CN107033072A - 一种基于半花菁的铜离子比率荧光探针及其制备与应用 - Google Patents
一种基于半花菁的铜离子比率荧光探针及其制备与应用 Download PDFInfo
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明涉及一种基于半花菁的铜离子比率荧光探针及其制备与应用，所述荧光探针，分子式为C20H17IN2O2；所述荧光探针的制备包括步骤有：(1)4‑甲基吡啶与碘甲烷反应得到1,4‑二甲基吡啶碘盐，即化合物1，(2)将化合物1与4‑羟基苯甲醛反应得到4‑(4‑羟基苯乙烯基)‑1‑甲基吡啶碘盐，即化合物2，(3)将化合物2与2‑吡啶甲酸反应得到铜离子比率荧光探针4‑(4‑吡啶甲酸酯苯乙烯基)‑1‑甲基吡啶碘盐，即化合物3；所述荧光探针的应用，是在纯水溶液中将荧光探针与铜离子进行反应，利用两个不同发射波长处荧光强度的比率(F503nm/F448nm)变化来检测铜离子的存在与否。本发明探针制备处理过程简单，荧光探针分子在铜离子与其他阳离子共存体系中，表现出较高的选择性和灵敏度。
Description
技术领域
本发明属于金属离子检测的荧光探针技术领域，具体涉及的是一种基于半花菁的铜离子比率荧光探针及其制备与应用。
背景技术
铜离子(Cu2+)是人体中第三丰富的元素，并且其在生物体的各种基本生理过程中具有重要的作用，如基因表达和信号转导等。但是细胞中Cu2+的浓度变化会导致各种疾病，包括阿尔茨海默(Alzheimes)病、缅克斯(Menkes)综合症、肝豆状核变性(Wilsons)病，甚至癌症等。此外，Cu2+被广泛的运用到工业和农业中，所以它也是一种严重的环境污染物。因此，寻找一种简便、快捷检测方法对Cu2+进行分析检测具有重要意义。现有测定Cu2+的方法主要是原子吸收光谱法和分光光度法，但前者需要复杂的仪器及熟练的技术人员及高昂的检测费用，后者需要繁琐的操作，所以都不是理想的识别和检测Cu2+浓度的方法。荧光探针具有灵敏度高、选择性好、成本低、样品用量少、设备简单等优点，并已成为检测重金属离子的有效手段。
目前关于Cu2+荧光探针的研究中，大多是基于单波长荧光发射强度改变的荧光探针，比如荧光淬灭或荧光增强。这些基于单波长发射的荧光探针易受一些因素的影响，比如：光漂白、探针分子的浓度、周围的微环境和光照射下的稳定性等。而比率荧光探针能够克服上述因素的影响。比率荧光探针是通过记录两个荧光发射峰的比率来实现对金属离子的检测的，它有利于增加响应范围，减少环境因素的影响。虽然文献已经报道了一些比率型的Cu2+荧光探针，但这些比率型荧光探针大多都是在纯有机溶剂或含有有机溶剂的水溶液中对Cu2+进行检测。实际上能够在纯水溶液中表现出识别性能的荧光探针才具有更广阔的使用价值。因此，迫切需要开发研究在纯水溶液中常温快速高效地检测Cu2+的新型比率荧光探针。
基于吡啶盐的半花菁4-(4-羟基苯乙烯基)-1-甲基吡啶碘盐不仅具有良好水溶性，而且具有典型的“推-拉”结构，表现出优良的光学性能。当羟基被吸电子基团2-吡啶甲酰基保护后，使其“推”电子的能力降低，并伴随吸收光谱和荧光光谱的变化，同时吡啶甲酸酯基团很容易被Cu2+水解。因此，本发明的基于半花菁的铜离子比率荧光探针是以4-(4-羟基苯乙烯基)-1-甲基吡啶碘盐作为荧光团，以吡啶甲酸酯作为识别单元的比率型荧光探针。经检索没有发现与本申请相近似的文献及专利申请。
发明内容
本发明的目的是针对现有技术的不足，通过分子设计，合成出一种在纯水溶液中检测铜离子并具有灵敏度高、选择性好和响应时间短的基于半花菁的铜离子比率荧光探针。
本发明还提供了上述基于半花菁的铜离子比率荧光探针的制备方法。
本发明还提供了上述基于半花菁的铜离子比率荧光探针的应用。
本发明解决其技术问题是采取以下技术方案实现的：
一种基于半花菁的铜离子比率荧光探针，它的分子式为C20H17IN2O2，结构式如下：
一种基于半花菁的铜离子比率荧光探针的制备方法，包括步骤如下：
(1)4-甲基吡啶与碘甲烷反应得到1,4-二甲基吡啶碘盐，即化合物1，其结构式如下：
(2)将步骤(1)得到化合物1与4-羟基苯甲醛反应得到4-(4-羟基苯乙烯基)-1-甲基吡啶碘盐，即化合物2，其结构式如下：
(3)将步骤(2)得到化合物2与2-吡啶甲酸反应得到铜离子比率荧光探针4-(4-吡啶甲酸酯苯乙烯基)-1-甲基吡啶碘盐，即化合物3。
而且，所述步骤(1)中化合物1获得的具体方法为：将4-甲基吡啶和碘甲烷溶于乙腈中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用乙酸乙酯洗涤，收集固体即为化合物1。
而且，所述4-甲基吡啶与碘甲烷的比例为1:1.25。
而且，所述步骤(2)中化合物2获得的具体方法为：将化合物1，4-羟基苯甲醛和哌啶溶于无水乙醇中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用无水乙醇洗涤，收集固体即为化合物2。
而且，所述化合物1与4-羟基苯甲醛和哌啶的比例为1:1.5:0.5。
而且，所述步骤(3)中化合物3获得的具体方法为：将化合物2，2-吡啶甲酸，1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐和4-二甲氨基吡啶溶于无水二氯甲烷中，在氩气保护下室温反应2小时，反应完全后，有固体析出，过滤并用无水二氯甲烷洗涤，收集固体即为铜离子比率荧光探针，即化合物3。
而且，所述化合物1与2-吡啶甲酸，1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐和4-二甲氨基吡啶的比例为1:1.5:1.5:0.6。
一种基于半花菁的铜离子比率荧光探针的应用，该应用是在纯水溶液中将荧光探针与铜离子进行反应，利用两个不同发射波长处荧光强度的比率(F503nm/F448nm)变化来检测铜离子的存在与否。
而且，在未加入铜离子前，所述反应溶液的最大荧光发射波长位于448nm处，当加入铜离子后，所述反应溶液的448nm处的荧光减弱，最大荧光发射波长红移至503nm处，所述检测铜离子的检出浓度下限为1.1nM。
本发明的优点及其效果
1、本发明探针的合成只需要三步就可以完成，且后处理过程简单。
2、本发明荧光探针分子在铜离子与其他阳离子共存体系中，表现出较高的选择性和灵敏度。
附图说明
图1为实施案例1中化合物2的1H NMR图谱；
图2为实施案例1中化合物2的13C NMR图谱；
图3为实施案例1中化合物2的ESI-MS图谱；
图4为实施案例1中化合物3的1H NMR图谱；
图5为实施案例1中化合物3的13C NMR图谱；
图6为实施案例1中化合物3的ESI-MS图谱；
图7中(a)为pH值对化合物2(503nm)和3(448nm)荧光强度的影响示意图，(b)为pH值对化合物2和3的荧光强度比率(F503nm/F448nm)的影响示意图；
图8为pH值对化合物3与Cu2+反应前后的荧光强度比率(F503nm/F448nm)的影响示意图；
图9中(a)为最佳测试条件下化合物3与Cu2+反应的吸收光谱变化示意图，(b)为化合物3与Cu2+反应时吸光度在342nm和374nm处随时间的变化示意图；
图10中(a)为最佳测试条件下化合物3与Cu2+反应的荧光光谱变化示意图，(b)为化合物3与Cu2+反应的荧光强度比率(F503nm/F448nm)随时间的变化示意图；
图11中(a)为化合物3与不同浓度Cu2+反应的荧光强度比率(F503nm/F448nm)随时间的变化示意图，(b)为化合物3的荧光强度比率(F503nm/F448nm)随Cu2+浓度的变化示意图；
图12为化合物3与不同金属离子反应前后的荧光强度比率(F503nm/F448nm)的变化示意图，(灰色柱代表探针只经标注的金属离子处理，黑色柱代表探针经标注的金属离子处理后，再添加Cu2+；1.无金属离子，2.Na+，3.K+，4.Ca2+，5.Mg2+，6.Ag+，7.Zn2+，8.Cd2+，9.Hg2+，10.Ba2+，11.Co2+，12.Ni2+，13.Mn2+，14.Pb2+，15.Al3+，16.Fe3+，17.Sn4+，18.Cu2+)；
图13为铜离子比率荧光探针化合物3的合成路线及其对Cu2+检测的反应机理示意图。
具体实施方式
以下对本发明实施例做进一步详述：需要强调的是，本发明所述的实施例是说明性的，而不是限定性的，因此本发明并不限于具体实施方式中所述的实施例，凡是由本领域技术人员根据本发明的技术方案得出的其它实施方式，同样属于本发明保护的范围。
实施例
(一)目标化合物铜离子荧光探针的制备
(1)化合物1的合成
将4-甲基吡啶(1.96ml，20mmol)和碘甲烷(1.56ml，25mmol)溶于乙腈(20ml)中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用乙酸乙酯洗涤，收集固体，产率为88％。
(2)化合物2的合成
将化合物1(2.35g,10mmol)，4-羟基苯甲醛(1.83g,15mmol)和哌啶(0.5mL,5mmol)溶于无水乙醇(30mL)中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用无水乙醇洗涤，收集固体，产率为80％。
化合物2的1H NMR图谱如图1所示，1H NMR(400MHz,d6-DMSO,ppm)δ8.66(d,J＝6.8Hz,2H),8.02(d,J＝6.8Hz,2H),7.89(d,J＝16.0Hz,1H),7.53(d,J＝8.8Hz,2H),7.10(d,J＝16.0Hz,1H),6.71(d,J＝8.4Hz,2H),4.16(s,3H)。
化合物2的13C NMR图谱如图2所示，13C NMR(100MHz,d6-DMSO,ppm)δ165.95,153.31,144.16,142.18,130.83,123.01,121.93,117.38,116.67,46.30。
化合物2的ESI-MS图谱如图3所示，ESI-MS m/z for C14H14NO+([M-I]+):calcd:212.1,found:212.2。
(3)化合物3的合成
将化合物2(652.4mg,1.92mmol)，2-吡啶甲酸(351.7mg,2.88mmol)，1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐(351.7mg,2.88mmol)和4-二甲氨基吡啶(140.7mg,1.15mmol)溶于无水二氯甲烷(20mL)中，在氩气保护下室温反应2小时，反应完全后，有固体析出，过滤并用无水二氯甲烷洗涤，收集固体，产率为47％。
化合物3的1H NMR图谱如图4所示，1H NMR(400MHz,d6-DMSO,ppm)δ8.98(d,J＝6.4Hz,2H),8.84-8.83(m,1H),8.29-8.25(m,3H),8.14-8.09(m,2H),7.90(d,J＝8.4Hz,2H),7.78-7.75(m,1H),7.61(d,J＝16.4Hz,1H),7.46(d,J＝8.8Hz,2H),4.31(s,3H)。
化合物3的13C NMR图谱如图5所示，13C NMR(100MHz,d6-DMSO,ppm)δ163.30,152.37,152.01,150.11,146.57,145.22,139.55,137.87,133.26,129.48,128.16,125.86,123.62,122.64,46.90。
化合物3的ESI-MS图谱如图6所示，ESI-MS m/z for C20H17N2O2 +([M-I]+):calcd:317.1,found:317.2。
(二)pH值变化对化合物2和化合物3荧光强度的影响
取实施例(一)中合成的化合物2和化合物3溶于二甲基亚砜中，分别制成2mmol/L的储备液。当pH值不同时，在室温下以342nm为激发光测量化合物2和化合物3的荧光性质，结果如图7和图8所示。图7(a)为pH值对化合物2在503nm处的荧光发射强度和化合物3在448nm处的荧光发射强度的影响，(b)为pH值对化合物2和化合物3的荧光强度比率(F503nm/F448nm)的影响；图8为pH值对化合物3与Cu2+反应前后的荧光强度比率(F503nm/F448nm)的影响。实验结果表明，在pH＝4.0-7.4时，化合物2和化合物3的荧光强度及比率几乎不受影响；当pH＝7.0时，化合物3与Cu2+反应的荧光强度比率(F503nm/F448nm)变化最大而且速度最快。
(三)化合物3的吸收光谱和荧光光谱研究
在最佳测试条件下，即20mM HEPES,pH 7.0,25℃，研究化合物3的吸收光谱和荧光光谱性质，结果如图9和图10所示。图9中(a)为化合物3与Cu2+反应的吸收光谱变化，(b)为化合物3与Cu2+反应时吸光度在342nm和374nm处随时间的变化；图10中(a)为化合物3与Cu2+反应的荧光光谱变化，(b)为化合物3与Cu2+反应的荧光强度比率(F503nm/F448nm)随时间的变化。实验结果证明，化合物3与Cu2+反应会引起吡啶甲酸酯基的水解，释放荧光团4-(4-羟基苯乙烯基)-1-甲基吡啶碘盐，如图13所示。因此，化合物3适用于Cu2+的快速检测。
(四)化合物3检测Cu2+的敏感度研究
为测试化合物3检测Cu2+的敏感度，不同Cu2+浓度(0–14μM)条件下化合物3与Cu2+反应的荧光强度比率(F503nm/F448nm)随时间的变化(如图11(a))及化合物3的荧光强度比率(F503nm/F448nm)随Cu2+浓度的变化(如图11(b))都进行了研究。从图11(a)可知，Cu2+浓度越高会使荧光强度比率(F503nm/F448nm)变化更快和更大。由图11(b)可以推算出化合物3检测Cu2+的检测限为1.1nM，远低于美国环保署(EPA)规定安全饮用水中最大Cu2+浓度(20μM)。
(五)化合物3对Cu2+的选择性研究
为测试化合物3对Cu2+的选择性，对化合物3与不同重金属离子反应前后的荧光强度比率(F503nm/F448nm)的变化进行了实验研究(如图12)。由图12可知，化合物3对Cu2+检测不受其他具有潜在竞争性的金属离子的干扰，对Cu2+检测具有高度的选择性。
Claims (10)
1.一种基于半花菁的铜离子比率荧光探针，其特征在于：它的分子式为C20H17IN2O2，结构式如下：
。
2.一种权利要求1所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于包括步骤如下：
(1)4-甲基吡啶与碘甲烷反应得到1,4-二甲基吡啶碘盐，即化合物1，其结构式如下：
(2)将步骤(1)得到化合物1与4-羟基苯甲醛反应得到4-(4-羟基苯乙烯基)-1-甲基吡啶碘盐，即化合物2，其结构式如下：
(3)将步骤(2)得到化合物2与2-吡啶甲酸反应得到铜离子比率荧光探针4-(4-吡啶甲酸酯苯乙烯基)-1-甲基吡啶碘盐，即化合物3。
3.根据权利要求2所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于：所述步骤(1)中化合物1获得的具体方法为：将4-甲基吡啶和碘甲烷溶于乙腈中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用乙酸乙酯洗涤，收集固体即为化合物1。
4.根据权利要求3所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于，所述4-甲基吡啶与碘甲烷的比例为1:1.25。
5.根据权利要求2所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于，所述步骤(2)中化合物2获得的具体方法为：将化合物1，4-羟基苯甲醛和哌啶溶于无水乙醇中，在氩气保护下加热回流反应10小时，反应完全后，冷却至室温，有固体析出，过滤并用无水乙醇洗涤，收集固体即为化合物2。
6.根据权利要求5所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于，所述化合物1与4-羟基苯甲醛和哌啶的比例为1:1.5:0.5。
7.根据权利要求2所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于，所述步骤(3)中化合物3获得的具体方法为：将化合物2，2-吡啶甲酸，1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐和4-二甲氨基吡啶溶于无水二氯甲烷中，在氩气保护下室温反应2小时，反应完全后，有固体析出，过滤并用无水二氯甲烷洗涤，收集固体即为铜离子比率荧光探针，即化合物3。
8.根据权利要求7所述的基于半花菁的铜离子比率荧光探针的制备方法，其特征在于，所述化合物1与2-吡啶甲酸，1-乙基-3-(3-二甲氨基丙基)碳二亚胺盐酸盐和4-二甲氨基吡啶的比例为1:1.5:1.5:0.6。
9.一种权利要求1所述的基于半花菁的铜离子比率荧光探针的应用，其特征在于：该应用是在纯水溶液中将荧光探针与铜离子进行反应，利用两个不同发射波长处荧光强度的比率(F503nm/F448nm)变化来检测铜离子的存在与否。
10.根据权利要求9所述的基于半花菁的铜离子比率荧光探针的应用，其特征在于：在未加入铜离子前，所述反应溶液的最大荧光发射波长位于448nm处，当加入铜离子后，所述反应溶液的448nm处的荧光减弱，最大荧光发射波长红移至503nm处，所述检测铜离子的检出浓度下限为1.1nM。
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Application publication date: 20170811 Assignee: Guangxi Kanglin Chemical Reagent Co.,Ltd. Assignor: HEZHOU University Contract record no.: X2023980046440 Denomination of invention: A Copper Ion Ratio Fluorescence Probe Based on Half Cyanine and Its Preparation and Application Granted publication date: 20190510 License type: Common License Record date: 20231108 |