HCy1,并非仅限本发明的内容,可以对其作一些简单的结构修改或改进。因此,对于本领域的技术人员,在不偏离本发明精神的情况下,可以做出合理的修改或改进。
Claims (10)
1.一种基于七甲川吲哚菁的甲醛荧光探针,其特征在于,化学结构式如(I)所示:
其中,
中的任意一种。
2.一种基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,包括如下步骤:
1)将1,1,2-三甲基-1H-苯并[e]吲哚化合物或吲哚化合物和烷基化试剂加入三口烧瓶中,并加入乙腈或三氯甲烷使其完全溶解;溶液在氮气气氛下回流反应5-20小时,反应完全后冷却至室温,减压除去溶剂,用乙醚洗涤2-5次,干燥后得到季铵化的吲哚啉衍生物1;
2)将N,N-二甲基甲酰胺和二氯甲烷加入三口烧瓶中,并在-10-0℃下冷却0.5-2小时;然后加入三氯氧磷和二氯甲烷的混合溶剂;继续将环己酮滴加到三口烧瓶中,溶液在氮气气氛下回流反应2-5小时,反应完全后冷却至室温,倒入冰,静置过夜;将混合液过滤,收集固体并干燥,得到黄色固体化合物2;
3)将季铵化的吲哚啉衍生物1和化合物2加入三口烧瓶中,并加入溶剂正丁醇和甲苯使其完全溶解;溶液在氮气气氛下加热至90-110℃,反应1-5小时后冷却至室温;随后将反应液用乙醚沉淀,并用柱层析法纯化产物,得到七甲川吲哚菁衍生物3;
4)将七甲川吲哚菁衍生物3和哌嗪加入三口烧瓶中,并加入溶剂N,N-二甲基甲酰胺使其完全溶解;溶液在氮气气氛下加热至25-100℃,反应5-20小时后冷却至室温,减压除去溶剂,用柱层析法纯化产物,得到七甲川吲哚菁衍生物4;
5)将七甲川吲哚菁衍生物4、碘化钠、碳酸钾和2-溴乙胺氢溴酸盐加入三口烧瓶中,并加入甲醇使其全部溶解;溶液在氮气气氛下回流反应5-20小时,反应完全后冷却至室温,减压除去溶剂,用柱层析法纯化产物,即得到基于七甲川吲哚菁的甲醛荧光探针。
3.根据权利要求2所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,步骤1)中1,1,2-三甲基-1H-苯并[e]吲哚化合物或吲哚化合物和烷基化试剂的摩尔比在1:1-1:5之间。
4.根据权利要求3所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,步骤2)中,N,N-二甲基甲酰胺和二氯甲烷的摩尔比在1:1-1:5之间;三氯氧磷和二氯甲烷的摩尔比在1:1-1:5之间。
5.根据权利要求4所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,步骤3)中,季铵化的吲哚啉衍生物1和化合物2的摩尔比在1:1-1:5之间,溶剂体积比为正丁醇:甲苯=7:3。
6.根据权利要求5所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,步骤4)中,七甲川吲哚菁衍生物3和哌嗪的摩尔比在1:1-1:10之间。
7.根据权利要求6所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,步骤5)中,七甲川吲哚菁衍生物4、碘化钠、碳酸钾和2-溴乙胺氢溴酸盐的摩尔比在1:0.1:0.1:1-1:1:1:5之间。
8.根据权利要求7所述的基于七甲川吲哚菁的甲醛荧光探针的制备方法,其特征在于,所述制备方法得到的基于七甲川吲哚菁的甲醛荧光探针的特征在于:1H NMR(400MHz,DMSO)δ8.19(d,J=8.5Hz,2H),8.09–7.97(m,4H),7.76(d,J=13.3Hz,4H),7.67(d,J=8.8Hz,2H),7.61(t,J=7.6Hz,2H),7.45(t,J=7.5Hz,2H),5.97(d,J=13.5Hz,2H),3.78(s,4H),3.65(s,6H),3.10(s,2H),2.78(d,J=15.8Hz,6H),2.55(s,4H),1.92(s,12H),1.83–1.74(m,2H).13C NMR(101MHz,DMSO)δ171.04,141.41,140.55,132.03,131.14,130.47,130.40,128.19,127.96,124.43,123.96,122.32,111.60,96.35,54.85,54.59,49.78,49.37,43.46,41.85,36.33,31.52,28.42,24.90,22.02。
9.一种基于七甲川吲哚菁的甲醛荧光探针的使用方法,其特征在于,将权利要求1所述的基于七甲川吲哚菁的甲醛荧光探针用于甲醛的检测。
10.根据权利要求9所述的基于七甲川吲哚菁的甲醛荧光探针的使用方法,其特征在于,将基于七甲川吲哚菁的甲醛荧光探针的1×10-6-1×10-4mol/L的甲醇溶液用于甲醛的检测,然后加入待测液混合均匀,最后进行荧光发射测定或者直接观察溶液颜色的变化;若有甲醛存在,探针溶液的荧光强度降低且探针溶液的颜色由蓝色变为绿色。
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