CN105924457B - 吡啶并苯并咪唑类铜离子比率荧光探针及其应用 - Google Patents

吡啶并苯并咪唑类铜离子比率荧光探针及其应用 Download PDF

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CN105924457B
CN105924457B CN201610347017.3A CN201610347017A CN105924457B CN 105924457 B CN105924457 B CN 105924457B CN 201610347017 A CN201610347017 A CN 201610347017A CN 105924457 B CN105924457 B CN 105924457B
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葛燕青
段桂运
曹晓群
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Taishan Medical University
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Abstract

本发明公开了一种吡啶并苯并咪唑‑罗丹明酰肼衍生物类Cu2+比率荧光探针，所述探针是吡啶并苯并咪唑取代的罗丹明酰肼，其化学结构式如式（1）所示。本发明的荧光探针在乙醇溶液中对Cu2+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。

Description

吡啶并苯并咪唑类铜离子比率荧光探针及其应用
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Cu2+比率荧光探针吡啶并苯并咪唑取代的罗丹明酰肼及其应用。
背景技术
罗丹明荧光染料因其吸收和发射均在可见光区域, 荧光量子产率高,摩尔消光系数大,光稳定性高,合成简便等,结构修饰后被广泛应用于进行检测金属离子的荧光探针或化学传感器的研究。
Cu2+是人体内继铁、锌之后第三丰富的过渡金属元素。它在许多生理过程中扮演着非常重要的角色,适量的铜能够促进铁元素的吸收,因此铜含量减少有可能导致贫血性疾病。Cu2+能参与体内酶反应,酶转录及一些氧化还原过程,同时还与人处于压力与恐慌下的生理反应密切相关。若体内Cu2+的代谢不正常,则可能导致各种疾病,如Menkes综合症, 家族性肌萎缩症,Wilson综合症,阿尔茨海默氏症等。 当人体内Cu2+含量过高,又会对生物体产生巨大的毒害作用。因此，对人体内铜离子的定性和定量检测成为近年来化学工作者们非常关注的领域。然而，目前铜离子探针几乎全部为单一的信号增强或减弱型探针，具有两个或多个信号响应变化的比率型荧光探针甚少。
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Cu2+比率荧光探针吡啶并苯并咪唑取代的罗丹明酰肼及其应用。
本发明的技术方案是：一种吡啶并苯并咪唑取代的罗丹明酰肼类Cu2+比率荧光探针，其化学结构式如式（1）所示：
本发明还包括吡啶并苯并咪唑取代的罗丹明酰肼类Cu2+比率荧光探针的应用，式（1）化合物在乙醇溶液中对Cu2+有独特的荧光选择性。
本发明还包括吡啶并苯并咪唑取代的罗丹明酰肼类Cu2+比率荧光探针的合成方法，在二氯甲烷溶液中，将吡啶并苯并咪唑与罗丹明酰肼按照1:1投料比例，在EDC和DMAP催化条件下，常温下反应2-5小时，得到吡啶并苯并咪唑取代的罗丹明酰肼。
配制吡啶并苯并咪唑取代的罗丹明酰肼的乙醇溶液，分别加入定量的MgCl2，CaCl2， AlCl3，SnCl2· 2H2O,PbSO4，CrCl3· 6H2O, MnCl2· 4H2O, FeCl3·6H2O, CoCl2·6H2O, NiCl2·6H2O, PdCl2，HgCl2, ZnCl2, CuCl2·2H2O, CdCl2·2½H2O, AgNO3的乙醇溶液，通过荧光光谱测试来研究对不同金属离子的选择性，测其荧光发射波谱强度变化发现：本发明所述吡啶并苯并咪唑取代的罗丹明酰肼即式（1）化合物对Cu2+有独特的荧光选择性，如图1所示。逐渐加入Cu2+至1当量后，化合物1在436nm处荧光强度明显降低，同时，在580nm处荧光强度明显增强，如图2所示。因此，吡啶并苯并咪唑取代的罗丹明酰肼作为Cu2+比率荧光探针具有巨大的应用。
本发明提供了一种吡啶并苯并咪唑取代的罗丹明酰肼类Cu2+比率荧光探针，实验证明本发明所述式（1）化合物可与Cu2+在乙醇溶液中以化学计量比1:1反应，在反应过程中，由于罗丹明与铜离子作用，水解开环，从而使供体吡啶并苯并咪唑与受体罗丹明发生能量传递，导致化合物1在436nm处荧光强度明显降低，同时，在580nm处荧光强度明显增强。由此可证实本发明所述式（1）化合物在乙醇溶液中对Cu2+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）的乙醇溶液中加入等当量的不同金属离子后的荧光强度变化比例柱状图，图1中纵坐标为580nm处的光强与436nm处的光强之比。
图2：式（1）化合物（10-5M）的乙醇溶液中进行Cu2+荧光滴定图。图中intensity为光强，Wavelength为波长，eq为倍数。
图3：式（1）化合物（10-5M）和等当量的Cu2+共存的乙醇溶液中加入等当量的其它金属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0.226g（1.0 mmol）吡啶并苯并咪唑羧酸，0.290g（1.5 mmol）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0.470g（1.0 mmol）罗丹明酰肼，常温下反应2-5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0.51g灰白色固体，产率75%。
核磁共振氢谱测定：1H NMR（400 MHz，CDCl3）：δ8.45 (d, J = 8.0 Hz,1H), 8.05(d, J = 8.0 Hz,1H),7.94 (m, 2H), 7.60 (m, 1H), 7.48 (m, 3H),7.10 (m, 1H),6.80 (d, J = 4.0 Hz,1H), 6.44 (s,1H), 6.34 (d, J = 4.0 Hz,1H), 4.04 (m, 2H),3.68 (s, 2H), 3.51 (d, J = 4.0 Hz,2H), 3.36 (m, 6H), 3.18 (m, 3H),2.74 (s,3H), 1.19 (t, J = 8.0 Hz, 6H)。
实施例2：
向式（1）化合物（10-5M）的乙醇溶液中分别加入2当量的Cr3+，Mn2+，Fe3+，Co2+,Ni2+,Cu2+,Zn2+,Cd2+,Hg2+和Ag+后，测其在436nm以及580nm荧光发射强度比值变化发现：式（1）化合物对Cu2+有独特的荧光选择性，加入1当量的Cu2+后，化合物1在436nm处荧光强度明显降低，同时，在580nm处荧光强度明显增强，I580/I436 = 30.4,如图2所示。
实施例3：
于式（1）化合物（10-5M）和1当量的Cu2+的乙醇溶液中分别加入2当量的Mg2+，Ca2+，Al3+,Sn2+, Pb2+,Cr3+，Mn2+，Fe3+，Co2+,Ni2+,Zn2+,Cd2+,Pd2+,Hg2+和Ag+后，测其在436nm以及580nm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)

1.一种吡啶并苯并咪唑-罗丹明酰肼衍生物类Cu2+比率荧光探针，其特征在于：它是吡啶并苯并咪唑取代的罗丹明酰肼，其化学结构式如式（1）所示：
式（1）化合物在乙醇溶液中对Cu2+有独特的荧光选择性。
2.权利要求1所述吡啶并苯并咪唑-罗丹明酰肼衍生物类Cu2+比率荧光探针的合成方法，其特征在于：在二氯甲烷溶液中，将4-甲基-吡啶并[1，2-a] 苯并咪唑-3-甲酸与2-（3-N,N-二乙基氨基-6-哌嗪基氧杂蒽基）苯甲酰肼按照1:1投料比例，在EDC和DMAP催化条件下，常温下反应2-5小时，得到4-甲基-吡啶并[1，2-a] 苯并咪唑-3-甲酸取代的2-（3-N,N-二乙基氨基-6-哌嗪基氧杂蒽基）苯甲酰肼。
CN201610347017.3A 2016-05-24 2016-05-24 吡啶并苯并咪唑类铜离子比率荧光探针及其应用 Expired - Fee Related CN105924457B (zh)

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CN108219773A (zh) * 2016-12-23 2018-06-29 泰山医学院 吡啶[1,2-a]并苯并咪唑衍生物类Hg2+比率荧光探针及其应用
CN109722238A (zh) * 2017-10-27 2019-05-07 泰山医学院 吡啶修饰的吡啶并[1,2-a]苯并咪唑类SO32-比率荧光探针及其应用
CN108395430A (zh) * 2018-03-07 2018-08-14 泰山医学院 吡啶并苯并咪唑苯并噁二唑类半胱氨酸探针及其应用
CN108484644B (zh) * 2018-05-23 2019-06-21 泰山医学院 吡唑并[1,5-a]吡啶取代的罗丹明酰肼类Cu2+比率型荧光探针及其应用
CN108774243B (zh) * 2018-08-22 2020-01-07 许昌学院 一种吡咯-罗丹明酰腙衍生物及其制备方法和应用

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