CN108285448A - 苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探针及其应用 - Google Patents

苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探针及其应用 Download PDF

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CN108285448A
CN108285448A CN201710946520.5A CN201710946520A CN108285448A CN 108285448 A CN108285448 A CN 108285448A CN 201710946520 A CN201710946520 A CN 201710946520A CN 108285448 A CN108285448 A CN 108285448A
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葛燕青
孔祥宇
刘爱坤
吉瑞雪
曹晓群
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Abstract

本发明公开了一种苯并咪唑修饰的吡啶并[1,2‑a]苯并咪唑类亚硫酸根比率荧光探针，所述探针是1‑（2’‑苯并咪唑）‑3‑(4‑苯基‑3’‑吡啶[1,2‑a]并苯并咪唑)‑2‑丙烯‑1‑酮，其化学结构式如式（1）所示。本发明的荧光探针在N，N‑二甲基甲酰胺的水溶液中对SO3 2‑有较高的灵敏度和独特的荧光选择性，与现有探针相比，具有快速、灵敏、不受背景干扰等优点，具有很好的应用前景。

Description

苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探 针及其应用
技术领域
本发明涉及一种苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类类SO3 2-比率荧光探针及其应用，属于有机小分子荧光探针领域。
背景技术
亚硫酸盐是一种常用的食品添加剂,少量的摄入亚硫酸盐不会对身体造成伤害,但是摄入过多的亚硫酸盐有可能造成胃肠障碍、肾功能障碍等疾病，引起剧烈腹痛。除此外,工业废水中含有过多亚硫酸盐,会导致水中溶解氧的浓度严重降低,从而对生态环境造成危害。所以,发明具有高度灵敏度、方便快捷检测亚硫酸盐含量的方法对食品安全和环境检测具有十分重要的意义。
目前，常用的亚硫酸根检测方法有滴定分析法、色谱分析法、电化学分析法、毛细管电泳法等,但是这些方法大多具有费时、需要预处理样品以及设备仪器昂贵等缺点。因此,一种便捷、快速、可靠的亚硫酸根的定量定性检测法对于食品安全及质量检测具有重要意义。
荧光探针技术由于价格低廉，灵敏度高，分子结构易于修饰优化等优点,在食品和环境检测检测中突显了广阔的应用前景,特别是在小分子及离子检测领域备受关注,成为了一个新的研究热点。荧光共振能量转移（FRET）是目前常用的一种非常有效的设计比率探针的方法。但目前能够用于构建FRET体系的染料还很少，而基于荧光共振能量转移原理用于检测亚硫酸盐的比率荧光探针更少。因此，开发新型荧光染料，用于构建亚硫酸根离子比率荧光探针是一项非常有意义的工作。
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苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针及其应用。
本发明的技术方案是：一种苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针，其化学结构式如式（1）所示：
（1）
本发明还包括苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针的应用，式（1）化合物在N，N-二甲基甲酰胺/水 (体积比2:3) 溶液中对SO3 2-有独特的荧光选择性。
本发明还包括苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针的合成方法，在乙醇溶液中，将4-苯基-吡啶[1,2-a]并苯并咪唑-3-甲醛与2-乙酰基苯并咪唑按照摩尔比1:2比例投料，以0.5毫升哌啶为催化剂，加热回流20小时，得到1-（2’-苯并咪唑）-3-(4-苯基-3’-吡啶[1,2-a]并苯并咪唑)-2-丙烯-1-酮。
配制苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针的N，N-二甲基甲酰胺/水溶液(体积比2:3)，分别加入定量的NaSO3，NaAco，NaBr，NaH2PO4，NaCl, Na2CO3，NaHCO3，NaF ，NaHPO4，NaHS，NaI，NaNO2，NaNO3，Na2S2O3，Na2SO4，FeCl3，CaCl2，Cu Cl2，KCl，NaCl，ZnCl2，Glu，Hcy，Cys的水溶液，通过荧光光谱测试来研究对不同离子及氨基酸的选择性，其荧光发射波谱强度变化表明：本发明所述苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针即式（1）化合物对SO3 2-有独特的荧光选择性，如图1所示。逐渐加入SO3 2-至10当量后，化合物1在564nm处荧光强度明显降低，同时，在440nm处荧光强度明显增强，如图1所示。因此，苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑衍生物即式（1）化合物作为SO3 2-比率荧光探针具有巨大的应用前景。
本发明提供了一种苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO3 2-比率荧光探针即式（1）化合物，实验证明本发明所述式（1）化合物可与SO3 2-在N，N-二甲基甲酰胺/水溶液中(体积比2:3)以化学计量比1:10反应，在反应过程中，由于亚硫酸根离子破坏了甲酰基吡啶1,2-a]并苯并咪唑与乙酰基苯并咪唑间的共轭双键，从而使双键断开，使供体吡啶[1,2-a]并苯并咪唑与受体乙酰基苯并咪唑发生能量传递，导致化合物1在564nm处荧光强度明显降低，同时，在440nm处荧光强度明显增强。由此可证实本发明所述式（1）化合物在N，N-二甲基甲酰胺/水(体积比2:3) 溶液中对Hg2+有独特的荧光选择性、较高的灵敏度及较强的抗其它离子干扰能力，具有巨大的应用前景。
附图说明
图1：式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中加入10当量的SO3 2-及等当量的不同阴离子、阳离子、氨基酸后的荧光强度变化图。图中FL Intensity为荧光强度，Wavelength为波长，equiv为倍数。
图2：式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中进行SO3 2-荧光滴定图。图中FL Intensity为荧光强度，Wavelength为波长，equiv为倍数。
图3：式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中进行SO3 2-紫外滴定图。图中Abs.为吸光度，Wavelength为波长，equiv为倍数。
图4：式（1）化合物合成方法反应式图。
图5：式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中加入10当量的SO3 2-等当量的不同阴离子、阳离子、氨基酸后的紫外强度变化图。图中Abs.为吸光度，Wavelength为波长，equiv为倍数。
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0.27g（1.0 mmol）4-苯基-吡啶[1,2-a]并苯并咪唑-3-甲醛，0.32g（2.0 mmol）2-乙酰基苯并咪唑，30 mL乙醇，0.5毫升哌啶，加热回流反应20小时。TLC检测反应完成后，停止加热，冷却至室温后过滤出固体，用冷乙醇洗涤3次，烘干，得0.27g橘红色固体，产率62.5%。
核磁共振氢谱测定：1H NMR（400 MHz，CDCl3）：δ=9.06 (d, J = 8.0 Hz, 1H),8.29(d, J = 8.0 Hz, 1H), 8.24 (d, J = 16.0 Hz, 1H), 8.12 (s, 1H), 7.90 (d, J =16.0 Hz, 1H), 7.81 (t, J = 8.0 Hz, 2H), 7.59 (d, J = 12.0 Hz,7H), 7.48 (t, J= 8.0 Hz, 1H), 7.39 (m, J = 8.0 Hz, 2H),7.31 (d, J = 8.0 Hz, 1H)。
实施例2：
向式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中分别加入10当量的SO3 2-，Aco-，Br-，H2PO4 -，Cl-，CO3 -，HCO3 -，F-，HPO42-，HS-，I-，NO2 -，NO3 -，S2O3 2-，SO4 2-，Fe3+，Ca2+，Cu2+，K+ ，Na+，Zn2+，Glu，Hcy 和Cys 后，测其在440nm以及564nm荧光发射强度比值变化发现：式（1）化合物对SO3 2-有独特的荧光选择性，加入10当量的SO3 2-后，化合物1在564nm处荧光强度明显降低，同时，在440nm处荧光强度明显增强，I440/I564 = 115.7,如图1所示。
实施例3：于式（1）化合物（10-5M）的N，N-二甲基甲酰胺/水 (体积比2:3)溶液中分别加入不同浓度的SO3 2-,随着亚硫酸根浓度的增加,探针的紫外光谱和荧光光谱发生明显变化，如图2和图3所示。

Claims (2)

1.本发明涉及一种苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类比率型亚硫酸根荧光探针，其特征在于：它是1-（2’-苯并咪唑）-3-(4-苯基-3’-吡啶[1,2-a]并苯并咪唑)-2-丙烯-1-酮，其化学结构式如式（1）所示：
（1）
式（1）化合物在N，N-二甲基甲酰胺的水溶液中对SO3 2-有独特的荧光选择性。
2.权利要求1所述1-（2’-苯并咪唑）-3-(4-苯基-3’-吡啶[1,2-a]并苯并咪唑)-2-丙烯-1-酮SO3 2-比率荧光探针的合成方法，其特征在于：在乙醇溶液中，将4-苯基-吡啶[1,2-a]并苯并咪唑-3-甲醛与2-乙酰基苯并咪唑按照摩尔比1:2比例投料，以0.5毫升哌啶为催化剂，加热回流20小时，得到1-（2’-苯并咪唑）-3-(4-苯基-3’-吡啶[1,2-a]并苯并咪唑)-2-丙烯-1-酮。
CN201710946520.5A 2017-10-12 2017-10-12 苯并咪唑修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探针及其应用 Pending CN108285448A (zh)

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Application publication date: 20180717