CN111825655A - 一种检测Hg2+用高灵敏性荧光探针及其制备方法和应用 - Google Patents
一种检测Hg2+用高灵敏性荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种检测Hg2+用高灵敏性荧光探针及其制备方法和应用。本发明利用天然可再生资源β‑蒎烯衍生物诺蒎酮为原料制得的N′‑(4′‑(6,6‑二甲基‑4,5,6,7‑四氢‑1H‑5,7‑桥亚甲基吲唑‑3‑基)‑[1,1′‑联苯]‑4‑亚甲基)吡啶‑2‑甲酰肼,能选择性地与Hg2+络合,并使其青色荧光迅速猝灭,检测极限达17nM,该化合物可作为专一性荧光探针用于检测Hg2+,具有很好的应用价值。
Description
技术领域
本发明属精细有机合成技术领域,涉及一种检测Hg2+用高灵敏性荧光探针及其制备方法。
背景技术
汞离子(Hg2+)是一种剧毒的重金属离子,广泛分布于土壤、河流、湖泊、地下水和工业废水中。Hg2+容易通过生物富集的方式进入生物体内,一旦人体摄入过量的汞离子,将对其神经、内脏、遗传基因等造成严重损伤。因此,开发快速便捷、高灵敏性和高选择性的用于检测Hg2+的方法在环境分析中非常重要。
近年来有一些关于有机荧光探针的合成研究以及用于Hg2+检测的报道,根据荧光探针发光基团的不同结构,通常包括:罗丹明类、BODIPY类、半花菁类、荧光素类、香豆素类和金属纳米配合物类等荧光探针。这些荧光探针大都需要有机溶剂的参与才能对汞离子进行检测且灵敏度较低。而采用可再生的天然萜烯为原料合成用于Hg2+检测的有机荧光探针的相关报道还非常少。
发明内容
针对现有技术中存在的不足,本发明所要解决的技术问题在于提供一种检测 Hg2+用高灵敏性荧光探针,可专一地与Hg2+反应,并在紫外光照射下其青色荧光迅速发生猝灭,可用于对Hg2+进行定性和定量分析。本发明所要解决的另一技术问题是提供一种检测Hg2+用高灵敏性荧光探针的制备方法。本发明还要解决的另一技术问题是提供一种高灵敏性荧光探针的应用。
为解决上述技术问题,本发明采用的技术方案为:
检测Hg2+用高灵敏性荧光探针,为N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼,结构式为:
所述的检测Hg2+用高灵敏性荧光探针的制备方法,其合成路线如下式所示:
具体的合成包括如下工艺步骤:
1)诺蒎酮与4-溴苯甲酸甲酯发生克莱森缩合反应,得到3-(4-溴苯甲酰基) 诺蒎酮;
2)3-(4-溴苯甲酰基)诺蒎酮与水合肼进行环化反应,得到3-(4-溴苯基)-6,6- 二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑;
3)3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑与4-甲酰基苯硼酸发生偶联反应,得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛;
4)4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛与吡啶-2-甲酰肼进行缩合,得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼。
步骤1)中,诺蒎酮与4-溴苯甲酸甲酯进行克莱森缩合得到3-(4-溴苯甲酰基) 诺蒎酮,具体的制备步骤为:
(1)将3mmol诺蒎酮、3~5mmol 4-溴苯甲酸甲酯、6~10mmol氢化钠和 40~60mL乙二醇二甲醚依次加入洁净干燥的三口烧瓶中,在氮气保护下加热回流反应6~8h,用TLC法跟踪监测反应进程,至诺蒎酮转化率达95%以上;
(2)反应液经冷却后,加入30~50mL去离子水淬灭反应,再用0.3~0.5L 乙酸乙酯萃取3次,合并的有机相再用饱和食盐水洗涤数次至中性,经无水硫酸钠干燥、过滤、浓缩后得到的固体产物,再用少量乙酸乙酯洗涤得到3-(4-溴苯甲酰基)诺蒎酮。
步骤2)中,在冰乙酸催化下,3-(4-溴苯甲酰基)诺蒎酮与水合肼发生环化反应,得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑,具体的制备步骤为:
(1)将0.5mol 3-(4-溴苯甲酰基)诺蒎酮、1.5~2.0mol水合肼、30~50mL乙醇加入三口烧瓶中,再加入0.1~0.2mL冰乙酸,加热回流反应4~6h,用TLC 法跟踪监测反应进程,直至3-(4-溴苯甲酰基)诺蒎酮转化率达到100%后终止反应;
(2)反应液经过浓缩除去乙醇后,加入0.1~0.2L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、浓缩后析出白色固体,用乙醇重结晶后抽滤洗涤得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑。
步骤3)中,以四(三苯基膦)钯作催化剂,3-(4-溴苯基)-6,6-二甲基-4,5,6,7- 四氢-1H-5,7-桥亚甲基吲唑与4-甲酰基苯硼酸进行偶联反应,得到4′-(6,6-二甲基 -4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛,具体的制备步骤为:
(1)在氮气保护下将5mmol 3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑、10~15mmol 4-甲酰基苯硼酸、0.25~0.3mmol四(三苯基膦)钯和 30~50mL1,4-二氧六环加入三口烧瓶中,然后将20~25mmol碳酸钾溶于10~15 mL去离子水后滴加到烧瓶中,在100℃下反应12~24h;
(2)反应液经过滤除去固体杂质后,滤液经减压蒸馏除去1,4-二氧六环溶剂,加入0.2~0.4L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、蒸去溶剂后,得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛粗产物;
(3)4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4- 甲醛粗产物经硅胶柱分离(200~300目,洗脱液石油醚/乙酸乙酯=3∶1,v/v),得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛。
步骤4)中,以哌啶作催化剂,4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛与吡啶-2-甲酰肼进行缩合反应,得到N′-(4′-(6,6- 二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼,具体的制备步骤为:
(1)将1mmol 4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′- 联苯基]-4-甲醛、1~2mmol吡啶-2-甲酰肼、10~15mL无水乙醇、1~3滴哌啶加入三口烧瓶中,回流反应12~24h,用TLC监测反应进程,直至4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛反应完全后停止反应;
(2)将反应液经浓缩除去部分乙醇后,冷却并析出固体,抽滤并用冷乙醇洗涤滤饼,得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′- 联苯]-4-亚甲基)吡啶-2-甲酰肼。
所述的N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼在检测Hg2+中的应用。能专一性地与Hg2+络合,在365nm紫外光下青色荧光迅速发生猝灭。
本发明以诺蒎酮为原料,与4-溴苯甲酸甲酯反应生成3-(4-溴苯甲酰基)诺蒎酮;3-(4-溴苯甲酰基)诺蒎酮再与水合肼进行环化反应得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑;3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢 -1H-5,7-桥亚甲基吲唑再与4-甲酰基苯硼酸进行偶联反应,得到化合物4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛;4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛继续与吡啶-2-甲酰肼缩合得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼。发现该化合物能专一性地识别Hg2+,可作为检测 Hg2+的荧光探针。
有益效果:与现有技术相比,本发明利用天然可再生资源β-蒎烯衍生物诺蒎酮为原料制得的N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′- 联苯]-4-亚甲基)吡啶-2-甲酰肼,能选择性地与Hg2+络合,并使其青色荧光迅速猝灭,检测极限达17nM,该化合物可作为专一性荧光探针用于检测Hg2+。
附图说明
图1是N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼与不同金属离子作用的荧光发射光谱猝灭选择性结果图;
图2是N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼与不同浓度的Hg2+反应的荧光光谱结果图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1
N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼的制备
1)3-(4-溴苯甲酰基)诺蒎酮的制备:
将3mmol诺蒎酮、3.6mmol 4-溴苯甲酸甲酯、9mmol氢化钠和60mL 乙二醇二甲醚依次加入三口烧瓶中,在氮气保护下加热回流反应,反应8h左右至诺蒎酮转化率达95%以上(TLC跟踪检测)。反应液经冷却后,加入30mL去离子水淬灭反应,再用0.3L乙酸乙酯萃取3次,合并的有机相再用饱和食盐水洗涤数次至中性,经无水硫酸钠干燥、过滤、浓缩后得到的固体产物,再用少量乙酸乙酯洗涤得到3-(4-溴苯甲酰基)诺蒎酮,得率为62.1%,纯度为98.7%。1H NMR(600 MHz,CDCl3)δ:15.48(s,1H),7.57(s,4H),2.68-2.64(m,2H),2.59(t,J=5.6Hz, 1H),2.572.53(m,1H),2.30-2.27(m,1H),1.45(d,J=9.9Hz,1H),1.35(s,3H),0.95(s,3H)。13C NMR(150MHz,CDCl3)δ:209.53,171.56,134.21,131.63,129.91, 124.77,104.19,54.91,39.94,39.69,28.39,27.85,25.93,21.66。
2)3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑的制备:
将0.5mol 3-(4-溴苯甲酰基)诺蒎酮、1.5mol水合肼、30mL乙醇加入三口烧瓶中,再加入0.1mL冰乙酸加热回流反应5h,用TLC法监测反应,直至3-(4- 溴苯甲酰基)诺蒎酮转化率达到100%后终止反应。反应液经过浓缩除去乙醇后,加入0.1L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、浓缩后析出白色固体,用乙醇重结晶后抽滤洗涤得到3-(4-溴苯基)-6,6- 二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑,得率69.3%,纯度为95.1%。1H NMR (600MHz,CDCl3)δ:7.50(d,J=2.4Hz,4H),7.08(s,1H),2.96-2.91(m,1H), 2.89-2.83(m,2H),2.74-2.69(m,1H),2.36-2.32(m,1H),1.40(s,3H),1.39(s,1H), 0.71(s,3H)。13C NMR(150MHz,CDCl3)δ:158.61,139.44,132.04,130.49,127.31, 121.55,109.88,41.64,41.49,41.23,32.49,26.39,26.19,21.61。
3)4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛的制备:
将5mmol 3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑、10mmol 4-甲酰基苯硼酸、0.25mmol四(三苯基膦)钯、40mL 1,4-二氧六环在氮气保护下加入三口烧瓶中搅拌并加热,然后将20mmol碳酸钾溶于10mL去离子水后滴加到烧瓶中在100℃下反应至过夜;反应液经过滤除去固体杂质后,滤液经减压蒸馏除去1,4-二氧六环溶剂,加入0.2L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、蒸去溶剂后,得到4′-(6,6-二甲基 -4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛粗产物。4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛粗产物经柱层析(200~300目硅胶,洗脱液石油醚/乙酸乙酯比为3:1),得到4′-(6,6-二甲基-4,5,6,7- 四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛,得率为61.2%,纯度为 98.5%。1H NMR(400MHz,CDCl3)δ:10.05(s,1H),7.94(d,J=8.1Hz,2H),7.76(t, J=8.7Hz,4H),7.66(d,J=8.3Hz,2H),5.29(s,1H),3.07-2.89(m,3H),2.74(d,J= 9.4Hz,1H),2.37(s,1H),1.45(d,J=9.6Hz,1H),1.41(s,3H),0.75(s,3H)。13C NMR(100MHz,CDCl3)δ:191.95,159.04,146.51,139.50,138.64,135.40,131.69,130.46,127.84,127.51,126.28,110.20,72.90,60.53,41.79,41.55,41.26,32.55,29.83,26.44,26.35,21.64,14.24。
4)N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4- 亚甲基)吡啶-2-甲酰肼的制备:
将1mmol 4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛、1mmol吡啶-2-甲酰肼、10mL无水乙醇、3滴哌啶加入三口烧瓶中,回流反应12~24h,用TLC监测反应进程,直至4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7- 桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛反应完全后停止反应。将反应液经浓缩除去部分乙醇后,冷却并析出固体,抽滤并用冷乙醇洗涤滤饼,得到N′-(4′-(6,6- 二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼,得率为91.4%,纯度为99.2%。1H NMR(600MHz,DMSO-d6)δ:12.49(s, 1H),12.18(s,1H),8.73(d,J=4.2Hz,1H),8.71(s,1H),8.15(d,J=7.7Hz,1H), 8.07(t,J=7.7Hz,1H),7.83(p,J=8.4Hz,8H),7.69-7.67(m,1H),2.99(d,J=12.8 Hz,1H),2.88(d,J=13.1Hz,1H),2.80(t,J=5.2Hz,1H),2.71(s,1H),2.31(s,1H), 1.39(s,3H),1.30(d,J=9.4Hz,1H),0.66(s,3H)。13C NMR(150MHz,DMSO-d6) δ:160.37,149.57,148.71,148.48,140.95,138.00,137.68,133.49,127.82,127.04, 127.00,126.81,125.53,122.69,108.78,40.98,40.52,32.11,26.07,26.00,21.36。
实施例2
将N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4- 亚甲基)吡啶-2-甲酰肼溶于DMF,配制成浓度为1mM的溶液,并用PBS缓冲溶液(pH=7.4,10mM)稀释到10μM使用。将不同的金属离子溶于去离子水并稀释到100μM使用,采用荧光光谱分析法测得不同的金属离子对N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼的荧光光谱,如图1所示。结果表明,相比于其他金属离子,只有Hg2+能够引起化合物的荧光光谱的明显改变,说明化合物可以专一性识别Hg2+。
实施例3
将N′-(4′-(6,6-二甲基-4,5,6,7-四氢一1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4- 亚甲基)吡啶-2-甲酰肼溶于DMF配制成浓度为1mM的溶液,再用PBS缓冲溶液(pH=7-4,10mM)稀释到10μM使用。同样将Hg2+溶于PBS缓冲溶液配成浓度为0、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1、2、4、6、8、10、15、 20μM的溶液。采用荧光光谱分析法测得不同浓度的Hg2+对N′-(4′-(6,6-二甲基 -4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼的荧光光谱,如图2所示。结果表明,化合物在460nm左右的荧光强度明显逐渐发生猝灭,说明化合物可以作为检测Hg2+的荧光探针。
Claims (9)
2.权利要求1所述的检测Hg2+用高灵敏性荧光探针的制备方法,其特征在于,包括如下步骤:
1)诺蒎酮与4-溴苯甲酸甲酯发生克莱森缩合反应,得到3-(4-溴苯甲酰基)诺蒎酮;
2)3-(4-溴苯甲酰基)诺蒎酮与水合肼进行环化反应,得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑;
3)3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑与4-甲酰基苯硼酸发生偶联反应,得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛;
4)4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛与吡啶-2-甲酰肼进行缩合,得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼。
3.根据权利要求2所述的检测Hg2+用高灵敏性荧光探针的制备方法,其特征在于,步骤1)中,诺蒎酮与4-溴苯甲酸甲酯发生克莱森缩合反应,得到3-(4-溴苯甲酰基)诺蒎酮;具体步骤为:
(1)将3mmol诺蒎酮、3~5mmol 4-溴苯甲酸甲酯、6~10mmol氢化钠和40~60mL乙二醇二甲醚依次加入洁净干燥的三口烧瓶中,在氮气保护下加热回流反应6~8h,用TLC法跟踪监测反应进程,至诺蒎酮转化率达95%以上;
(2)反应液经冷却后,加入30~50mL去离子水淬灭反应,再用0.3~0.5L乙酸乙酯萃取3次,合并的有机相再用饱和食盐水洗涤数次至中性,经无水硫酸钠干燥、过滤、浓缩后得到的固体产物,再用少量乙酸乙酯洗涤得到3-(4-溴苯甲酰基)诺蒎酮。
4.根据权利要求2所述的检测Hg2+用高灵敏性荧光探针的制备方法,其特征在于,步骤2)中,3-(4-溴苯甲酰基)诺蒎酮与水合肼进行环化反应,得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑;具体步骤为:
(1)将0.5mol 3-(4-溴苯甲酰基)诺蒎酮、1.5~2.0mol水合肼、30~50mL乙醇加入三口烧瓶中,再加入0.1~0.2mL冰乙酸,加热回流反应4~6h,用TLC法跟踪监测反应进程,直至3-(4-溴苯甲酰基)诺蒎酮转化率达到100%后终止反应;
(2)反应液经过浓缩除去乙醇后,加入0.1~0.2L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、浓缩后析出白色固体,用乙醇重结晶后抽滤洗涤得到3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑。
5.根据权利要求2所述的检测Hg2+用高灵敏性荧光探针的制备方法,其特征在于,步骤3)中,3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑与4-甲酰基苯硼酸发生偶联反应,得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛;具体步骤为:
(1)在氮气保护下将5mmol 3-(4-溴苯基)-6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑、10~15mmol 4-甲酰基苯硼酸、0.25~0.3mmol四(三苯基膦)钯和30~50mL 1,4-二氧六环加入三口烧瓶中,然后将20~25mmol碳酸钾溶于10~15mL去离子水后滴加到烧瓶中,在100℃下反应12~24h;
(2)反应液经过滤除去固体杂质后,滤液经减压蒸馏除去1,4-二氧六环溶剂,加入0.2~0.4L乙酸乙酯,用饱和食盐水洗涤数次直至中性;有机相经无水硫酸钠干燥、过滤、蒸去溶剂后,得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛粗产物;
(3)4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛粗产物经硅胶柱分离(200~300目,洗脱液石油醚/乙酸乙酯=3∶1,v/v),得到4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛。
6.根据权利要求2所述的一种检测Hg2+用高灵敏性荧光探针的制备方法,其特征在于,步骤4)中,4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛与吡啶-2-甲酰肼进行缩合,得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼;具体步骤为:
(1)将1mmol 4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛、1~2mmol吡啶-2-甲酰肼、10~15mL无水乙醇、1~3滴哌啶加入三口烧瓶中,回流反应12~24h,用TLC监测反应进程,直至4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯基]-4-甲醛反应完全后停止反应;
(2)将反应液经浓缩除去部分乙醇后,冷却并析出固体,抽滤并用冷乙醇洗涤滤饼,得到N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼。
7.权利要求1所述的N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼在检测Hg2+中的应用。
8.根据权利要求7所述的应用,其特征在于,所述的N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼能与Hg2+进行专一性反应,在365nm紫外光下其青色荧光发生猝灭。
9.根据权利要求7所述的应用,其特征在于,所述的N′-(4′-(6,6-二甲基-4,5,6,7-四氢-1H-5,7-桥亚甲基吲唑-3-基)-[1,1′-联苯]-4-亚甲基)吡啶-2-甲酰肼作为检测Hg2+的荧光探针。
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