CN104926846B - 氟硼吡咯化合物及其制备方法与应用 - Google Patents
氟硼吡咯化合物及其制备方法与应用 Download PDFInfo
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- 239000000523 sample Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 6
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- 229910001385 heavy metal Inorganic materials 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- OVTCUIZCVUGJHS-UHFFFAOYSA-N dipyrrin Chemical compound C=1C=CNC=1C=C1C=CC=N1 OVTCUIZCVUGJHS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了氟硼吡咯化合物及其制备方法与应用。它是将相应水杨醛乙醇溶液与相应二胺基氟硼吡咯化合物混合,两者的摩尔比1:1,加热回流,用冰乙醇充分洗涤,真空干燥得到氟硼吡咯荧光化合物。本发明公开的氟硼吡咯化合物能够实现对水中Pb2+定量检测。具有较好的光稳定性,较高的荧光量子产率,对Pb2+具有高选择性和高灵敏性,可有效避免水体系中其他物种干扰。可实现简单、快速、准确定量检测铅离子。主要应用于土壤、水中Pb2+检测。
Description
技术领域
本发明属于分析化学和化学传感器应用技术领域,涉及氟硼吡咯衍生物制备及其对Pb2+荧光检测应用方法,更具体的说是一种采用氟硼吡咯荧光探针简便、高效、快速、高灵敏度、低检测限检测Pb2+新方法。
背景技术
重金属铅作为环境中普遍存在重金属之一,具有高毒性、不可降解性、污染隐蔽性等特点,并可通过食物链在生物体内富集,对生物体造成毒害,甚至对人类身体健康造成危害。
近年来,应用光化学传感器对有毒重金属检测成为研究热点之一。与传统ICP-AES、AAS及比色等对金属离子检测方法相比,荧光分子探针技术具有高灵敏、高选择、需要样品量少、可实现原位检测等特点,因此受到人们广泛关注。目前,已报道的对Pb2+检测荧光探针多是基于荧光猝灭方法建立起来的,该方法往往受其他荧光猝灭剂干扰,影响检测准确程度。
针对上述问题,我们建立一种新型基于荧光响应增强氟硼吡咯荧光探针检测Pb2+方法。本方法可实现简单、快速、准确定量检测铅离子。
发明内容
本发明提供了一种高灵敏、高选择性检测Pb2+氟硼吡咯衍生物制备及其应用方法。
本发明提供的用于检测Pb2+氟硼吡咯衍生物通式如下:
所述通式中R1= R2 = R3 = H,或 R1= R2 = R3 = CH3,或 R1= R2 = R3 = CH2CH3,或R1= R2 = CH3、R3 = OCH3,或R1= R2 = CH2CH3、R3 = OCH3。
本发明进一步公开了氟硼吡咯荧光化合物制备方法:它是将相应水杨醛乙醇溶液与相应二胺基氟硼吡咯化合物混合,两者的摩尔比1:1,加热回流1-5h,过滤,用冰乙醇充分洗涤,真空干燥,氟硼吡咯荧光化合物。
本发明的氟硼吡咯荧光化合物作为对Pb2+选择性识别探针识别性能可通过测其与不同重金属离子的DMSO、乙腈和乙醇的水溶液荧光光谱来确定。实验结果表明:氟硼吡咯荧光化合物具有较好的光稳定性,较高的荧光量子产率,对Pb2+具有高选择性和高灵敏性,可有效避免水体系中其他物种干扰。
附图说明:
图1 为pH=7.2主体BODIPY1与各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)相互作用图。
具体实施方式
为了更充分的解释本发明的实施,提供下述制备方法实施实例。这些实施实例仅仅是解释、而不是限制本发明的范围。为简单和清楚的目的,以下论述中对公知的技术方法的描述、溶液的配制过程进行不再赘述。需要说明的是:本发明实施例1-6所用到的相应醛、相应芳香胺化合物参考下面的文献制备:
(1)相应醛参考文献:Goswami S, Das A K, Maity A K, et al. Visual andnear IR (NIR) fluorescence detection of Cr3+ in aqueous media viaspirobenzopyran ring opening with application in logic gate and bio-imaging,Dalton Trans., 43 (1): 231-239. Knight P D, White A J P, Williams C K,Dinuclear zinc complexes using pentadentate phenolate ligands,Inorg. Chem.2008, 47(24): 11711-11719.)
(2)相应芳香胺化合物参考文献:Ziessel R, Bonardi L, Retailleau P, etal, Isocyanate-, isothiocyanate-, urea-, and thiourea-substituted borondipyrromethene dyes as fluorescent probes, J. Org. Chem., 2006, 71(8): 3093-3102. Gabe Y, Urano Y, Kikuchi K, et al, Highly sensitive fluorescence probesfor nitric oxide based on boron dipyrromethene chromophore rational design ofpotentially useful bioimaging fluorescence probe, J. Am. Chem. Soc., 2004,126(10): 3357-3367.)
实施例1
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛乙醇溶液中加入等物质的量相应芳香胺化合物回流3h,抽滤,室温风干,得目标化合物BODIPY1,产率66.5%。
1H NMR ( CDCl3, 400 MHz):1.254(s, 6H, -CH3), 2.342(s, 3H, -CH3), 2.567(s, 6H, -CH3), 4.792 (s, 2H, -CH2), 6.002 (s, 2H, pyrrole-H), 7.199 (s, 1H, -OH), 7.346-7.430 (m, 6H, Ar-H), 8.694 (s, 1H, CH),9.87 (s, 1H, OH);ESI-MS:486.56 ([M-H+]-);Anal.Calcd for C28H28BF2N3O2: C, 69.00; H, 5.80; B,2.22;F,7.79;N, 8.63; O,6.57;Found: C, 69.01; H, 5.79; O, 6.57.
制备BODIPY1荧光探针溶于DMSO中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY1荧光强度明显增强的即为Pb2+(如图1所示)。在498nm光照射下,只有含有Pb2+ BODIPY1溶液发出强烈绿色荧光,其他离子BODIPY1溶液则发出较弱荧光。当向含有Pb2+ BODIPY1溶液中分别加入其他阳离子(Ni2+、Co2+、Sr2+、Zn2 +、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+),30min后测其荧光发射光谱,发现其他阳离子对Pb2+检测几乎没有影响。
实施例2
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛化合物乙醇溶液中加入等物质的量相应芳香胺化合物,回流3h,抽滤,室温风干,得目标化合物BODIPY1,产率66.5%。
1H NMR ( CDCl3, 400 MHz):1.254(s, 6H, -CH3), 2.342(s, 3H, -CH3), 2.567(s, 6H, -CH3), 4.792 (s, 2H, -CH2), 6.002 (s, 2H, pyrrole-H), 7.199 (s, 1H, -OH), 7.346-7.430 (m, 6H, Ar-H), 8.694 (s, 1H, CH),9.87 (s, 1H, OH);ESI-MS:486.56 ([M-H+]-);Anal.Calcd for C28H28BF2N3O2: C, 69.00; H, 5.80; B,2.22;F,7.79;N, 8.63; O,6.57;Found: C, 69.01; H, 5.79; O, 6.57.
制备BODIPY1荧光探针溶于乙醇中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY1荧光强度明显增强的即为Pb2+。在498nm光照射下,只有含Pb2+ BODIPY1溶液发出强烈绿色荧光,其他离子BODIPY1溶液则发出较弱荧光。当向含有Pb2+ BODIPY1溶液中分别加入其他阳离子(Ni2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+),30min后测其荧光发射光谱,发现其他阳离子对Pb2+检测几乎没有影响。
实施例3
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛化合物乙醇溶液中加入等物质的量相应芳香胺化合物,回流5h,抽滤,室温风干,得目标化合物BODIPY2,产率61.5%。
1H NMR ( CDCl3, 400 MHz):1.471(s, 6H, -CH3), 2.597 (s, 6H, -CH3),3.986 (s, 3H, -OMe), 4.802 (s, 2H, -CH2), 6.062 (s, 2H, pyrrole-H), 7.239 (s,1H, -OH), 7.351-7.511 (m, 6H, Ar-H), 8.944 (s, 1H, CH), 9.962 (s, 1H, OH);ESI-MS:502.36 ([M-H+]-);Anal.Calcd for C28H28BF2N3O3: C, 66.81; H, 5.61; B,2.15;F,7.55;N, 8.35; O,9.54;Found: C, 66.78; H, 5.66; O, 9.57.
制备BODIPY2荧光探针溶于乙腈中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY2荧光强度明显增强的即为Pb2+。在498nm光照射下,只有含有Pb2+ BODIPY2溶液发出强烈绿色荧光,其他离子BODIPY2溶液则发出较弱荧光。当向含有Pb2+ BODIPY1溶液中分别加入其他阳离子(Ni2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+),30min后测其荧光发射光谱,发现其他阳离子对Pb2+检测几乎没有影响。
实施例4
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛化合物乙醇溶液中加入等物质的量相应芳香胺化合物,回流3.5h,抽滤,室温风干,得目标化合物BODIPY3,产率63.5%。
1H NMR ( CDCl3, 400 MHz):1.521(s, 6H, -CH3), 2.331 (s, 6H, -CH3),4.662 (s, 2H, -CH2), 6.102 (s, 2H, pyrrole-H), 7.131 (s, 1H, -OH), 7.343-7.508 (m, 7H, Ar-H), 8.914 (s, 1H, CH), 9.771 (s, 1H, OH);ESI-MS:472.46 ([M-H+]-);Anal.Calcd for C27H26BF2N3O2: C, 68.51; H, 5.54; B,2.28;F,8.03;N, 8.88;O,6.76;Found: C, 68.48; H, 5.50; O, 6.71.
制备BODIPY3荧光探针溶于乙腈中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY3荧光强度明显增强的即为Pb2+。在498nm光照射下,只有含有Pb2+ BODIPY3溶液发出强烈绿色荧光,其他离子BODIPY3溶液则发出较弱荧光。当向含有Pb2+ BODIPY3溶液中分别加入其他阳离子(Ni2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+),30min后测其荧光发射光谱,发现其他阳离子对Pb2+检测几乎没有影响。
实施例5
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛化合物乙醇溶液中加入等物质的量相应芳香胺化合物,回流4h,抽滤,室温风干,得目标化合物BODIPY4,产率65.5%。
1H NMR ( CDCl3, 400 MHz):0.998 (t, 6H, -CH3), 2.561 (dd, 4H, -CH2),4.652 (s, 2H, -CH2), 6.072 (s, 2H, pyrrole-H), 7.122 (s, 1H, -OH), 7.243-7.408 (m, 7H, Ar-H), 8.944 (s, 1H, CH), 9.781 (s, 1H, OH);ESI-MS:528.48 ([M-H+]+);Anal.Calcd for C31H34BF2N3O2: C, 70.33; H, 6.47; B,2.04;F,7.18;N, 7.94;O,6.04;Found: C, 70.28; H, 6.50; O, 6.05.
制备BODIPY4荧光探针溶于DMSO中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY4荧光强度明显增强的即为Pb2+。在498nm光照射下,只有含有Pb2+ BODIPY4溶液发出强烈绿色荧光,其他离子BODIPY4溶液则发出较弱荧光。
实施例6
检测Pb2+氟硼吡咯荧光化合物结构式如下:
在搅拌条件下,向含有相应醛化合物乙醇溶液中加入等物质的量相应芳香胺化合物,回流4h,抽滤,室温风干,得目标化合物BODIPY5,产率60.5%。
1H NMR ( CDCl3, 400 MHz):2.365 (s, 3H, -CH3), 4.622 (s, 2H, -CH2),6.082-6.989 (m, 6H, pyrrole-H), 7.111 (s, 1H, -OH), 7.113-7.458 (m, 6H, Ar-H), 8.954 (s, 1H, CH), 9.881 (s, 1H, OH);ESI-MS:430.18 ([M-H+]+);Anal.Calcdfor C24H20BF2N3O2: C, 66.84; H, 4.67; B,2.51;F,8.81;N, 9.74; O,7.42;Found: C,66.80; H, 4.60; O, 7.46.
制备BODIPY5荧光探针溶于乙腈中,制成0.6uM储备液。从储备液中取出3ml加入到10ml试管中,加入3ml 3.0uM各阳离子(Ni2+、Pb2+、Co2+、Sr2+、Zn2+、Ca2+、Hg2+、Cr2+、Na+、Cd2+、K+、Cu2+、Fe2+、Al3+、Mg2+、Ba2+)的HEPES缓冲液(pH = 7.2, 20mM),测量其荧光性质。以498nm为激发波长,测量502nm处荧光发射强度。导致BODIPY5荧光强度明显增强的即为Pb2+。在498nm光照射下,只有含有Pb2+ BODIPY5溶液发出强烈绿色荧光,其他离子BODIPY5溶液则发出较弱荧光。
实施例7
从实施例1的荧光探针储备液中取出3ml,加入到10ml试管中,向其中加入3ml水样,在498nm光照射下,若发出强烈绿色荧光,则表明水样中含有Pb2+,若不发出绿色荧光,则表明水样中无Pb2+。
Claims (3)
1.具有如下结构式的氟硼吡咯化合物:
所述通式中R1= R2 = R3 = H,或 R1= R2 = R3 = CH3,或 R1= R2 = R3 = CH2CH3,或R1=R2 = CH3、R3 = OCH3,或R1= R2 = CH2CH3、R3 = OCH3。
2.权利要求1所述氟硼吡咯化合物的制备方法,其特征在于:将相应水杨醛乙醇溶液与相应meso-(4-胺苯基)氟硼吡咯化合物混合,两者的摩尔比1:1,加热回流1-5h,过滤,用冰乙醇充分洗涤,真空干燥,即得氟硼吡咯化合物。
3.权利要求1所述氟硼吡咯化合物在制备用于Pb2+快速检测氟硼吡咯荧光探针方面的应用。
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