CN105647512B - 一种Cu2+荧光探针、制备方法及其应用 - Google Patents
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Abstract
本发明公开了一种Cu2+荧光探针、制备方法及其应用。本发明以2,4‑二甲基吡咯、对甲氧基苯甲醛和水杨酰肼为原料，经过四个合成步骤得到荧光探针。所述的荧光探针在N,N‑二甲基甲酰胺与水的混合溶液中，能够很好的识别Cu2+，并且不受其它金属离子和常见阴离子的干扰，具有很高的灵敏度，荧光探针溶液无论是在可见光还是365nm紫外灯下颜色都发生了明显的变化。
Description
技术领域
本发明属于荧光探针检测技术领域，特别是一种Cu2+荧光探针、制备方法及其应用。
背景技术
随着人们生活质量的日益提高，人们对于环境污染问题以及生命体中各种微量元素的探究也变得迫在眉睫，与这方面相关的报道也在不断地增多。Cu2+也是一种广泛存在于环境中的一种重金属离子，也在人体中起着维持机体正常工作的微量元素，人体细胞内的造血就需要这种微量元素，一些酶的反应还有一些生命体内的氧化还原过程也是需要铜离子的参与。如果生命体内的Cu2+代谢遭到破坏，就可能导致一些疾病，比如说威尔逊氏症、阿兹海默症、家族性肌萎缩侧索硬化症、帕金森综合症和门克斯氏综合症等。
人们致力于寻找一种快速而灵敏的检测方法，其中包括传统的原子吸收光谱法，原子发射光谱法，电化学法等。其中紫外可见分光光度分析法的特点是分析速度快，仪器简单，操作方便。水环境中Cu2+的检测方法也有很多，例如原子吸收法，比色法，荧光淬灭法，极谱仪法，电化学发光分析法以及电修饰法等。近年来人们也研究了各种荧光分子探针对Cu2+进行检测，其中罗丹明B的衍生物具有摩尔消光系数大，吸收波长长，水溶性好等优点，也被用于检测中。由于如下结构的化合物也具有荧光量子产率高，摩尔消光系数大，光稳定性强等特点，其光物理性能如此优越，非常适合应用于各种生物荧光探针的分析领域当中，所以近年来围绕着该类的荧光探针分子结构的创新以及开发一直都是众多有机化学工作者的兴趣热点。
发明内容
本发明的目的在于提供一种高选择性的、高灵敏性的、荧光增强型的，能够实现在水溶液中对Cu2+检测的荧光探针。
实现本发明目的的技术解决方案为：一种Cu2+荧光探针，所述荧光探针具有如下结构：
上述Cu2+荧光探针的制备方法，包括如下步骤：
步骤一：将对甲氧基苯甲醛和2,4-二甲基吡咯置于容器中，再倒入溶剂二氯甲烷，滴加催化剂三氟乙酸，在室温下搅拌过夜，再加入四氯苯醌，继续搅拌5 个小时以上，滴加三乙胺和三氟化硼乙醚后继续反应得到化合物；
步骤二：将1,2-二氯乙烷于置于容器中，之后加入N,N-二甲基甲酰胺，搅拌均匀后，滴入草酰氯，搅拌30min以上，之后在室温下继续反应2h以上得到化合物；
步骤三：在0℃以下的反应浴中，于步骤一制得的化合物中滴加步骤二制得的化合物，最后在常温下搅拌过夜反应得到化合物；
步骤四：将步骤三制得的化合物置于容器中，在乙醇溶液中回流使其溶解，慢慢滴入水杨酰肼的乙醇溶液，1小时内滴加完毕，最后制备得目标化合物。
步骤一中，2,4-二甲基吡咯与对甲氧基苯甲醛与三氟化硼乙醚的摩尔比为24:11:11，四氯苯醌与三氟化硼乙醚的摩尔比为1.5:1，三乙胺与三氟化硼乙醚的摩尔比为1:1，三氟乙酸与三氟化硼乙醚的摩尔比为100:1。
步骤二中，N,N-二甲基甲酰胺与草酰氯的摩尔比为1:1。
步骤三中，步骤二制得的化合物与步骤一制得的化合物的摩尔比为30:1～20:1。
步骤四中，步骤三制得的化合物与水杨酰肼的摩尔比为1:2～1:3，回流反应时间为4小时以上。
一种Cu2+荧光探针的应用，所述应用是将上述荧光探针用于检测溶液中Cu2+。
本发明与现有技术相比，其优点有：
1、制得的荧光探针溶液无论是在可见光还是紫外灯(365nm)下颜色都发生了明显的变化。
2、制得的荧光探针能够很好的识别Cu2+，并且不受其它金属离子(K+，Na+，Li+， Mg2 +，Ca2+，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+，Hg2+， Bi2+，Pb2+，Ni2+，Sn2+)和常见阴离子(Cl-，SO4 2-，NO3 -，OAc-，Br-)的干扰，具有很高的灵敏度和抗干扰性。
3、制得的荧光探针对Cu2+和其它离子的检测结果的不同，都可以通过紫外光谱和荧光光谱检测出来。
4、温度和pH(4～10)对于制得的荧光探针检测Cu2+没有影响，适用于生理环境下的检测。
附图说明
图1为本发明的目标化合物荧光探针溶液在未加和分别加入不同阳离子(Cu2+，K+，Na+，Li+，Mg2+，Ca2+，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+， Hg2+，Bi2+，Pb2+，Ni2+，Sn2+)的紫外吸收光谱图。
图2为本发明的目标化合物荧光探针溶液在未加和分别加入不同阳离子(Cu2+，K+，Na+，Li+，Mg2+，Ca2+，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+， Hg2+，Bi2+，Pb2+，Ni2+，Sn2+)的荧光发射光谱图。
图3为本发明的目标化合物荧光探针溶液未加和分别加入铜盐(CuCl2，CuSO4，CuNO3， Cu(OAc)2，CuBr2)之后的荧光探针荧光强度条状图，其中，黑条代表未加入铜盐荧光探针的荧光强度，白条代表加入铜盐荧光探针的荧光强度。
图4为本发明的目标化合物荧光探针溶液加入其它金属离子(K+，Na+，Li+，Mg2+，Ca2+，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+，Hg2+，Bi2+，Pb2+， Ni2+，Sn2+)和再加入Cu2+之后的荧光探针荧光强度条状图，其中，黑条代表加入荧光探针与其它金属离子荧光强度，白条代表荧光探针与其它金属离子再加入Cu2+荧光强度。
具体实施方式
(一)目标产物荧光探针合成路线如下所示
(二)可见光和紫外灯(365nm)颜色对比测试
合成的荧光探针溶解在N,N-二甲基甲酰胺与水(7:3)的混合溶液中，配置成10μM的稀溶液，放置于22个白色菌种瓶中，留一个空白，之后依次加入不同金属离子(K+， Na+，Li+，Mg2+，Ca2+，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+， Hg2+，Bi2+，Pb2+，Ni2+，Sn2+，Cu2+)在可见光和紫外灯(365nm)下进行颜色对比。
(三)紫外光谱测试
在合成的荧光探针溶解在N,N-二甲基甲酰胺与水(7:3)的混合溶液中，配置成10μM的稀溶液，并对该溶液进行紫外光谱测试，之后再加入金属阳离子(K+，Na+， Li+，Mg2+，Ca2 +，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+，Hg2+， Bi2+，Pb2+，Ni2+，Sn2+，Cu2+)进行紫外光谱测试。
(四)荧光光谱测试
在合成的荧光探针溶解在N,N-二甲基甲酰胺与水(7:3)的混合溶液中，配置成 10μM的稀溶液，并对该溶液进行荧光光谱测试，之后再加入金属阳离子(K+，Na+， Li+，Mg2+，Ca2 +，Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+，Hg2+， Bi2+，Pb2+，Ni2+，Sn2+)和铜盐(CuCl2，CuSO4，CuNO3，Cu(OAc)2，CuBr2)进行荧光光谱测试。
实施例1荧光探针的合成
1、化合物[1]的合成
在氩气的保护之下，将称取的1.5g(0.011mol)对甲氧基苯甲醛和2,4-二甲基吡咯2.3g(0.024mol)加入500mL的三口烧瓶中，再倒入250mL干燥二氯甲烷，滴入0.01mL三氟乙酸，溶液呈酒红色，在室温下搅拌过夜，TLC跟踪反应，当对甲氧基苯甲醛几乎完全消失时，加入4.04g四氯苯醌，继续搅拌约5个小时，滴加1.11 mL三乙胺和1.25mL三氟化硼乙醚后继续反应，TLC跟踪，当对甲氧基苯甲醛几乎完全反应时，停止反应，先水洗三次，再用二氯甲烷萃取水层，合并有机层，无水硫酸镁干燥，过滤，减压旋蒸去除二氯甲烷后得粗产物，粗产品用石油醚﹕乙酸乙酯＝50﹕1作为洗脱剂进行柱层析，得红色化合物[1]1.50g。
化合物[1]，红色固体，产率为38.43％。
1H-NMR(CDCl3,500MHz)δ(TMS,ppm)：7.17(d,J＝8.4Hz,2H,Ar-H),7.01(d,J＝8.4Hz，2H， Ar-H),5.97(s,2H,pyrrol-H),3.87(s,3H,OCH3),2.55(s,6H,CH3),1.43(s,6H,CH3).
2、化合物[2]的合成
在冰水浴下，量取90mL1,2-二氯乙烷于250mL的三口烧瓶中，在氩气的保护下加入3mL N,N-二甲基甲酰胺(DMF)，搅拌均匀后，用滴管缓慢注入5mL草酰氯，有大量白色固体出现，停止注入后继续搅拌30min，撤去冰水浴，在室温下反应约 2h，即制得氯代亚胺盐。在-15℃的低温反应浴中，称取637mg(1.8mmol)化合物 [1]于500mL的三口烧瓶中，缓慢加入上述制得的氯代亚胺盐，滴加完毕后，继续搅拌30min，将反应液于30℃下搅拌过夜。停止反应后，将反应液缓慢倒入饱和碳酸氢钠水溶液中，搅拌约2h后，用二氯甲烷多次萃取，合并有机层，无水硫酸镁干燥，过滤，减压旋蒸去除二氯甲烷后得粗产物，粗产品用石油醚﹕乙酸乙酯＝30﹕1作为洗脱剂进行柱层析，得深红色化合物[2]463mg。
化合物[2]，深红色固体，产率为67.83％。
1H-NMR(CDCl3,500MHz)δ(TMS,ppm)：10.02(s,1H,CHO),7.17-7.19(m,2H,ArH),7.05(d,J＝8.7Hz,2H,ArH),6.16(s,1H,pyrrol-H),3.90(s,3H,OCH3),2.83(s,3H,CH3),2.62(s,3H,CH3),1.72(s,3H,CH3),1.49(s,3H,CH3)；
13C-NMR(d6-DMSO,125MHz)δ(TMS,ppm):185.89,161.40,160.57,156.34,147.33,143.78,142.87,134.50,130.20,129.03,126.27,126.09,123.89,114.89,55.37,15.05,12.97,11.75.
EI-MS:m/z＝383.13[M+H+].
3、目标化合物荧光探针的合成
称取382mg(1.00mmol)化合物[2]于100mL的三口烧瓶中，再加入20ml乙醇，回流下使其溶解。称取304mg(2.00mmol)水杨酰肼溶于20mL乙醇，用恒压滴液漏斗缓慢滴加至三口烧瓶中，约1小时滴加完毕，TLC跟踪反应，当化合物[2]不再继续消失时，停止反应，趁热过滤，固体用二氯甲烷溶解，无水硫酸镁干燥，过滤，旋蒸去除溶剂，得粗产品，用石油醚﹕乙酸乙酯＝10﹕1作为洗脱剂进行柱层析，得红色目标化合物104mg。
目标化合物，红色固体，产率﹕20.16％。
1H-NMR(500MHz,d6-DMSO)δ(TMS，ppm):12.00(s,1H,NH-N),11.65(s,1H,OH),8.44(s, 1H,CH＝N),7.84(d,J＝10.0Hz,1H,Ar-H),7.43-7.40(m,1H,Ar-H),7.31(d,J＝5.0Hz,2H, Ar-H),7.13(d,J＝10.0Hz,2H,Ar-H),6.92(t,J＝10.0Hz,2H,Ar-H),6.28(s,1H,Pyrrol-H), 3.83(s,3H,OCH3),2.73(s,3H,CH3),2.48(s,3H,CH3),CH3),1.56(s,3H,CH3),1.41(s, 3H,CH3).
13C-NMR(125MHz,d6-DMSO)δ(TMS，ppm)：165.09,160.53,160.03,158.09,154.10,145.29,144.06,143.25,140.18,134.27,132.83,130.74,129.72,128.49,126.17,123.75,123.15,119.25,117.83,115.80,115.27,55.75,14.90,14.33,12.41.
ESI-MS:m/z＝517.2339[M+H+].
实施例2可见光和紫外灯(365nm)颜色对比测试
配置好荧光探针溶液(1.0×10-5mol/L)，吸取3mL置于5mL透明菌种瓶，留一个空白，再吸取12μL金属离子溶液(1.0×10-2mol/L)(K+，Na+，Li+，Mg2+，Ca2+， Fe2+，Al3+，Zn2+，Ag+，Ba2+，Fe3+，Cd2+，Co2+，Mn2+，Cr3+，Hg2+，Bi2+，Pb2+，Ni2+， Sn2+,Cu2+)加入瓶中，用移液枪搅拌一分钟，静置一小时。对比可见光和紫外灯 (365nm)下的变化，观察在N,N-二甲基甲酰胺与水(DMF﹕H2O)＝7﹕3体系中，荧光探针(10μM)溶液在不加和加入4倍当量的不同金属离子3小时后肉眼和紫外灯下的颜色变化。结果表明，加入Cu2+的荧光探针(10μM)溶液在3小时以后具有较大的颜色变化，肉眼观察由粉红色变成了橙黄色，在365nm紫外灯下，则发出强烈的绿色荧光，说明荧光探针对于Cu2+有很好的单一选择性。
实施例3紫外光谱测试
配置好荧光探针溶液(1.0×10-5mol/L)，吸取3mL置于比色皿中，预先设置吸收波长范围(300nm～700nm)。先做空白试验，扣除空白再进行紫外吸收光谱操作，得到我们的最大吸收波长。
如图1所示是在N,N-二甲基甲酰胺与水(DMF﹕H2O)＝7﹕3体系中，在荧光探针 (10μM)溶液中加入了12μL金属离子溶液(1.0×10-2mol/L)(Li+，Na+，K+，Mg2+， Ca2+，Ba2+，Al3+，Pb2 +，Cr3+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Ag+，Zn2+，Cd2+，Hg2+， Sn2+，Fe3+，Bi3+)10分钟后的紫外吸收光谱图。由该图可知，只有Cu2+的加入引起了荧光探针吸收光谱的明显变化，荧光探针(10μM)溶液对其它常见金属离子均无识别作用。因此，荧光探针对于Cu2+的识别具有较高的选择性。
实施例4荧光光谱测试
配置好荧光探针溶液(1.0×10-5mol/L)，吸取3mL置于比色皿中，预先设置激发波长得到一个发射光谱，再通过得到的发射波长反扫得到一个激发光谱，通过我们得到的激发光谱，选取需要的激发波长进行荧光发射波长的测定。
如图2所示是在N,N-二甲基甲酰胺与水(DMF﹕H2O)＝7﹕3体系中，在荧光探针 (10μM)溶液中加入12μL金属离子溶液(1.0×10-2mol/L)(Li+，Na+，K+，Mg2+， Ca2+，Ba2+，Al3+，Pb2+，Cr3+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Ag+，Zn2+，Cd2+，Hg2+， Sn2+，Fe3+，Bi3+)10分钟后的荧光光谱图。由该图可知，只有Cu2+的加入引起了荧光探针发射光谱的明显变化，荧光探针(10μM)溶液对其它常见金属离子均无识别作用。因此，荧光探针对于Cu2+的识别具有较高的选择性，
如图3与4所示常见阴离子(NO3 -，Cl-，SO4 2-，Br-，OAc-)与常见金属离子(Li+， Na+，K+，Mg2+，Ca2+，Ba2+，Al3+，Pb2+，Cr3+，Mn2+，Fe2+，Co2+，Ni2+，Cu2+，Ag+， Zn2+，Cd2+，Hg2+，Sn2+，Fe3+，Bi3+)以1：1或者2：1的比例与Cu2+共存的情况下进行荧光测试，发现其它金属阳离子并没有对Cu2+的响应产生干扰，因此，荧光探针对于Cu2+的识别具有很高的单一选择性，且不受常见阴离子与阳离子干扰。
Claims (7)
1.一种Cu2+荧光探针，其特征在于，所述荧光探针具有如下结构：
2.如权利要求1所述的Cu2+荧光探针的制备方法，其特征在于，包括如下步骤：
步骤一：将对甲氧基苯甲醛和2,4-二甲基吡咯置于容器中，加入溶剂二氯甲烷后，滴加催化剂三氟乙酸，在室温下搅拌过夜，再加入四氯苯醌，继续搅拌5小时以上，滴加三乙胺和三氟化硼乙醚后继续反应得到化合物；
步骤二：将1,2-二氯乙烷于置于容器中，之后加入N,N-二甲基甲酰胺，搅拌均匀后，滴入草酰氯，搅拌30min以上，之后在室温下继续反应2h以上得到化合物；
步骤三：在0℃以下的反应浴中，于步骤一制得的化合物中滴加步骤二制得的化合物，最后在常温下搅拌过夜反应得到化合物；
步骤四：将步骤三制得的化合物置于容器中，在乙醇溶液中回流使其溶解，慢慢滴入水杨酰肼的乙醇溶液，1小时内滴加完毕，最后制备得目标化合物。
3.如权利要求2所述的制备方法，其特征在于，步骤一中，2,4-二甲基吡咯与对甲氧基苯甲醛与三氟化硼乙醚的摩尔比为24:11:11，四氯苯醌与三氟化硼乙醚的摩尔比为1.5:1，三乙胺与三氟化硼乙醚的摩尔比为1:1，三氟乙酸与三氟化硼乙醚的摩尔比为100:1。
4.如权利要求2所述的制备方法，其特征在于，步骤二中，N,N-二甲基甲酰胺与草酰氯的摩尔比为1:1。
5.如权利要求2所述的制备方法，其特征在于，步骤三中，步骤二制得的化合物与步骤一制得的化合物的摩尔比为30:1～20:1。
6.如权利要求2所述的制备方法，其特征在于，步骤四中，步骤三制得的化合物与水杨酰肼的摩尔比为1:2～1:3，回流反应时间为4小时以上。
7.一种如权利要求1-6任一所述的Cu2+荧光探针在检测溶液中Cu2+中的应用。
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