CN108358934A - 咪唑并吡啶苯并噻唑类亚硫酸根荧光探针及其应用 - Google Patents

咪唑并吡啶苯并噻唑类亚硫酸根荧光探针及其应用 Download PDF

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CN108358934A
CN108358934A CN201810178697.XA CN201810178697A CN108358934A CN 108358934 A CN108358934 A CN 108358934A CN 201810178697 A CN201810178697 A CN 201810178697A CN 108358934 A CN108358934 A CN 108358934A
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葛燕青
吕花营
吉瑞雪
段桂运
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Abstract

本发明公开了一种咪唑并[1,5‑a]吡啶苯并噻唑类亚硫酸根离子比率荧光探针，所述探针是1‑乙基‑2‑（N‑（1‑氯‑3‑丁基‑7‑咪唑并[1,5‑a]吡啶甲酰基）‑4‑（哌嗪基）‑苯基乙烯）苯并噻唑碘化物，其化学结构式如式（1）所示。本发明的荧光探针在PBS缓冲溶液中（pH=7.40）对亚硫酸根离子有较好的荧光选择性和较高的灵敏度以及较强的抗其它离子干扰能力，具有巨大的应用前景。

Description

咪唑并吡啶苯并噻唑类亚硫酸根荧光探针及其应用
技术领域
本发明涉及有机小分子荧光探针领域，尤其涉及一种新型亚硫酸根离子荧光探针1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物及其应用。
背景技术
二氧化硫是空气主要污染物之一，当其浓度超过一定量后，会引起各种疾病，如肺癌、神经疾病等。二氧化硫溶于水后形成亚硫酸根和亚硫酸氢根，并3:1 (体积比)的比例平衡存在于水中，因此，对亚硫酸根的选择性和灵敏性检测对人类健康具有重要意义。
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，现广泛应用于离子的测定。尽管已有多种亚硫酸根荧光探针被报道，但是目前多数探针为单一信号的增强或减弱型探针，具有两个或多个信号响应变化的比率型探针甚少。
发明内容
针对现有技术的不足，本发明解决的问题是提供一种两个信号响应变化的亚硫酸根离子比率荧光探针1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物及其应用。
本发明的技术方案是：一种咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针，其化学结构式如式（1）所示：
本发明还包括咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针的应用，式（1）化合物在在PBS缓冲溶液中（pH=7.40）对亚硫酸根离子有较好的荧光选择性。
本发明还包括咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针的合成方法，将1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酸与1-乙基-2-（4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物按照物质的量比1:1投料，在EDC和DMAP催化条件下，室温下反应5-8小时，得到1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物。
配制咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针的二甲亚砜溶液，分别加入定量的NaCl, MgCl2·6H2O, Zn(CH3COO)2, FeCl3·6H2O, CuCl2, F-，Br-，I-，HCO3 -，NO3 -，ClO-，SO4 2-，SCN-，S2O3 2-，S2-， SO3 2- 的水溶液，通过荧光光谱测试来研究对不同阴阳离子的选择性，测其荧光发射波谱强度变化发现： 本发明所述咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针即式（1）化合物对亚硫酸根离子有较好的荧光选择性，如图1所示。逐渐加入亚硫酸根离子至30当量后，化合物1在477nm处荧光强度明显增强，同时，在576nm处荧光强度明显减弱，如图2所示。因此，咪唑并吡啶苯并噻唑类亚硫酸根离子比率荧光探针具有巨大的应用前景。
附图说明
图1：式（1）化合物（5×10-6M）的PBS溶液中（pH=7.40）加入30当量的不同阴阳离子后的荧光强度变化比例柱状图，图1中纵坐标为576nm处的光强与477nm处的光强之比。
图2：式（1）化合物（5×10-6M）的PBS溶液中（pH=7.40）进行亚硫酸根离子荧光滴定图。
图3：式（1）化合物（5×10-6M）和30当量的亚硫酸根离子共存的PBS溶液中（pH=7.40）加入30当量的其它阴阳离子后荧光强度比率的变化柱状图。
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0.253g（1.0 mmol）咪唑并[1,5-a]吡啶羧酸，0.290g（1.5mmol）1-（3-二甲氨基丙基）-3-乙基碳二亚胺（EDC），0.180g（1.5 mmol）4-二甲氨基吡啶(DMAP)，20 mL无水二氯甲烷，常温下反应30 分钟，然后加入0.477g（1.0 mmol）1-乙基-2-（4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物，常温下反应5-8小时。TLC检测反应完成后，加入100 mL二氯甲烷，30 mL水洗三次，二氯甲烷层硫酸钠干燥，浓缩，柱层析得0.39g红色固体，产率54.9%。
核磁共振氢谱测定： 1H NMR (DMSO-d6, 400 MHz), δ 8.11 (d, J = 4.0 Hz,3H), 7.92 (m, 2H), 7.81 (d, J = 4.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.71(t, J = 4.0 Hz, 1H), 7.61 (t, J = 4.0 Hz, 1H), 7.53 (s, 1H), 6.84 (d, J = 8.0Hz, 2H), 6.72 (d, J = 8.0 Hz, 1H), 5.11 (q, J = 8.0 Hz, 2H), 3.80 (s, 4H),3.45 (s, 4H), 2.96 (t, J = 8.0 Hz, 2H), 1.83 (m, 2H), 1.58 (t, J = 8.0 Hz,3H), 1.45 (m, 2H), 0.97 (t, J = 8.0 Hz, 3H).
实施例2：
向式（1）化合物（5×10-6M）的PBS溶液中加入30当量的Na+, Mg2+, Zn2+, Fe3+, Cu2+,F-, Br-，I-, HCO3 -，NO3 -，ClO-，SO4 2-，SCN-，S2O3 2-，S2-和SO3 2-后，测其在477nm以及576nm荧光发射强度比值变化发现：式（1）化合物对SO3 2-有较好的荧光选择性，其在477nm处荧光强度明显增强，同时，在576nm处荧光强度明显降低，I477/I576 = 9.1,如图1所示。
实施例3：
向式（1）化合物（5×10-6M）和30当量的SO3 2-的PBS溶液中分别加入30当量的Na+, Mg2+,Zn2+, Fe3+, Cu2+, F-, Br-，I-, HCO3 -，NO3 -，ClO-，SO4 2-，SCN-，S2O3 2-和S2-后，测其在477nm以及576nm荧光发射强度比值变化发现：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)

1.一种咪唑并[1,5-a]吡啶苯并噻唑类亚硫酸根离子比率荧光探针，其特征在于：它是1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物，其化学结构式如式（1）所示：
式（1）化合物在PBS缓冲溶液中（pH=7.40）对亚硫酸根离子有较好的荧光选择性。
2.权利要求1所述1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物的合成方法，其特征在于：在二氯甲烷溶液中，将1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酸与1-乙基-2-（4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物按照物质的量比1:1投料，在EDC和DMAP催化条件下，室温下反应5-8小时，得到1-乙基-2-（N-（1-氯-3-丁基-7-咪唑并[1,5-a]吡啶甲酰基）-4-（哌嗪基）-苯基乙烯）苯并噻唑碘化物。
CN201810178697.XA 2018-03-05 2018-03-05 咪唑并吡啶苯并噻唑类亚硫酸根荧光探针及其应用 Pending CN108358934A (zh)

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Citations (1)

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CN106518860A (zh) * 2016-11-07 2017-03-22 山东大学 一种基于荧光共振能量转移机理的靶向线粒体的次氯酸比例荧光探针及其应用

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CN106518860A (zh) * 2016-11-07 2017-03-22 山东大学 一种基于荧光共振能量转移机理的靶向线粒体的次氯酸比例荧光探针及其应用

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