CN107090002A - 一种检测汞离子的反应型萘酰亚胺荧光探针及其制备方法与应用 - Google Patents
一种检测汞离子的反应型萘酰亚胺荧光探针及其制备方法与应用 Download PDFInfo
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- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 title claims abstract description 36
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Abstract
本发明属于汞离子荧光识别检测剂领域,涉及一种检测汞离子的反应型萘酰亚胺荧光探针及其制备方法与应用。该制备方法由已知化合物N‑正丁基‑4‑羟基‑1,8‑萘酰亚胺与二甲基硫代磷酰氯进行缩合反应,得到一种在CH3CH2OH/HEPES(10 mM,pH=7.4,1/9,v/v)体系中,可以用做Hg2+的高选择性和高灵敏性的荧光探针HgL1。探针HgL1合成步骤短,产率高,该探针为一例典型的荧光化学剂量计型荧光探针。利用荧光化学剂量计对离子进行检测时,荧光信号的强度变化与分析物的浓度有着密切的关系,表现为累加效应。本发明的探针具有高选择性和高灵敏性等优点。
Description
技术领域
本发明属于汞离子荧光识别检测剂领域,涉及一种反应型的基于萘酰亚胺的汞离子检测荧光探针及其制备方法与应用。
背景技术
汞是一种典型的有毒重金属,可以对生物体的神经系统造成永久性的损伤。汞主要以离子的形式进入生物体中,并在生物体内富集。环境中汞离子对动植物和人体健康造成巨大的威胁。汞离子具备较强的嗜硫性,过量的汞离子与生物体内含S的蛋白质或者酶发生反应,从而引起一系列的疾病。对生物体的神经系统和正常代谢活动造成极大的伤害,如汞离子过量可以导致不可逆的DNA损伤、肺水肿、肾衰竭以及多种类型的自闭症等症状。正是由于汞离子的剧毒性,世界上多个国家和相关组织均对汞离子在饮用水和工业废水中的含量做了严格的要求,如美国环保局(EPA)就严格规定在饮用水中的汞离子含量不得超过2ppb。对环境中汞离子的快速检测尤为重要,比如对环境中和食品中汞离子残留的检测有着重要的意义。
荧光探针由于具有成本较低、操作仪器简单、检测限低、实时监测等优点,荧光探针法检测金属离子近年来受到广泛关注。基于“turn-on”机理的荧光传感材料可减少检测错误,对复杂体系检测更准确。萘酰亚胺结构的可修饰性表现在可以通过改变4位或萘酰亚胺氮原子上连接的取代基进而得到新的化合物,通过改变识别基团可以得到多种具有不同性能的荧光探针。此类化合物的分子结构具有以下优点:有大的平面共轭基团,有较强的荧光,光化学与光物理具有光稳定性好、荧光发射波长适中且Stocks位移大。
发明内容
本发明为解决高选择、高灵敏检测河水、湖水、工业废水及土壤中汞离子检测的技术问题,公开了一种反应型的基于萘酰亚胺的汞离子检测荧光探针及其制备方法与应用,该制备方法由已知化合物N-正丁基-4-羟基-1,8-萘酰亚胺与二甲基硫代磷酰氯进行缩合反应,得到一种在CH3CH2OH/HEPES(10mM,pH=7.4,1/9,v/v)体系中,可以用做Hg2+的高选择性和高灵敏性的荧光探针HgL1。
为解决上述技术问题,本发明采用以下技术方案:
一种检测汞离子的反应型萘酰亚胺荧光探针,所述荧光探针结构式如下所示:
所述的反应型萘酰亚胺荧光探针的制备方法,
合成路线如下所示:
制备步骤如下:
(1)避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺与无水三乙胺混合后,溶于无水二氯甲烷溶液中,然后在冰浴条件下滴加二甲基硫代磷酰氯的无水二氯甲烷溶液开始反应,滴加完毕后,室温条件下继续反应(2-10)小时;
(2)将步骤(1)中的反应液用饱和氯化钠溶液洗涤、分离有机相,有机相经无水硫酸钠干燥、过滤、减压除去溶剂,经硅胶柱层析分离,即得到反应型萘酰亚胺荧光探针HgL1。
所述制备方法制备的反应型萘酰亚胺荧光探针的产率为60-90%。
所述步骤(1)中N-正丁基-4-羟基-1,8-萘酰亚胺的制备方法为:
a.N-正丁基-4-溴-1,8萘酰亚胺(compound 2)的合成:将4-溴-1,8-萘二甲酸酐(10.90g,39.0mmol)与正丁胺(13.9mL,142.0mmol)溶解于150mL的无水乙醇中,回流反应15小时,薄层色谱检测反应完全后,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:20),经硅胶柱层析分离得到10.3g的浅黄色固体,即N-正丁基-4-溴-1,8萘酰亚胺;
b.N-正丁基-4-甲氧基-1,8萘酰亚胺(compound 3)的合成:将N-正丁基-4-溴-1,8萘酰亚胺(7.50g,22.6mmol),甲醇钠(21.30g,394.0mmol)和五水硫酸铜(0.65g,2.6mmol),回流反应6小时,薄层色谱检测反应完全后,减压除去溶剂得黄色固体混合物。用一定量的二氯甲烷溶解黄色固体混合物,用饱和氯化钠溶液洗涤三次,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:15),经硅胶柱层析分离得到4.1g的黄白色颗粒粉末,即N-正丁基-4-甲氧基-1,8萘酰亚胺;
c.N-正丁基-4-羟基-1,8萘酰亚胺(compound 4)的合成:将N-正丁基-4-甲氧基-1,8萘酰亚胺(3.80g,13.5mmol)与170mL的57%的氢碘酸混合,回流反应12小时,薄层色谱检测反应完全后,冷却反应体系至0℃,有大量固体析出,过滤并用水洗涤固体,所得固体用乙酸乙酯和石油醚重结晶,过滤晶体,真空干燥得到黄色针状固体1.7g。合并重结晶过程所得滤液并浓缩,用乙酸乙酯和石油醚为洗脱剂(体积比为1:10),经硅胶柱层析分离得到1.2g的黄色针状固体,即N-正丁基-4-羟基-1,8萘酰亚胺。
所述步骤(1)中,避光条件通过采用锡箔纸包裹反应容器得到。
所述步骤(1)中,N-正丁基-4-羟基-1,8-萘酰亚胺:三乙胺:二甲基硫代磷酰氯的物质的量比为1:(1-10):(1-4)。
所述步骤(2)中,硅胶柱层析分离采用的洗脱液为乙酸乙酯和石油醚,其中乙酸乙酯:石油醚的体积比为1:(2-10)。
所述的反应型萘酰亚胺荧光探针作为检测河水、湖水、工业废水及土壤中汞离子的应用。
本发明的有益效果在于:
(1)探针HgL1合成步骤短,产率高,该探针为一例典型的荧光化学剂量计型荧光探针。该类由于可以和目标分析物发生不可逆的化学反应,对分析物表现出高选择性,突显出其在重金属离子检测中的优势。利用荧光化学剂量计对离子进行检测时,荧光信号的强度变化与分析物的浓度有着密切的关系,表现为累加效应,该类探针具有高选择性和高灵敏性等优点。
(2)通过紫外-可见光谱实验、荧光光谱实验研究等实验结果,推测出HgL1识别二价汞离子的可能机理如附图12所示:探针溶液体系中加入Hg2+,由于Hg2+具有较强的嗜硫性,Hg2+与探针HgL1分子结构中‘P=S’中的S原子结合,生成并脱去一分子的HgS,释放出强烈的荧光信号,生成具有荧光的产物HgL1-Hg,从而实现对汞离子的高效专一检测。通过HR-MS对产物HgL1-Hg的结构进行了确证(附图13)。实验结果表明,HgL1-Hg理论计算值为270.1130,HR-MS结果显示为270.1122,该数据确证了附图12所示作用机理。
(3)探针HgL1对汞离子的最低检测限为50nM,该检测限表明探针HgL1对Hg2+的识别非常灵敏,满足中国国家标准对工业废水中汞离子限量标准的要求,具备较强的实际应用价值。
附图说明
图1为本发明的荧光探针HgL1的核磁共振磷谱图;
图2为本发明的荧光探针HgL1的核磁共振氢谱图;
图3为本发明的荧光探针HgL1的核磁共振碳谱图;
图4为本发明的荧光探针HgL1的高分辨质谱图;
图5为本发明的荧光探针HgL1紫外选择性图;
图6为本发明的荧光探针HgL1荧光选择性图,激发波长445nm;
图7为本发明的荧光探针HgL1识别Hg2+的抗金属阳离子干扰性图,激发波长445nm,发射波长549nm;
图8为本发明的荧光探针HgL1识别Hg2+的抗阴离子干扰性图,激发波长445nm,发射波长549nm;
图9为本发明的荧光探针HgL1荧光滴定图,激发波长445nm;
图10为最低检测限图,激发波长445nm,发射波长549nm;
图11为本发明的荧光探针HgL1识别汞离子的机理验证荧光发射图,激发波长445nm;
图12为本发明的荧光探针HgL1识别机理图;
图13为本发明的荧光探针HgL1识别机理验证高分辨图。
具体实施方式
一种检测汞离子的反应型萘酰亚胺荧光探针,所述荧光探针结构式如下所示:
所述的反应型萘酰亚胺荧光探针的制备方法,
合成路线如下所示:
制备步骤如下:
(1)避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺与无水三乙胺混合后,溶于无水二氯甲烷溶液中,然后在冰浴条件下滴加二甲基硫代磷酰氯的无水二氯甲烷溶液开始反应,滴加完毕后,室温条件下继续反应(2-10)小时;
(2)将步骤(1)中的反应液用饱和氯化钠溶液洗涤、分离有机相,有机相经无水硫酸钠干燥、过滤、减压除去溶剂,经硅胶柱层析分离,即得到反应型萘酰亚胺荧光探针HgL1。
所述制备方法制备的Hg2+荧光探针分子HgL1的产率为60-90%。
所述步骤(1)中N-正丁基-4-羟基-1,8-萘酰亚胺的制备方法为:
a.N-正丁基-4-溴-1,8萘酰亚胺(compound 2)的合成:将4-溴-1,8-萘二甲酸酐(10.90g,39.0mmol)与正丁胺(13.9mL,142.0mmol)溶解于150mL的无水乙醇中,回流反应15小时,薄层色谱检测反应完全后,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:20),经硅胶柱层析分离得到10.3g的浅黄色固体,即N-正丁基-4-溴-1,8萘酰亚胺;
b.N-正丁基-4-甲氧基-1,8萘酰亚胺(compound 3)的合成:将N-正丁基-4-溴-1,8萘酰亚胺(7.50g,22.6mmol),甲醇钠(21.30g,394.0mmol)和五水硫酸铜(0.65g,2.6mmol),回流反应6小时,薄层色谱检测反应完全后,减压除去溶剂得黄色固体混合物。用一定量的二氯甲烷溶解黄色固体混合物,用饱和氯化钠溶液洗涤三次,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:15),经硅胶柱层析分离得到4.1g的黄白色颗粒粉末,即N-正丁基-4-甲氧基-1,8萘酰亚胺;
c.N-正丁基-4-羟基-1,8萘酰亚胺(compound 4)的合成:将N-正丁基-4-甲氧基-1,8萘酰亚胺(3.80g,13.5mmol)与170mL的57%的氢碘酸混合,回流反应12小时,薄层色谱检测反应完全后,冷却反应体系至0℃,有大量固体析出,过滤并用水洗涤固体,所得固体用乙酸乙酯和石油醚重结晶,过滤晶体,真空干燥得到黄色针状固体1.7g。合并重结晶过程所得滤液并浓缩,用乙酸乙酯和石油醚为洗脱剂(体积比为1:10),经硅胶柱层析分离得到1.2g的黄色针状固体,即N-正丁基-4-羟基-1,8萘酰亚胺。
所述步骤(1)中,避光条件通过采用锡箔纸包裹反应容器得到。
所述步骤(1)中,N-正丁基-4-羟基-1,8-萘酰亚胺:三乙胺:二甲基硫代磷酰氯的物质的量比为1:(1-10):(1-4)。
所述步骤(2)中,硅胶柱层析分离采用的洗脱液为乙酸乙酯和石油醚,其中乙酸乙酯:石油醚的体积比为1:(2-10)。
所述的反应型萘酰亚胺荧光探针作为检测河水、湖水、工业废水及土壤中汞离子的应用。
本发明中制备荧光探针HgL1的过程中所使用的化学试剂、溶剂、金属离子等均购自阿拉丁试剂公司。在荧光探针HgL1的结构确证过程采用Bruke公司DTX-400型核磁共振谱仪,溶剂为氘代氯仿,以TMS为内标记录核磁共振氢谱和碳谱。采用Thermo公司的Q-ExactiveHR-MS质谱仪记录高分辨质谱数据。采用日本日立公司F-7000荧光光谱仪记录荧光光谱。
下面结合具体实施例对本发明进行进一步的解释说明:
实施例1
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(269mg,1mmol)与三乙胺(270μL,2mmol)混合于20mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(241μL,4mmol)的二氯甲烷(15mL)溶液,冰浴条件下反应完全后(8小时),反应液用饱和氯化钠溶液(25mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:5),经硅胶柱层析分离得到288.8mg的浅黄色固体,即为荧光探针分子HgL1,产率为80%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例2
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(269mg,1mmol)与三乙胺(540μL,4mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(482μL,4mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(4小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:8),经硅胶柱层析分离得到252mg的浅黄色固体,即为荧光探针分子HgL1,产率为70%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例3
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(1mmol)与三乙胺(1mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(1mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(10小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:2),经硅胶柱层析分离得到235mg的浅黄色固体,即为荧光探针分子HgL1,产率为65%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例4
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(1mmol)与三乙胺(10mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(2mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(6小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:10),经硅胶柱层析分离得到307mg的浅黄色固体,即为荧光探针分子HgL1,产率为85%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例5
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(1mmol)与三乙胺(6mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(1mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(10小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:8),经硅胶柱层析分离得到282mg的浅黄色固体,即为荧光探针分子HgL1,产率为78%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例6
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(1mmol)与三乙胺(8mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(1mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(2小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:5),经硅胶柱层析分离得到296mg的浅黄色固体,即为荧光探针分子HgL1,产率为82%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例7
探针HgL1的合成:
避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺(1mmol)与三乙胺(5mmol)混合于25mL无水二氯甲烷溶液中,冰浴条件下滴加入二甲基硫代磷酰氯(1mmol)的二氯甲烷(20mL)溶液,冰浴条件下反应完全后(9小时),反应液用饱和氯化钠溶液(40mL*3)洗涤,有机相用无水硫酸钠干燥,过滤,减压除去溶剂,用乙酸乙酯和石油醚为洗脱剂(体积比为1:2),经硅胶柱层析分离得到271mg的浅黄色固体,即为荧光探针分子HgL1,产率为75%。
核磁共振测定:31P NMR(162MHz,CDCl3):δ=97.05ppm;1H NMR(CDCl3,400MHz)δ0.98(t,J=7.4Hz,3H),1.46(q,J=7.2Hz,2H),1.73(m,2H),2.22(s,3H),2.25(s,3H),4.19(t,J=7.6Hz,2H),7.79(m,2H),8.39(d,J=8.0Hz,1H),8.59(d,J=8.0Hz,1H),8.63(d,J=7.2Hz,1H);13C NMR(CDCl3,100MHz)δ13.85,20.38,24.15,24.88,30.21,40.26,117.17,117.23,119.29,122.94,125.80,126.94,128.35,129.61,131.78,131.86,163.49,164.08.高分辨质谱测定:HR-ESI-MS calcd for C18H21NO3PS+:362.0980,found 362.0972[M+H+],(具体图谱见附图1-4)。
实施例1制备的探针HgL1的应用例
溶液的配制:
金属无机盐:硝酸铅,硝酸银,硝酸镉,其他均为氯化物(K+,Na+,Ca2+,Mg2+,Ba2+,Zn2 +,Fe2+,Fe3+,Mn2+,Co2+,Ni2+,Hg2+)且厂家均为阿拉丁试剂公司。准确称量相应无机金属盐,溶解在去离子水中配制成10mM的金属离子溶液备用。
1mM的探针溶液配制:准确称量上述实施例1中合成的荧光探针(HgL1),HgL1溶解在CH3CH2OH溶液中配制1mM的溶液备用。
选择性实验:
对金属离子的专一选择性是衡量金属离子类荧光探针分子是否高效的重要标准。首先,用紫外-可见光谱仪考察了探针HgL1对金属离子选择性。如附图5所示,单独的探针分子HgL1(10μM)在CH3CH2OH/HEPES(10mM,pH=7.4,1:9,v/v)溶液中在450nm附近紫外吸收强度比较低,当加入10当量的各种常见金属离子(K+,Na+,Li+,Ca2+,Mg2+,Ba2+,Zn2+,Cd2+,Fe2+,Mn2+,Pb2+,Co2+,Fe3+,Cr3+,Al3+,Ni2+,Sn2+,Sn4+)后,其紫外吸收强度与单独探针分子紫外吸收强度基本一致,只有加入10当量的Hg2+的加入使其在450nm处的紫外吸收明显增强。以上实验结果表明:该探针在紫外-可见光谱中对二价汞离子具备较好的专一识别能力。
其次,使用荧光光谱仪对该探针对金属离子的荧光选择性进行了测试。如附图6所示,单独的探针HgL1(10μM)在CH3CH2OH/HEPES(10mM,pH=7.4,1:9,v/v)溶液中具有较低的荧光发射强度(激发波长为445nm),当加入10当量的Hg2+后溶液体系荧光发射强度明显增强,但是加入其它常见金属离子(10当量,金属离子种类同紫外选择性实验)时,其溶液体系荧光发射强度没有明显变化。以上实验结果表明,该探针对二价汞离子具有较好的专一选择性。
荧光干扰性实验:
为了测试该探针分子对Hg2+检测的抗干扰能力,在荧光发射光谱中分别测试了其金属阳离子干扰性和常见阴离子干扰性实验。如附图7所示,在HgL1(10μM)在CH3CH2OH/HEPES(10mM,pH=7.4,1:9,v/v)溶液中分别加入测试的各种金属阳离子(100μM)测试其荧光发射强度(549nm),然后再向含有各种金属离子的溶液中加入50μM的Pd0溶液,由附图7可知,在其他金属阳离子存在时加入二价汞离子与单独加入二价汞离子时所得到的荧光强度(549nm)基本相同,该结果表明探针HgL1对二价汞离子的检测具有较强的抗金属阳离子干扰能力。按照相同的方法,测试了该探针对常见阴离子(NO3-,NO2-,F-,Cl-,Br-,H2PO4-,HPO4 2-,PO4 3-,HSO4-,SO4 2-,HCO3 -,CO3 2-)的抗干扰能力,如附图8所示,结果表明探针HgL1对二价汞离子的识别具有较强的抗阴离子干扰能力。
最低检测限实验:
良好的最低检测限是评价荧光探针是否具有实际应用价值的重要标准之一。在此采用荧光光谱仪滴定法来测定其对Hg2+的最低检测限,在CH3CH2OH/HEPES(10mM,pH=7.4,1:9,v/v)溶液中,固定探针HgL1浓度为10μM,测定加入不同浓度的Hg2+后溶液体系的荧光发射响应强度,结果表明随着Hg2+浓度的不断增加,体系荧光发射强度不断增强(附图9),研究发现溶液体系荧光发射强度值在Hg2+浓度为0.1-1μM间呈良好的线性(R2=0.990,附图10),经计算(3σ/k)得出该探针分子HgL1对Hg2+的检测限为50nM,该检测限表明探针HgL1对Hg2+的识别非常灵敏,满足中国国家标准对工业废水中汞离子限量标准的要求。
为了进一步研究探针HgL1对汞离子的识别机理,在此进行了碘化钾滴定实验。碘离子是一种常见的汞离子络合剂。如附图11所示,分别测定单独HgL1(10μM)的荧光发射光谱、加入10当量汞离子后的荧光发射光谱、再加入30当量KI后的荧光发射光谱,结果表明加入KI后与不加入KI的溶液体系荧光发射光谱强度变化不大,该实验结果表明探针HgL1对汞离子的识别作用是不可逆的。
Claims (6)
1.一种检测汞离子的反应型萘酰亚胺荧光探针,其特征在于,所述荧光探针结构式如下所示:
。
2.如权利要求1所述的检测汞离子的反应型萘酰亚胺荧光探针的制备方法,其特征在于,步骤如下:
(1)避光条件下,将N-正丁基-4-羟基-1,8-萘酰亚胺与无水三乙胺混合后,溶于无水二氯甲烷溶液中,然后在冰浴条件下滴加二甲基硫代磷酰氯的无水二氯甲烷溶液开始反应,滴加完毕后,室温条件下继续反应(2-10)小时;
(2)将步骤(1)中的反应液用饱和氯化钠溶液洗涤、分离有机相,有机相经无水硫酸钠干燥、过滤、减压除去溶剂,经硅胶柱层析分离,即得到反应型基于萘酰亚胺的Hg2+荧光探针分子HgL1。
3.如权利要求2所述的检测汞离子的反应型萘酰亚胺荧光探针的制备方法,其特征在于:所述步骤(1)中,避光条件通过采用锡箔纸包裹反应容器得到。
4.如权利2要求所述的检测汞离子的反应型萘酰亚胺荧光探针的制备方法,其特征在于:所述步骤(1)中,N-正丁基-4-羟基-1,8-萘酰亚胺:三乙胺:二甲基硫代磷酰氯的物质的量比为1:(1-10):(1-4)。
5.如权利要求2所述的检测汞离子的反应型萘酰亚胺荧光探针的制备方法,其特征在于:所述步骤(2)中,硅胶柱层析分离采用的洗脱液为乙酸乙酯和石油醚,其中乙酸乙酯:石油醚的体积比为1:(2-10)。
6.如权利要求1~5任一项所述的检测汞离子的反应型萘酰亚胺荧光探针作为检测河水、湖水、工业废水及土壤中汞离子的应用。
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