CN106317062B - 一种测定镉离子的比率型荧光探针的制备与应用 - Google Patents

一种测定镉离子的比率型荧光探针的制备与应用 Download PDF

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CN106317062B
CN106317062B CN201610709210.7A CN201610709210A CN106317062B CN 106317062 B CN106317062 B CN 106317062B CN 201610709210 A CN201610709210 A CN 201610709210A CN 106317062 B CN106317062 B CN 106317062B
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吕媛媛
顾伟
黄文斌
沈王兴
宣贵达
沈洁
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Abstract

本发明公开了一种比率型镉离子荧光探针及其制备方法和应用。该方法包括：将5,10,15,20‑四溴苯基卟啉、二‑2‑吡啶甲基胺(DPA)、碘化钾、碳酸钾以1:4:4:4的摩尔比溶于乙腈中，氮气保护下，加热至回流，反应6~9 h，硅胶色谱分离得到目标镉离子荧光探针（PD）。该探针制备方法简单、条件温和、后处理简便，在检测镉离子时显示比色和比率型荧光的双重变化，检测过程便捷，结果准确。

Description

一种测定镉离子的比率型荧光探针的制备与应用
技术领域
本发明涉及一种测定镉离子的比率型荧光探针的制备，具体涉及一种以二 -2-吡啶甲基胺(DPA)为识别基团、卟啉分子为荧光发色团的荧光探针的制备方法，以及该探针分子应用于溶液中镉离子的比色及比率型荧光检测。
背景技术
随着现代化工业的快速发展，重金属离子污染问题日趋严重。其中，镉是一种毒性非常强的重金属，由于镉离子(Cd2+)具有生物富集作用、半衰期长(二三十年)、不宜分解等特点，一旦通过生物链进入人体并在体内富集，可引起人肺功能紊乱、肾功能不全、钙代谢紊乱、骨骼损伤以及大大增加患癌的几率。近年来，我国发生多起镉污染事件，其中最典型的是2013年发生的湖南大米镉含量超标事件，引发了人们对镉离子污染的强烈关注。我国政府已将镉污染防治列为“十三五规划”重大专项。人们迫切需要快速、准确、低成本并能选择性地分析检测镉离子的方法。因此，现场环境检测方法、移动实验室和便携式检测仪器等概念近年来被许多研究人员提出。其中，通过比色法或以荧光为输出信号的化学传感方法尤为引入注目。
目前，基于小分子荧光探针法检测镉离子已有大量报道，但一般设计的荧光探针通常表现为荧光发光-淬灭(on-off)或荧光淬灭-恢复发光(off-on)，即在同一发射峰位荧光强度发生改变。这种响应模式存在着检测背景高，信号干扰严重等问题。卟啉(Porphyrin)是一类由四个吡咯环通过次甲基相连构成的共轭大环化合物，具有高的荧光量子产率、大的Stokes位移、相对长的激发和发射波长，且光稳定性好、对微环境敏感，是一类性能优异的近红外荧光发色团信号分子，广泛应用于光化学分子探针的构建。卟啉化合物的易修饰性可使其大环***联接不同的取代基与活性官能团，通过分子设计和化学反应可将其与不同的识别单元结合，合成一系列光物理和光化学性质可调的功能探针，应用于各种检测领域中(Coordination Chemistry Reviews 1999,190-192:683-706；Talanta2000,51:209-224；Sensors and Actuators B:Chemical 2013,179:21-31.)。卟啉化合物优异的光学性能，可实现极低浓度离子的比色/荧光快速检测，且多数表现为比率型的荧光响应行为：即以两个发射峰强度的比值作为检测信号，该模式可以有效地降低环境变化对于荧光信号的影响，使得检测过程具有更强的特异性(Sensors 2013,13:3131-3141；Sensors 2013,13:15758-15769)。
因此，可通过巧妙的分子结构设计，将卟啉分子与一些能选择性识别镉离子的分子单元相结合，利用该单元与镉离子络合后改变整个分子结构，从而改变所连卟啉发色团分子的光物理性能来实现对镉离子的灵敏检测。
发明内容
本发明针对现有荧光探针所存在的制备复杂、响应性差及背景干扰严重等问题，提供了一种以二-2-吡啶甲基胺(DPA)为识别基团、卟啉分子为荧光发色团的比率型镉离子荧光探针及其制备方法。
本发明提供的比率型镉离子荧光探针(PD)，具有如下结构通式：
一种比率型镉离子荧光探针(PD)的制备方法，包括如下步骤：
将5,10,15,20-四溴苯基卟啉、二-2-吡啶甲基胺(DPA)、碘化钾、碳酸钾以 1:4:4:4的摩尔比溶于有机溶剂中，氮气保护下，加热至回流，反应6～9h，硅胶色谱分离得到目标镉离子荧光探针(PD)。
所述的比率型镉离子荧光探针(PD)的制备方法，具体包括如下步骤：
(1)将市售四(4-氨基苯基)卟啉(TATPP)溶于浓盐酸中，形成0.03mmol/mL 的溶液，冰浴下逐滴滴入亚硝酸钠水溶液，反应10min；然后逐滴加入碘化钾水溶液，继续反应20min后，升温至室温，反应2.5h。产物用氨水中和至pH 为8，采用二氯甲烷萃取，有机层用水洗至中性，减压蒸去二氯甲烷。粗产品用硅胶色谱柱分离，二氯甲烷为展开剂，收集第一色带产物，得到5,10,15,20- 四溴苯基卟啉(TBrTPP)。
TATPP的结构式为：
TBrTPP的结构式为：
(2)将5,10,15,20-四溴苯基卟啉(TBrTPP)、二-2-吡啶甲基胺(DPA)、碘化钾、碳酸钾以1:4:4:4的摩尔比溶于有机溶剂中，有机溶剂的体积与5,10,15,20- 四溴苯基卟啉的量成正比，保持5,10,15,20-四溴苯基卟啉在溶液中的浓度为0.01 mmol/mL。加热回流,反应6～9h后，采用薄层色谱法(TLC)验证无5,10,15,20- 四氨基苯基卟啉原料剩余，硅胶色谱分离粗产品，收集第一色带产物。
所述步骤(1)中，TATPP的浓盐酸溶液浓度为0.03mmol/mL，亚硝酸钠水溶液的浓度为0.2mmol/mL，溴化钾水溶液的浓度为0.2mmol/mL，这些比例的选取可保证所有原料在溶剂中可充分溶解，利于反应高效进行。
所述步骤(1)中，TATPP的浓盐酸溶液：亚硝酸钠水溶液：溴化钾水溶液的体积比优选33:5:5，实验表明，该比例可保证氨基重氮化反应较为充分，避免自偶合反应及其他副反应的生成，促使TATPP较高效率转化为TBrTPP。
所述步骤(2)中的有机溶剂是乙腈。
所述步骤(2)中的加热回流的加热温度为乙腈的沸点(76℃左右)。
所述步骤(2)中薄层色谱展开剂是二氯甲烷：甲醇＝9:1(体积比)。
所述步骤(2)中硅胶色谱分离展开剂是二氯甲烷：甲醇＝9:1(体积比)。
所述步骤(2)中5,10,15,20-四溴苯基卟啉、二-2-吡啶甲基胺(DPA)、碘化钾、碳酸钾的摩尔比优选为1:4:4:4，实验表明，该比例可最高效率促进 5,10,15,20-四溴苯基卟啉转化为最终产物PD，避免副产物的生成。
所述步骤(2)中有机溶剂的体积与5,10,15,20-四溴苯基卟啉的量成正比，保持5,10,15,20-四溴苯基卟啉在溶液中的浓度为0.01mmol/mL，这个比例可使得反应原料在溶剂用量最少的情况下能最充分溶解，更利于反应充分进行。
所述步骤(2)中反应时间为6～9h，反应结束的标志是采用步骤(2)中所述薄层色谱法(TLC)验证无5,10,15,20-四氨基苯基卟啉原料剩余。
所述的比率型镉离子荧光探针(PD)可与镉离子发生特有的配位反应(如下 所示)。
所述的比率型镉离子荧光探针(PD)与镉离子配位后可引起卟啉信号基团的颜色变化及荧光发射出现比率型响应。
本发明具有如下优点：
(1)本发明的镉离子荧光探针(PD)的合成方法，条件温和、步骤简单，后处理简便；
(2)本发明使用卟啉分子作为信号报告基团，该分子为近红外荧光发色团分子，光学性能优异、对微环境敏感、可获得较大的Stocks位移，增强了反应信号的灵敏度；
(3)本发明的镉离子荧光探针(PD)能够对镉离子显示出比色/荧光的双重敏感性质，通过肉眼或荧光光谱仪即可实现微量镉离子的快速检测，灵敏度高；
(4)本发明的镉离子荧光探针(PD)对镉离子的荧光响应为比率型，可以有效地降低环境变化对于荧光信号的影响，使得检测过程具有更强的特异性与准确性。
附图说明
图1为本发明所述的镉离子荧光探针(PD)的1H NMR谱图；
图2为本发明所述的镉离子荧光探针(PD)的荧光光谱图；
图3为本发明所述的镉离子荧光探针(PD)加入镉离子前后的颜色变化图；
图4为本发明所述的镉离子荧光探针(PD)的镉离子滴定荧光光谱图。
具体实施方式
实施例1
将市售四(4-氨基苯基)卟啉(TATPP)(675mg，0.10mmol)溶于33mL 浓盐酸中，冰浴下逐滴滴入5mL的亚硝酸钠水溶液(NaNO2的浓度为0.2 mmol/mL)，反应10min；然后逐滴加入5mL溴化钾水溶液(KBr的浓度为0.2 mmol/mL)，继续反应20min后，升温至室温，反应2.5h。产物用氨水中和至 pH为8，采用二氯甲烷萃取，有机层用水洗至中性，减压蒸去二氯甲烷，真空干燥箱内干燥2h。粗产品用硅胶色谱柱分离，二氯甲烷为展开剂，收集第一色带产物，得到5,10,15,20-四溴苯基卟啉(TBrTPP)。
将5,10,15,20-四溴苯基卟啉(TBrTPP)(93mg,0.1mmol)、二-2-吡啶甲基胺(DPA)(70.5μL，0.4mmol)、碘化钾(66.7mg,0.4mmol)、碳酸钾(55.2mg， 0.4mmol)溶于10mL乙腈中，加热回流反应8h后，采用薄层色谱法(TLC) (展开剂比例二氯甲烷：甲醇＝9:1(v/v))，验证无5,10,15,20-四氨基苯基卟啉原料剩余后，旋转蒸发溶剂，硅胶色谱分离粗产品(展开剂比例二氯甲烷：甲醇＝9:1(v/v))，收集第一色带产物。采用核磁共振氢谱(1H NMR)(图1)以及荧光光谱(图2)验证其化学结构。1H NMR的溶剂采用氘代DMSO(DMSO-d6)，1H NMR(DMSO-d6,500Hz):δ-2.79(s,2H),5.59(s,16H),6.51(d,8H),7.06(m, 8H),7.88(m,16H),8.05(m,6H),8.19(m,6H),8.81(m,10H),8.93(m,2H)。荧光光谱仪的参数如下：激发波波长为420nm；接收波波段为600nm～725nm。
应用例1
荧光探针(PD)对溶液中镉离子的比色检测：由于镉离子可与PD配位，引起卟啉信号基团发生颜色改变，因此可将一定浓度的PD分子溶液中加入等浓度的镉离子溶液，肉眼观察PD溶液的颜色变化。具体过程如下：将PD溶解在DMSO中，配成浓度为10μM的溶液，将氯化镉溶于蒸馏水，配成10μM 的溶液。在5mL菌种瓶中加入上述PD溶液0.4mL(10μM)，再加入10μM的氯化镉水溶液0.4mL，采用DMSO稀释定容至4.0mL，静置5分钟后，肉眼观察溶液颜色变化，结果如图3所示。从图3可以看出，Cd2+可引起PD溶液的颜色由粉红转变为绿色，说明PD探针对镉离子可实现肉眼的比色检测。
应用例2
荧光探针(PD)对溶液中不同浓度镉离子的荧光滴定：将PD溶解在DMSO 中，配成浓度为10μM的溶液；将氯化镉溶于蒸馏水，配成不同浓度的水溶液。在10mL容量瓶中加入PD溶液1.0mL(10μM)后，再分别加入不同浓度的镉离子水溶液1.0mL，采用DMSO稀释定容至10.0mL，静置5分钟后，采用荧光光谱测定加入不同浓度镉离子的荧光变化谱图。结果如图4所示。
荧光光谱仪的参数如下：激发波波长为420nm；接收波波段为620nm～720 nm。

Claims (5)

1.一种测定镉离子的比率型荧光探针，其特征在于，所述的探针分子的结构式如下：
2.一种如权利要求1所述的测定镉离子的比率型荧光探针的制备方法，包括如下步骤：
将5,10,15,20-四溴苯基卟啉、二-2-吡啶甲基胺(DPA)、碘化钾、碳酸钾以1:4:4:4的摩尔比溶于有机溶剂中，氮气保护下，加热至回流，反应6～9h，硅胶色谱分离得到目标测定镉离子的比率型荧光探针(PD)。
3.根据权利要求2所述的制备方法，其特征在于，所述的有机溶剂是乙腈。
4.根据权利要求2所述的制备方法，其特征在于，5,10,15,20-四溴苯基卟啉在溶液中的浓度为0.01mmol/mL。
5.根据权利要求2所述的制备方法，其特征在于，反应的加热温度为乙腈的沸点。
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