CN108558875A - 一种能够检测硫化氢的小分子荧光探针及其应用 - Google Patents

一种能够检测硫化氢的小分子荧光探针及其应用 Download PDF

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CN108558875A
CN108558875A CN201810506210.6A CN201810506210A CN108558875A CN 108558875 A CN108558875 A CN 108558875A CN 201810506210 A CN201810506210 A CN 201810506210A CN 108558875 A CN108558875 A CN 108558875A
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benzimidazole
pyridine
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葛燕青
吉瑞雪
刘爱坤
徐志扬
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Taishan Medical University
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    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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Abstract

本发明公开了一种能够检测H2S的荧光探针，所述探针是苯并咪唑并[1,2‑a]吡啶衍生物，其化学结构式如式（1）所示。本发明的荧光探针在PBS缓冲溶液（pH=7.40）中对H2S有较好的荧光选择性、较高的灵敏度及较强的抗其它离子干扰能力，应用前景广泛。

Description

一种能够检测硫化氢的小分子荧光探针及其应用
技术领域
本发明涉及有机小分子荧光探针领域，尤其涉及一种苯并咪唑并[1,2-a]吡啶衍生物H2S荧光探针的合成及其应用。
背景技术
硫化物是表示水体质量的重要参数之一， 其存在能够消耗水体中的氧气，导致水生生物的死亡。在有机物丰富、pH 值较低的水域， 硫化物极易生成具有恶臭气味的有毒气体H2S。一方面，H2S 是生成具有强腐蚀性物质硫酸的前驱体， 对环境有很大的危害；而且还是一种强烈的神经毒素，人体吸入不同浓度的H2S会产生头痛、头晕、呕吐、顷刻死亡等症状， 严重威胁着人类的生存与发展。但是另一方面， 有研究表明， H2S 是除了一氧化氮(NO) 和一氧化碳( CO) 之外的第 3 种气体信号分子，具有调剂免疫系统和器官功能、保护神经细胞和维持机体氧化还原平衡等重要作用， 与许多生理病理学过程密切相关。因此，对H2S进行快速、灵敏、准确的检测十分重要。
荧光探针因选择性好，灵敏度高，操作简单，成本低并且可以实现实时监测等优点，现广泛应用于细胞内H2S 含量的测定。尽管已有多种检测H2S 荧光探针被报道，但荧光探针局限于香豆素，罗丹明等荧光团。因此开发一种新型的荧光团是非常重要的。
发明内容
本发明解决的问题是提供一种苯并咪唑并[1,2-a]吡啶衍生物H2S荧光探针的合成及其应用。
本发明的技术方案是：一种苯并咪唑并[1,2-a]吡啶衍生物的H2S 荧光探针，其化学结构式如式（1）所示：
(1)
本发明还包括苯并咪唑并[1,2-a]吡啶衍生物H2S 荧光探针的应用，式（1）化合物在PBS缓冲溶液（pH=7.40）对H2S 有较好的荧光选择性。
本发明还包括苯并咪唑并[1,2-a]吡啶衍生物H2S 荧光探针的合成方法，在乙腈溶液中，将4-氰基-1-(2-羟基苯基)苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯与2,4-二硝基氯苯，三乙胺按照摩尔比1:2:2投料，加热回流12小时，得到2,4-二硝基氯苯取代4-氰基-1-(2-羟基苯基)苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯的化合物。
配制苯并咪唑并[1,2-a]吡啶衍生物的二甲亚砜溶液，分别加入定量的MgCl2,CaCl2, AlCl3, SnCl2 .2H2O, PbSO4, CrCl3· 6H2O, MnCl2· 4H2O, FeCl3·6H2O, LiCl,KCl, CuCl2 .2H2O, FeCl2·4H2O, CoCl2·6H2O, NiCl2·6H2O, PdCl2, ZnCl2, HgCl2·2H2O, CdCl2·2½H2O, AgNO3, NaAc, NaBr, NaCl, NaHCO3, NaF, NaHS, NaI, NaNO2,NaNO3, Na2SO4, Na2SO3的水溶液，通过荧光光谱测试来研究对不同阴离子的选择性，测其荧光发射波谱强度变化发现：本发明所述荧光探针即式（1）化合物对H2S 有较好的荧光选择性，如图1所示。逐渐加入H2S 至200当量后，化合物1在543nm处荧光强度明显下降，如图2所示。因此，苯并咪唑并[1,2-a]吡啶衍生物作为H2S荧光探针具有巨大的应用。
附图说明
图1：式（1）化合物（1×10-5M）的PBS缓冲溶液（pH=7.40）中加入200当量的不同金属离子、阴离子后的荧光强度变化柱状图，图1中纵坐标为543nm处的荧光强度。
图2：式（1）化合物（1×10-5M）的PBS缓冲溶液（pH=7.40）中进行H2S荧光滴定图。图中FL Intensity为光强，Wavelength为波长，equiv为倍数。
图3：式（1）化合物（1×10-5M）和200当量的其它阴阳离子共存的PBS缓冲溶液（pH=7.40）中加入200当量H2S 的后荧光强度变化的柱状图。
图4是式（1）化合物合成方法反应式图。
具体实施方式
实施例1：式（1）化合物的合成方案如下式所示：
具体合成步骤如下：
在50 mL圆底烧瓶中依次加入0.20g（0.54 mmol）4-氰基-1-(2-羟基苯基)苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯，0.21g （1.08 mmol）2,4-二硝基氯苯，0.1g （1.08 mmol）三乙胺，20 mL乙腈，加热回流12小时。冷却后沉淀产生，抽滤，固体柱层析得0.12g黄色固体，产率42.85%。
实施例2：
向式（1）化合物（10-5M）的PBS缓冲溶液中（pH=7.40）分别加入200当量的Mg2+, Ca2+,Al3+, Pb2+, Mn2+, Fe3+, Fe2+, Cr3+, Co2+, Li+, Ni2+, Zn2+, Hg2+, Cd2+, Na+, Ag+, K+,Cu2+, HCO3 -, Ac-, NO2 -, SO4 2-, SO3 2-, F-, NO3 -, Br-, I-后，测其在543nm荧光发射强度变化发现：式（1）化合物对H2S 有较好的荧光选择性，加入200当量的H2S 后，化合物1在543nm处荧光强度明显降低。如图1，图2所示。
实施例3：
分别于式（1）化合物（10-5M）和200当量的Mg2+, Ca2+, Al3+, Pb2+, Cr3+, Mn2+, Fe3+,Fe2+, Co2+, Li+, Ni2+, Zn2+, Hg2+, Cd2+, Pd2+, Na+, Ag+, K+, Cu2+, HCO3 -, Ac-, NO2 -,SO4 2-, SO3 2-, F-, NO3 -, Br-, I-不同阴阳离子溶液中，加入200当量的H2S 后，测其在543nm荧光发射强度变化发现：式（1）化合物对其它离子有较强的抗干扰能力，如图3所示。

Claims (2)

1.一种苯并咪唑并[1,2-a]吡啶衍生物H2S 荧光探针，其特征在于：它是由2，4-二硝基氯苯取代4-氰基-1-（2-羟基苯基）苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯，其化学结构式如式（1）所示：
(1)
式（1）化合物在PBS缓冲溶液（pH=7.40）中对H2S有较好的荧光选择性。
2.权利要求1所述苯并咪唑并[1,2-a]吡啶衍生物H2S 荧光探针的合成方法，其特征在于：在乙腈溶液中，将4-氰基-1-(2-羟基苯基)苯并咪唑并[1,2-a]吡啶-3-羧酸乙酯与2，4-二硝基氯苯，三乙胺按照摩尔比1:2:2投料，加热回流12小时，得到由苯并咪唑并[1,2-a]吡啶衍生物。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974169A (zh) * 2014-04-09 2015-10-14 中国科学院大连化学物理研究所 一种荧光素类h2s荧光探针及其制备、应用
CN105017297B (zh) * 2014-04-28 2017-02-15 中国科学院烟台海岸带研究所 一种氟硼吡咯类衍生荧光化合物及其应用
CN106867521A (zh) * 2017-03-29 2017-06-20 叶凤池 一种新型萘酰亚胺h2s荧光探针及其制备方法与应用
CN107383037A (zh) * 2017-07-18 2017-11-24 渤海大学 一种长波长型h2s荧光探针及其合成方法和应用
CN107459483A (zh) * 2016-09-22 2017-12-12 武汉大学 一种细胞膜靶向h2s荧光探针及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974169A (zh) * 2014-04-09 2015-10-14 中国科学院大连化学物理研究所 一种荧光素类h2s荧光探针及其制备、应用
CN105017297B (zh) * 2014-04-28 2017-02-15 中国科学院烟台海岸带研究所 一种氟硼吡咯类衍生荧光化合物及其应用
CN107459483A (zh) * 2016-09-22 2017-12-12 武汉大学 一种细胞膜靶向h2s荧光探针及其制备方法和应用
CN106867521A (zh) * 2017-03-29 2017-06-20 叶凤池 一种新型萘酰亚胺h2s荧光探针及其制备方法与应用
CN107383037A (zh) * 2017-07-18 2017-11-24 渤海大学 一种长波长型h2s荧光探针及其合成方法和应用

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Application publication date: 20180921