CN104860879B - 一种丙二腈异佛尔酮类铜离子荧光探针及其制备方法 - Google Patents

一种丙二腈异佛尔酮类铜离子荧光探针及其制备方法 Download PDF

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CN104860879B
CN104860879B CN201510178114.XA CN201510178114A CN104860879B CN 104860879 B CN104860879 B CN 104860879B CN 201510178114 A CN201510178114 A CN 201510178114A CN 104860879 B CN104860879 B CN 104860879B
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cyanoacetyl
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isophorone
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张大同
安瑞冰
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Abstract

本发明公开了一种丙二腈异佛尔酮类铜离子荧光探针及其制备方法，属于分析检测技术领域。本发明的丙二腈异佛尔酮类铜离子荧光探针具有良好的荧光性能，可以在缓冲溶液中选择性的识别铜离子，表现为检测限低(仅为0.2 µM)、大Stokes位移、荧光增强、长波长发射和可见光下变色，运用其荧光增强和可见光下变色可对铜离子进行裸眼检测；运用其对铜离子的荧光增强响应可以对铜离子进行定性或定量分析；能进入HeLa细胞，且与细胞中铜离子作用后显示红色荧光成像。因此本发明制备的铜离子荧光探针可应用于环境和生物细胞中的铜离子检测。

Description

一种丙二腈异佛尔酮类铜离子荧光探针及其制备方法
技术领域
本发明涉及分析检测技术领域，特别涉及一种丙二腈异佛尔酮类铜离子荧光探针及其制备方法。
背景技术
铜是人体所必需的第三大过渡金属元素，在很多的生物生命体系中起了重要的生理作用。人体中缺乏铜离子能够导致神经衰退性疾病，比如阿尔茨海默病、Menkes综合征、Wilson病和Prion病等。人体摄入过多的铜离子会与氧分子作用产生活性氧物种，损害蛋白质、核酸和脂质。另外，由于工业和生活上铜的广泛使用，其对环境也造成了严重污染。因此，能够高灵敏、高选择性的检测生物体内以及环境中的铜离子越来越受到人们的重视。
荧光化学传感器由于具有高灵敏度、可实时或者远程检测等优点，在识别分子或离子领域中的应用得到了蓬勃发展。在检测金属离子方面，荧光分析方法比比色和分光光度法灵敏度高。与传统金属离子检测方法，如原子吸收光谱，电感耦合等离子体质谱等方法相比，荧光检测方法操作简单且检测限低，不需要进行复杂的多级样本制备，而且设备仪器简单。因此，荧光探针检测因其兼备便捷、专一和灵敏的优点，并能对环境体系和生命体系中的分析对象进行实时原位检测而具有广泛的应用前景。
最近几年，能够在水溶液中识别检测离子的荧光探针由于可应用到生物细胞内的离子检测，因而引起人们极大的兴趣和重视。设计合成高灵敏、高选择性、可在水溶液中检测离子的荧光探针备受人们关注。
近年来报道的铜离子荧光探针存在很多缺陷，比如只能在纯有机溶剂体系或含水量少的溶剂体系检测铜离子（G. Ajayakumar, K. Sreenath, K. R. Gopidas,Phenothiazine attached Ru(bpy)3 2+ derivative as highly selective "turn-ON"luminescence chemodosimeter for Cu2+, Dalton Trans., 7 (2009) 1180-1186）；需要特殊的反应条件（N. Li, Y. Xiang, A. J. Tong, Highly sensitive and selective "turn-on" fluorescent chemodosimeter for Cu2+ in water via Cu2+-promotedhydrolysis of lactone moiety in coumarin, Chem. Commun., 46 (2010) 3363-3365）；对铜离子的选择性和灵敏度低（V. Dujols, F. Ford, W. Czarnik, A Long-Wavelength Fluorescent Chemodosimeter Selective for Cu(II) Ion in Water, J.Am. Chem. Soc., 119 (1997) 7386-7387）；荧光易被铜离子淬灭（J. X. Yin, X. Ma, G.H. Wei, D. B. Wei, Y. G. Du, A highly selective and sensitive sugar–rhodamine“turn-on”fluorescent sensor for divalent copper ion detection inacetonitrile, Sens. Actuators B: Chem., 177 (2013) 213-217）等，这些缺陷的存在限制其广泛应用。
发明内容
为了弥补以上不足，本发明提供了一种化学性质稳定且对铜离子的响应具有高灵敏度和高选择性的丙二腈异佛尔酮类铜离子荧光探针及其制备方法。
本发明的技术方案为：
一种丙二腈异佛尔酮类铜离子荧光探针，为如下结构式（1）所示的化合物；
（1）。
所述丙二腈异佛尔酮类铜离子荧光探针的制备方法，结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈与吡啶甲酸反应制得结构式（1）所示的化合物；
（1） （2）。
进一步的，结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈与吡啶甲酸在4-二甲氨基吡啶和二环己基碳二亚胺存在的条件下在有机溶剂中反应。
反应方程式如下：
作为优选方案，结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈、吡啶甲酸和二环己基碳二亚胺（DCC）的摩尔比为1:1:1-1:2:2；4-二甲氨基吡啶（DMAP）的用量为2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈用量的30%-70%。该物料比范围下，产率高，易提纯。
作为优选方案，所述有机溶剂为四氢呋喃、二氯甲烷或氯仿。以四氢呋喃、二氯甲烷或氯仿为溶剂可在室温下反应，且产率高。
作为优选方案，结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈、吡啶甲酸4-二甲氨基吡啶和二环己基碳二亚胺依次加入到反应容器，加入有机溶剂溶解，室温下反应5-15h。
所述丙二腈异佛尔酮类铜离子荧光探针在铜离子识别与检测中的应用。
本发明的有益效果为：
本发明的丙二腈异佛尔酮类铜离子荧光探针具有良好的荧光性能，可以在缓冲溶液中选择性的识别铜离子，表现为检测限低(仅为0.2 µM)、大Stokes位移、荧光增强、长波长发射和可见光下变色，运用其荧光增强和可见光下变色可对铜离子进行裸眼检测；运用其对铜离子的荧光增强响应可以对铜离子进行定性或定量分析；能进入HeLa细胞，且与细胞中铜离子作用后显示红色荧光成像。因此本发明制备的铜离子荧光探针可应用于环境和生物细胞中的铜离子检测。
本发明的制备方法原料易得，容易监测和控制，产品易于分离、纯度高。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1制得的荧光探针溶液在可见光下颜色变化对比图，其中第一排为纯探针溶液及探针与一个当量的其他金属离子的混合溶液，第二排为在第一排的基础上加入一个当量的铜离子；
图2为实施例1制得的荧光探针溶液及探针与一个当量的金属离子的混合溶液的紫外-可见吸收图谱；
图3为实施例1制得的荧光探针溶液随着硝酸铜加入5 min后荧光变化图谱（λex =426 nm），其中硝酸铜浓度为0-40 µM；
图4为图3中590nm处的荧光强度随着铜离子浓度变化的散点图；
图5为实施例1制得的荧光探针溶液及探针与一个当量的金属离子的混合溶液的荧光发射图谱。
具体实施方式
实施例1
丙二腈异佛尔酮类铜离子荧光探针化合物的合成
在50mL的单口烧瓶中，依次将2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈（300 mg, 1.0 mmol）、2-吡啶甲酸(191 mg, 1.3 mmol)、4-二甲氨基吡啶(76 mg, 0.6 mmol)和二环己基碳二亚胺(320 mg, 1.6 mmol)溶于10 mL干燥四氢呋喃中，室温搅拌反应10 h，过滤，滤液减压除去溶剂，将所得残留物用二氯甲烷溶解，二氯甲烷溶液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶，产率60%。
其中，2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈可根据公布号为“CN 101967373 A”的中国发明专利中公开的方法制备；也可直接购买。
本实施例制得的丙二腈异佛尔酮类铜离子荧光探针化合物，其分子式为C25H21N3O2，核磁氢谱分析为1H NMR (400 MHz, CDCl3) δ 8.87 (d, J = 4.0 Hz, 1H),8.30 (d, J = 8.0 Hz, 1H), 7.95 (td, J = 8.0, 2 Hz, 1H),7.61 – 7.59 (m, 3H),7.33 (d, J = 8.8 Hz, 2H), 7.08 (d, J = 16.1 Hz, 1H), 6.98 (d, J = 16.2 Hz,1H), 6.87 (s, 1H), 2.62 (s, 2H), 2.49 (s, 2H), 1.10 (s, 6H). 核磁碳谱分析为13CNMR (100 MHz, CDCl3) δ 168.63,153.01, 151.35, 149.59, 136.87, 135.28, 133.22,128.97, 128.16, 127.10, 125.45, 123.26, 121.87, 112.89, 112.11, 42.50, 38.74,31.52, 27.50.高分辨质谱分析为HRMS (ESI) calcd for [M+H]+ C25H21N3O2: 396.1712,found: 396.1715.
实施例2
丙二腈异佛尔酮类铜离子荧光探针化合物的合成
在50mL的单口烧瓶中，依次将2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈（300 mg, 1.0 mmol）、2-吡啶甲酸(220 mg, 1.5mmol)、4-二甲氨基吡啶(76mg, 0.6 mmol)和二环己基碳二亚胺(360 mg, 1.8 mmol)溶于10 mL干燥四氢呋喃中，室温搅拌反应7 h，过滤，滤液减压除去溶剂，将所得残留物用二氯甲烷溶解，二氯甲烷溶液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶，产率56%。
实施例3
丙二腈异佛尔酮类铜离子荧光探针化合物的合成
在50mL的单口烧瓶中，依次将2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈（300 mg, 1.0 mmol）、2-吡啶甲酸(147 mg, 1.0 mmol)、4-二甲氨基吡啶(76 mg, 0.6 mmol)和二环己基碳二亚胺(200 mg, 1.0mmol)溶于10 mL干燥四氢呋喃中，室温搅拌反应14 h，过滤，滤液减压除去溶剂，将所得残留物用二氯甲烷溶解，二氯甲烷溶液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶，产率54.5%。
实施例4
丙二腈异佛尔酮类铜离子荧光探针化合物的合成
在50mL的单口烧瓶中，依次将2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈（300 mg, 1.0 mmol）、2-吡啶甲酸(147 mg, 1.0 mmol)、4-二甲氨基吡啶(76 mg, 0.6 mmol)和二环己基碳二亚胺(320 mg, 1.6 mmol)溶于10 mL干燥二氯甲烷中，室温搅拌反应8 h，过滤，滤液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶，产率55.5%。
实施例5
丙二腈异佛尔酮类铜离子荧光探针化合物的合成
在50mL的单口烧瓶中，依次将2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈（300 mg, 1.0 mmol）、2-吡啶甲酸(147 mg, 1.0 mmol)、4-二甲氨基吡啶(76 mg, 0.6 mmol)和二环己基碳二亚胺(320 mg, 1.6 mmol)溶于10 mL干燥氯仿中，室温搅拌反应12 h，过滤，滤液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶，产率54%。
实施例6
丙二腈异佛尔酮类铜离子荧光探针对铜离子的光物理检测应用研究
将实施例1制备的基于丙二腈异佛尔酮类铜离子荧光探针溶于乙腈中，配制成浓度为1mM的储备液。然后用乙腈/HEPES（10 mM, pH = 7.4, 1:4, v/v）配制浓度为10 µM探针测试溶液。
丙二腈异佛尔酮类铜离子荧光探针在426 nm激发下，在545 nm处有较弱的荧光发射，当向探针溶液中加入铜离子时，荧光最大发射波长红移到590 nm处，Stokes位移达到164 nm；当铜离子加入量在0.5 µM-10 µM内，探针在590 nm处的荧光强度与铜离子浓度成较好的线性，且检测限仅为0.2 µM；当铜离子加入量为两个当量以上时，荧光强度趋于稳定，且荧光增强12倍；加入其他常见金属离子后，没有引起探针紫外-可见吸收和荧光发射的显著变化。
由图1可知，在可见光下肉眼观察，向纯探针溶液中加入Ag+、Al3+、Ca2+、Cd2+、Co2+、Fe3+、Hg2+、K+、Na+、Ni2+、Pb2+、Zn2+离子后，与纯探针溶液颜色基本相同，均呈淡淡的黄色；而加入Cu2+后，在可见光下肉眼观察到，溶液颜色变为深黄色。
由图2可知， 向纯探针溶液中加入Ag+、Al3+、Ca2+、Cd2+、Co2+、Fe3+、Hg2+、K+、Na+、Ni2+、Pb2+、Zn2+离子后，与纯探针溶液的紫外-可见吸收光谱基本一致；而加入Cu2+后，探针溶液的紫外-可见吸收明显发生红移。
由图3可知，Cu2+的加入，引起了探针最大发射波长的红移，并且随着Cu2+浓度增大，荧光强度逐渐增大。
由图4可知，当铜离子加入量在0.5 µM-10 µM内时，探针在590 nm处的荧光强度与铜离子浓度成较好的线性；本发明的荧光探针对Cu2+的检测限非常低，仅为0.2 µM；当铜离子加入量为两个当量以上时，荧光强度趋于稳定，且荧光增强12倍。
由图5可知，向纯探针溶液中加入Ag+、Al3+、Ca2+、Cd2+、Co2+、Fe3+、Hg2+、K+、Na+、Ni2+、Pb2+、Zn2+离子后，与纯探针溶液的荧光发射图谱基本一致；而加入Cu2+后，探针溶液的荧光发射强度明显增强。
由此得出结论，本发明制备的基于丙二腈异佛尔酮类铜离子荧光探针对铜离子具有很高的选择性和灵敏性，且可用于铜离子的定量和定性检测。

Claims (4)

1.一种丙二腈异佛尔酮类铜离子荧光探针，其特征在于，为如下结构式（1）所示的化合物；
（1）。
2.如权利要求1所述丙二腈异佛尔酮类铜离子荧光探针的制备方法，其特征在于：结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈与吡啶甲酸反应制得结构式（1）所示的化合物；
（1） 2）；
结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈、吡啶甲酸、4-二甲氨基吡啶和二环己基碳二亚胺依次加入到反应容器，加入有机溶剂溶解，室温下反应5-15h，过滤，滤液减压除去溶剂，将所得残留物用二氯甲烷溶解，二氯甲烷溶液用1%稀盐酸洗涤，无水硫酸钠干燥，减压蒸干溶剂得粗品，以二氯甲烷/石油醚混合溶液重结晶得黄色结晶产品；结构式（2）所示的化合物2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈、吡啶甲酸和二环己基碳二亚胺的摩尔比为1:1:1-1:2:2；4-二甲氨基吡啶的用量为2-[3-(4-羟基苯乙烯基)-5,5-二甲基-环己-2-烯-1-亚基]丙二腈用量的30%-70%。
3.如权利要求2所述丙二腈异佛尔酮类铜离子荧光探针的制备方法，其特征在于：所述有机溶剂为四氢呋喃、二氯甲烷或氯仿。
4.如权利要求1所述丙二腈异佛尔酮类铜离子荧光探针在铜离子识别与检测中的应用。
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