CN110357913B - 一种用于检测次氯酸根离子的荧光探针及其制备方法和应用 - Google Patents
一种用于检测次氯酸根离子的荧光探针及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种用于检测次氯酸根离子的荧光探针及其制备方法和应用。本发明以3‑(4″‑甲酰基‑1′,1″‑联苯‑4′‑羰基)诺蒎酮为原料,与羟胺进行缩合反应,得到3‑(4″‑甲酰基‑1′,1″‑联苯‑4′‑甲醛肟)诺蒎酮;3‑(4″‑甲酰基‑1′,1″‑联苯‑4′‑甲醛肟)诺蒎酮与三氟化硼乙醚反应,得到3‑(4″‑甲酰基‑1′,1″‑联苯‑4′‑甲醛肟)诺蒎酮基氟硼络合物。本发明制备的3‑(4″‑甲酰基‑1′,1″‑联苯‑4′‑甲醛肟)诺蒎酮基氟硼络合物能与ClO‑离子进行专一性反应,在365nm紫外光下,溶液的荧光颜色由黄色变为绿色,在自然光下,溶液颜色由无色变为黄色,对ClO‑离子具有专一性和高灵敏度的特点,可作为荧光探针在检测次氯酸根离子方面具有很好的应用前景。
Description
技术领域
本发明属精细有机合成技术领域,涉及一种专一性强高灵敏度的用于检测次氯酸根离子的荧光探针及其制备方法和应用。
背景技术
次氯酸(HClO)是一种生命系统中重要的弱酸性活性氧,在各种生理学过程中起着非常重要的作用。在白细胞包括单核细胞、中性粒细胞和巨噬细胞中,在髓过氧化物酶(MPO)的催化下过氧化氢氧化氯离子生成内源性次氯酸。然而,过量的次氯酸则会导致组织损伤和多种疾病如神经元变性坏死、心血管疾病、风湿性关节炎、哮喘和动脉粥样硬化等。次氯酸在生物学上具有重要性,实时监测细胞内的次氯酸的动态分布,对医疗诊断邻域有着重要的意义。
近年来,多种分析方法用于对ClO-离子的分析检测,例如:高效液相、电化学、电泳等。然而,与其他分析方法相比,荧光分析方法具有选择性高、灵敏度高、操作简单等优点。但是已经报道的ClO-离子荧光探针,依然处在很多不足,例如:仅只有荧光颜色变化、灵敏度不高、检测受其他离子影响,反应时间长等。因此开发颜色比率型ClO-离子荧光探针意义重大。
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是提供一种次氯酸根离子荧光探针,可专一性与次氯酸根离子反应,用于检测次氯酸根离子的含量。本发明解决的另一技术问题是提供一种上述次氯酸根离子荧光探针的制备方法。本发明还解决一个技术问题是提供一种该次氯酸根离子荧光探针的应用。
为解决上述技术问题,本发明采用的技术方案为:
一种用于检测次氯酸根离子的荧光探针,为3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物,结构式为:
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备方法,包括如下步骤:
1)3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮与羟胺反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮;
2)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮与三氟化硼乙醚反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物。
步骤1)中3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮与羟胺反应,得到3-(4″-甲酰基-1′,1″-联苯-4,-甲醛肟)诺蒎酮,具体制备过程为:
(1)将0.04mol 3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮、0.06mol羟胺和30mL乙酸乙酯依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应6h,用薄层色谱法跟踪反应进程;
(2)反应液加入50mL乙酸乙酯,再用蒸馏水洗涤,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂后,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物;
(3)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物经柱层析(100~200目硅胶,洗脱液石油醚/乙酸乙酯比为15∶1),得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮。
步骤2)中3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮与三氟化硼乙醚反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物,具体制备过程为:
(1)将0.02mol 3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮、0.04mol三氟化硼乙醚和15mL二氯甲烷依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应2h,用薄层色谱法跟踪反应进程;
(2)反应液经蒸馏去除溶剂二氯甲烷后,加入50mL乙酸乙酯,再用蒸馏水洗涤至中性,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂后,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物;
(3)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物经柱层析(100~200目硅胶,洗脱液石油醚/乙酸乙酯比为20∶1),得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物。
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物在检测ClO-中的应用。
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物作为颜色比率型荧光探针在检测ClO-中的应用。
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物能与ClO-离子进行专一性反应,在365nm紫外光下,溶液的荧光颜色由黄色变为绿色,在自然光下,溶液颜色由无色变为黄色。
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物作为荧光比率型荧光探针在检测ClO-中的应用。
所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物能与ClO-离子进行专一性反应,化合物在550nm的荧光强度明显减弱,在485nm的荧光强度明显增强。
有益效果:与现有技术相比,本发明制备新型的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物对次氯酸根离子具有专一性络合作用,在365nm紫外光下,溶液的荧光颜色由黄色变为绿色,在自然光下,溶液的颜色由无色变为黄色。在550nm的荧光强度明显减弱,在485nm的荧光强度明显增强。该化合物对次氯酸根离子具有高选择性和高灵敏性,可作为比率型荧光探针在检测次氯酸根离子方面具有很好的应用前景。
附图说明
图1是不同阴离子和活性氧对3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物荧光光谱图的影响结果图;Analytes包括:HSO3 -,HS-,F-,Cl-,AcO-,NO3 -,HSO4 -,H2PO4 -,ClO4 -,8O4 2-,CO3 2-,ClO-,H2O2,ROO·,HO·,NO;
图2是不同浓度ClO-离子对3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的紫外吸收光谱图影响结果图;
图3是不同浓度ClO-离子对3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物荧光光谱图的影响结果图。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例1
3-3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备方法,反应式如下:
具体步骤如下:
1、3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮的制备:
将0.04mol 3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮、0.06mol羟胺和30mL乙酸乙酯依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应6h,用薄层色谱法跟踪反应进程。反应液加入50mL乙酸乙酯,再用蒸馏水洗涤,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物。3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物经柱层析(100~200目硅胶,洗脱液石油醚/乙酸乙酯比为15:1),得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮。熔点为161.5-162.5℃,得率为59.2%,纯度为98.2%。1H NMR(400MHz,CDCl3)δ:15.58(s,1H),8.20(s,1H),7.85-7.78(m,2H),7.76-7.68(m,2H),7.67(d,J=4.1Hz,4H),2.79-2.73(m,2H),2.65-2.52(m,2H),2.32(tt,J=6.1,3.1Hz,1H),1.49(d,J=9.7Hz,1H),1.36(s,3H),1.27(d,J=10.4Hz,1H),0.99(s,3H).13C NMR(100MHz,CDCl3)δ:209.36,172.23,149.91,141.96,141.64,134.55,131.60,128.81,127.57,127.47,126.79,104.06,54.81,39.89,39.57,28.41,27.79,25.84,21.56.HRMS(m/z):[M+H]+calculated for C23H23NO3+H+,362.1716;found,362.1751.
2、3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备:
将0.02mol 3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮、0.04mol三氟化硼乙醚和15mL二氯甲烷依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应2h,用薄层色谱法跟踪反应进程。反应液经蒸馏去除溶剂二氯甲烷后,加入50mL乙酸乙酯,再用蒸馏水洗涤至中性,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物。3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物经柱层析(100-200目硅胶,洗脱液石油醚/乙酸乙酯比为20∶1),得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物。熔点为217.4-218.4℃,得率为78.2%,纯度为97.5%。1H NMR(400MHz,CDCl3)δ:8.20(s,1H),8.08-7.93(m,2H),7.85-7.61(m,6H),3.00-2.84(m,2H),2.82(t,J=5.5Hz,1H),2.71(dt,J=11.0,5.7Hz,1H),2.44(tt,J=6.0,3.1Hz,1H),1.52(d,J=10.1Hz,1H),1.44(s,3H),1.26(d,J=2.3Hz,1H),0.99(s,3H).13C NMR(100MHz,CDCl3)δ:202.52,178.66,149.76,144.69,140.83,132.54,132.21,130.19,127.68,127.60,127.03,104.57,51.38,40.51,39.80,28.50,28.40,25.53,21.49.HRMS(m/z):[M+H]+calculated for C23H22BF2NO3+H+,410.1965;found,410.1962.
实施例2
将固体3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物和HSO3 -,HS-,F-,Cl-,AcO-,NO3 -,HSO4 -,H2PO4 -,ClO4 -,SO4 2-,CO3 2-,ClO-,H2O2,ROO·,HO·,NO·等16种的不同的阴离子和活性氧溶于PBS缓冲溶液(10mM,pH=7.2,6/4(v/v))中,配制成浓度为1.0×10-6M的探针溶液和浓度为1.0×10-5M的16种不同阴离子溶液。在激发波长为350nm的条件下测得不同阴离子存在下的荧光强度变化,如图1所示。结果表明,在ClO-离子存在下,溶液最大发射波长由550nm蓝移到485nm。紫外灯下溶液荧光颜色由黄变成绿色,说明该化合物对ClO-离子具有较好的选择性。
实施例3
将3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物溶于PBS缓冲液(pH=7.2,10mM,6/4(v/v)),配制成浓度为1.0×10-6M的溶液,同样将ClO-溶于PBS缓冲溶液配成浓度为0、1、2、4、6、8、10、20、40、60、80、100、200×10-7M的溶液。测得不同浓度的ClO-离子对3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的紫外吸收光谱,如图2所示。结果表明,化合物在280nm左右的紫外吸收强度明显减弱,在360nm左右的紫外吸收强度明显增强。说明3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物可以作为颜色比率型探针的对ClO-进行检测。
实施例4
将3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物溶于PBS缓冲液(pH=7.2,10mM,6/4(v/v)),配制成浓度为1.0×10-6M的溶液,同样将ClO-溶于PBS缓冲溶液配成浓度为0、1、2、4、6、8、10、20、40、60、80、100、200×10-7M的溶液。测得不同浓度的ClO-离子对3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的荧光光谱,如图3所示。结果表明,化合物在550nm左右的荧光强度明显减弱,在485nm左右的荧光强度明显增强。说明3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮基氟硼络合物可以作为荧光比率型探针的对ClO-进行检测。
Claims (9)
2.权利要求1所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备方法,其特征在于,包括如下步骤:
1)3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮与羟胺反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮;
2)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮与三氟化硼乙醚反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物。
3.根据权利要求2所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备方法,其特征在于,步骤1)中3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮与羟胺反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮,具体制备过程为:
(1)将0.04mol 3-(4″-甲酰基-1′,1″-联苯-4′-羰基)诺蒎酮、0.06mol羟胺和30mL乙酸乙酯依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应6h,用薄层色谱法跟踪反应进程;
(2)反应液加入50mL乙酸乙酯,再用蒸馏水洗涤,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂后,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物;
(3)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮粗产物经柱层析,100~200目硅胶,洗脱液石油醚/乙酸乙酯比为15:1,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮。
4.根据权利要求2所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物的制备方法,其特征在于,步骤2)中3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮与三氟化硼乙醚反应,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物,具体制备过程为:
(1)将0.02mol 3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮、0.04mol三氟化硼乙醚和15mL二氯甲烷依次加入配有搅拌器、温度计和回流冷凝器的三口烧瓶中,在回流状态下反应2h,用薄层色谱法跟踪反应进程;
(2)反应液经蒸馏去除溶剂二氯甲烷后,加入50mL乙酸乙酯,再用蒸馏水洗涤至中性,有机相经无水硫酸钠干燥、过滤、浓缩回收溶剂后,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物;
(3)3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物粗产物经柱层析,100~200目硅胶,洗脱液石油醚/乙酸乙酯比为20:1,得到3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物。
5.权利要求1所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物在检测ClO-中的应用,所述的应用为非疾病诊断和治疗应用。
6.权利要求1所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物作为颜色比率型荧光探针在检测ClO-中的应用,所述的应用为非疾病诊断和治疗应用。
7.根据权利要求6所述的应用,其特征在于,所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物能与ClO-离子进行专一性反应,在365nm紫外光下,溶液的荧光颜色由黄色变为绿色,在自然光下,溶液颜色由无色变为黄色。
8.权利要求1所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物作为荧光比率型荧光探针在检测ClO-中的应用,所述的应用为非疾病诊断和治疗应用。
9.根据权利要求8所述的应用,其特征在于,所述的3-(4″-甲酰基-1′,1″-联苯-4′-甲醛肟)诺蒎酮基氟硼络合物能与ClO-离子进行专一性反应,化合物在550nm的荧光强度明显减弱,在485nm的荧光强度明显增强。
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