CN108129435A - 一种新型铁离子荧光探针及其制备方法 - Google Patents
一种新型铁离子荧光探针及其制备方法 Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 44
- 239000000523 sample Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 iron ion Chemical class 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
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- GLNDAGDHSLMOKX-UHFFFAOYSA-N coumarin 120 Chemical class C1=C(N)C=CC2=C1OC(=O)C=C2C GLNDAGDHSLMOKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
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- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 4
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- NEKNNCABDXGBEN-UHFFFAOYSA-L disodium;4-(4-chloro-2-methylphenoxy)butanoate;4-(2,4-dichlorophenoxy)butanoate Chemical compound [Na+].[Na+].CC1=CC(Cl)=CC=C1OCCCC([O-])=O.[O-]C(=O)CCCOC1=CC=C(Cl)C=C1Cl NEKNNCABDXGBEN-UHFFFAOYSA-L 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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Abstract
本发明公开了一种新型检测铁离子的荧光探针及其制备方法,属于分子探针技术领域。该探针结构式如下:;本发明的铁离子荧光探针制备方法简单。该探针以荧光增强、颜色发生明显改变的方式检测铁离子,在水体系中能够高选择性识别铁离子,而对其它金属离子(银离子、铝离子、钙离子、钴离子、铜离子、镍离子、钾离子、镁离子、钠离子、镍离子、锌离子)都没有响应。该探针加入到水体系中所得溶液为橙色,当与铁离子作用后,溶液的荧光明显增强、颜色变为黄色,对铁离子的选择性高,而且现象明显,便于识别。
Description
技术领域
本发明涉及一种荧光探针,尤其涉及一种基于香豆素衍生物的铁离子荧光探针以及制备方法,该荧光探针能够在水体系中高效识别铁离子,属于有机小分子荧光探针领域。
背景技术
铁离子在自然界广泛分布,是许多生物系统和化学品中重要的过渡金属物种之一。但是,水或食物受铁离子污染后,经饮用或食用进入人体后导致含量过高时,会对心、肝、胰造成极大的损坏,严重时甚至会造成生命危险。因此,实现铁离子在水介质中的快速、灵敏检测是非常重要的。
近年来,因为小分子有机荧光探针能够与特定目标分析物发生作用后,荧光信号发生变化,以达到检测特定目标分析物的目的,从而受到科学界的广泛关注。目前用于铁离子检测的荧光探针存在种类较少、检测信号不明显的缺点,能够在水介质中实现对铁离子检测的更是少之又少。因此,设计、研究一种可以在水体系中对铁离子进行定量检测且具有特异选择性、高灵敏度、响应时间快等特征荧光探针具有重要的现实意义。
发明内容
针对现有技术的不足,本发明提供了一种新型基于香豆素衍生物的铁离子荧光探针,该探针加入到水或有机溶剂后所得溶液为橙色,当与铁离子作用后,溶液的荧光明显增强、颜色变为黄色。
本发明还提供上述荧光探针的制备方法,该制备方法中原材料价格低廉,生产成本低;对温度的要求低,反应过程容易控制,产品易于分离、纯度高、收率高。
本发明还提供了上述荧光探针在水体系中的应用。
本发明采用的技术方案如下:
一种基于香豆素衍生物的铁离子荧光探针,其特征在于,探针分子式为C24H22N2O4,其结构式为:
所示化合物名称为2氢-1-苯并吡喃-2-酮,7-(二乙基氨基)-3-[N-(4-甲基-2-氧-2氢-1-苯并吡喃-7-取代)亚氨基]甲基,简称为希夫碱类化合物1。
一种上述荧光探针的制备方法,包括以下步骤:
(1)二乙胺基水杨醛、丙二酸二乙酯、哌啶溶于无水乙醇中,于100℃-130℃反应15-20h,得橙色固体为化合物S-1,其结构式如下;
S-1
(2)将步骤(1)所得化合物S-1与7-氨基-4-甲基香豆素溶于无水乙醇中,于75℃-115℃反应8-12h,得到希夫碱类化合物铁离子荧光探针。
所述步骤(2)中的7-氨基-4-甲基香豆素结构式为:
本发明制备方法的合成路线为:
本发明制备方法中,步骤(1)采用下述方法完成:
a.将摩尔比为1:2:1的二乙胺基水杨醛:丙二酸二乙酯:哌啶加入到有机溶剂中,在120℃条件下回流18h,减压抽滤分离取溶液;再向其中加入浓盐酸与冰醋酸,在115℃条件下搅拌19h,冷却至室温,将所得溶液倒入冰水中,用NaOH溶液调节pH = 6,得到沉淀物,室温搅拌1h,抽滤水洗干燥,得到中间产物;
所述的反应物总量与有机溶剂体积比为2:5;
所述的浓盐酸或冰醋酸与有机溶剂的体积比为2:3;
b.将重蒸过的N,N-二甲基甲酰胺加入到POCl3中,在N2环境中搅拌30min,得红色澄清溶液;
所述的N,N-二甲基甲酰胺与POCl3的体积比为1:1;
将a步所得中间产物溶解在重蒸过的N,N-二甲基甲酰胺中,逐滴加入到b步所得红色澄清溶液中,在70℃环境中搅拌16h后,倒入冰水中,用NaOH溶液调节至pH = 5.2,产生的沉淀过滤水洗干燥,用无水乙醇重结晶,得到化合物S-1,其名称为7-N,N-二乙胺基香豆素-3-甲醛。
本发明制备方法中,步骤(2)采用下述方法完成:
将化合物S-1和7-氨基-4-甲基香豆素分别放入装有有机溶剂的烧杯和圆底烧瓶中,将装有7-氨基-4-甲基香豆素的圆底烧瓶加热,之后,将化合物S-1加入到圆底烧瓶中并滴入2-4滴冰醋酸,反应10h后,冷却至室温,之后置于冰箱中静置10min,析出沉淀,过滤,用有机溶剂洗涤,干燥,得到目标产物。
一种原料过量,不影响反应;溶剂的用量只要能使原料完全混溶即可。
所述步骤(1)中:有机溶剂优选为无水乙醇;更优选地,所述的分离提纯方法为:将反应产物冷却后抽滤,冰醋酸洗涤,乙醇重结晶。
所述步骤(2)中:有机溶剂优选为无水乙醇;更优选地,所述的分离提纯方法为:将反应产物冷却后抽滤,无水乙醇洗涤,乙醇重结晶。
本发明的有益效果如下:
1、本发明的基于香豆素衍生物的铁离子荧光探针,其结构是一种新型的希夫碱类化合物,可以应用于水体系中铁离子的检测,通过荧光增强、颜色发生明显改变的方式检测铁离子。该探针加入到水体系中所得溶液为橙色,当与铁离子作用后,溶液的荧光明显增强、颜色变为黄色,对铁离子的选择性高,而且现象明显,便于识别;
2、本发明的制备方法简单,容易控制,产品易于分离、收率高、纯度高。
附图说明
图1为本发明实施例2所制备的基于香豆素衍生物的铁离子荧光探针的核磁共振氢谱;
图2为本发明实施例2所制备的基于香豆素衍生物的铁离子荧光探针的核磁共振碳谱;
图3为本发明实施例3铁离子荧光探针检测铁离子滴定的吸收光谱曲线变化;
图4为本发明实施例3铁离子荧光探针检测铁离子滴定的荧光光谱曲线变化;
图5为本发明实施例4加入不同金属离子之后的荧光强度变化的对比图。
具体实施方式
下面通过具体实施例对本发明做进一步说明,但不限于此。实施例中所用原料,如无特殊说明均为常规市购产品。
实施例1
制备7-N,N-二乙胺基香豆素-3-甲醛
将二乙胺基水杨醛(0.97g,5mmol)、丙二酸二乙酯(1.6g,10mmol)、哌啶(1.0ml)加入到15mL乙醇溶剂中,在120℃条件下回流18h,减压抽滤分离取溶液;再向其中加入20ml浓盐酸与20mL冰醋酸,在115℃条件下搅拌19h,冷却至室温,将所得溶液倒入50ml冰水中,逐滴加入NaOH溶液调节ph = 5,得到沉淀物,室温搅拌1h,抽滤水洗干燥,得到中间产物。
a.将重蒸过的N,N-二甲基甲酰胺 7mL加入到7mL POCl3中,在氮气保护下搅拌35min,溶液逐渐变成红色澄清溶液;
b.将a步所得中间产物溶解在30mLN,N-二甲基甲酰胺中,逐滴加入到红色澄清溶液中,生成深红色悬浮液,在70℃环境中搅拌16h,倒入300mL冰水中,用NaOH溶液调节pH = 5.2,产生大量沉淀,过滤水洗干燥,用无水乙醇重结晶,得到7-N,N-二乙胺基香豆素醛;
合成路线如下:
。
实施例2
制备希夫碱类化合物(基于香豆素衍生物的铁离子荧光探针)
将摩尔比为1:1的7-N,N-二乙胺基香豆素-3-甲醛(0.74g,3mmol)和7-氨基-4-甲基香豆素(0.52g,3mmol)分别放入装有无水乙醇的烧杯和圆底烧瓶中,将装有7-氨基-4-甲基香豆素的圆底烧瓶加热至70℃,待3min后,将7-N,N-二乙胺基香豆素醛在1min内加入到圆底烧瓶中,待体系颜色变为橙色后,滴入3滴冰醋酸,反应10h后,冷却至室温,之后置于冰箱中静置10min,析出沉淀,过滤,用有机溶剂洗涤,干燥,得到目标产物,产率64%。对所得化合物进行核磁共振图谱分析,1H NMR(400MHz, CDCl3)δ: 1.26 (t, J = 7.2Hz, 6H), 2.45(d, J = 1.2 Hz, 3H), 3.47 (q, J = 7.2 Hz, 4H), 6.24(d, J = 1.2 Hz, 1H), 6.52(d, J = 2.4 Hz, 1H), 6.65(dd, J = 9.2 Hz, 2.4 Hz, 1H), 7.14-7.16(m, 2H), 7.43(d, J = 8.8 Hz, 1H), 7.60(d, J = 8.8 Hz, 1H), 8.54(s,1H), 8.73(s,1H)。13C NMR(101MHz, CDCl3)δ: 12.65, 18.84, 45.29, 97.38, 108.95, 109.88, 110.03, 114.07,114.69, 117.41, 117.95, 125.46, 131.42, 142.27, 152.34, 152.57, 154.59,155.38, 156.99, 158.07, 161.24, 162.32.
合成路线如下:
。
实施例3
制备的基于香豆素衍生物的铁离子荧光探针的光物理性质检测
化合物在N,N-二甲基甲酰胺与水的混合溶液(体积比为9:1)对铁离子有很快的响应时间(<4 s),故对其做随铁离子加入量的吸收光谱和荧光光谱变化曲线。如图3所示,化合物在λ = 470 nm存在强吸收,当向溶有化合物的混合溶液中加入铁离子时,原λ = 470 nm的吸收峰逐渐降低,同时吸收峰蓝移,最终在λ = 450 nm形成一个新的吸收峰,同时在350 nm处吸光度不断增加,当铁离子加入量到4.2当量时,吸收曲线不在发生变化,反应达到饱和。如图4所示,以350 nm作为激发波长,随着铁离子加入量的增加,化合物在416 nm的荧光峰的荧光强度逐渐增高,最终荧光强度增加为原来的2倍。
实施例4
化合物在N,N-二甲基甲酰胺与水的混合溶液(体积比为9:1)中,向溶液中加入过量其它金属离子,测试加入不同金属离子之后的荧光光谱,激发波长为350 nm,发射波长为416nm,结果如图5所示。由图5可知,常见的金属离子如银离子、铝离子、钙离子、钴离子、铜离子、镍离子、钾离子、镁离子、钠离子、镍离子、锌离子等,荧光强度只有加入铁离子后变化明显,其它金属离子荧光强度几乎没有发生变化,表明不对检测结果产生任何干扰,可以证明该荧光探针对铁离子具有较高的选择性。
由以上现象,我们可以得出结论,该希夫碱化合物对铁离子有很好的响应,并且响应时间短以及灵敏度高,具有检测铁离子的功能。
Claims (5)
1.一种检测铁离子的荧光探针,其特征在于,探针分子式为C24H22N2O4,结构式为:
根据权利要求1所述的基于香豆素衍生物的铁离子荧光探针的制备方法,其特征在于,它包括以下步骤:
二乙胺基水杨醛、丙二酸二乙酯、哌啶溶于无水乙醇中,于100℃-130℃反应15-20h,得橙色固体为化合物S-1,其结构式如下:
;
(2)将步骤(1)所得化合物S-1与7-氨基-4-甲基香豆素溶于无水乙醇中,于75℃-115℃反应8-12h,得到希夫碱类化合物铁离子荧光探针。
2.根据权利要求2所述的制备方法,其特征在于,所述步骤(2)中化合物S-1与7-氨基-4-甲基香豆素的摩尔比为1:1-1.3。
3.根据权利要求2所述的制备方法,其特征在于,所述步骤(2)的分离提纯方法为:将反应产物冷却后过滤,无水乙醇洗涤。
4.根据权利要求2所述的制备方法,其特征在于,所述的有机溶剂为无水乙醇。
5.一种权利要求1或2所述的希夫碱类化合物荧光探针的应用,其特征在于,用于检测水体系中的铁离子。
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