CN113135949B - 一种四苯乙烯硼酸酯衍生物的次氯酸盐荧光探针 - Google Patents
一种四苯乙烯硼酸酯衍生物的次氯酸盐荧光探针 Download PDFInfo
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Abstract
本发明公开了一种新型检测次氯酸盐荧光探针的制备方法及应用。该探针分子式为C44H40BNO2，具有如下所示结构：
。该探针在良溶剂中荧光微弱而在不良溶剂水中具有强绿色荧光，表现出明显的聚集诱导发光现象。荧光探针在PBS缓冲溶液中呈现明亮的绿色荧光，但当与次氯酸盐作用后，荧光猝灭。荧光探针在PBS缓冲溶液中与次氯酸盐作用后，几秒钟内反应剧烈，1分钟内达到稳定。本发明荧光探针对次氯酸盐的检测具有优异的选择性，超高的灵敏性，以及较快的反应时间，现象明显，并且具有在纯水环境中依然无损探针识别次氯酸盐的效果。
Description
技术领域
本发明涉及一种检测次氯酸盐的荧光探针，具体涉及一种四苯乙烯衍生物的次氯酸盐荧光探针制备方法以及在水体系中对次氯酸盐识别的应用。
背景技术
四苯乙烯衍生物作为一类重要的聚集诱导发光（AIE）活性体，具有类似扭曲的螺旋桨状结构。近年来，四苯乙烯衍生物因优异的聚集诱导发光性质、大斯托克斯位移、优异的光稳定性和低毒性等光物理性质得到了越来越多的研究。
次氯酸（HClO）是活性氧物质（ROS）中最重要的氧化剂之一，它在免疫系统中占据重要位置，例如对病原微生物和病毒的抵抗力等等。当生物体内的次氯酸盐浓度不稳定时，会引起一系列疾病，如帕金森氏病，阿尔茨海默氏病，脑缺血和癌症。因此，对次氯酸盐的检测已成为人类关注的焦点。其中荧光探针以其高选择性，良好的灵敏性以及操作简单，可实时分析等优点，受到了人们的广泛青睐。目前关于不同骨架次氯酸盐检测的荧光探针报道虽多，但是这些探针各有优缺点。然而，基于聚集诱导发光（AIE）的荧光探针不仅继承了传统有机分子荧光探针的优点，同时克服了其最大的缺点（聚集诱发的猝灭，ACQ），在高浓度或聚集时也能提供良好的荧光。
发明内容
针对目前次氯酸盐荧光探针的发展现状及存在的不足，本发明提供了一种四苯乙烯衍生物的次氯酸盐荧光探针。探针分子式为C44H40BNO2，简称TPE-Bpin，如式（I）所示的结构：
上述荧光探针的制备方法采用以下步骤：（1）4-（二苯胺基）苯硼酸、苯甲酰溴溶于甲苯和无水乙醇（v:v=8:1）中。N2保护下，加入四（三苯磷）钯和碳酸钾回流20 h，用二氯甲烷萃取，得固体为TPE-Ac，其结构式如下：
（2）将4-溴二苯甲酮与TPE-Ac、锌粉溶于四氢呋喃中，0℃氩气保护下滴加四氯化钛在75℃下回流过夜。然后将反应用10%碳酸钾水溶液淬灭，并用二氯甲烷萃取。有机层用去离子水洗涤，过滤，将该溶液真空浓缩并通过柱色谱法纯化，得到呈固体产物TPE-Br，其结构式如下：
（3）将TPE-Br与双（频哪醇）二硼、乙酸钾溶于无水N,N-二甲基甲酰胺（DMF），Pd(dppf)Cl2作为催化剂，氮气保护下，85℃的条件下反应24 h，萃取干燥后利用硅胶色谱柱状分离法对其进行提纯处理，得到式（I）所示化合物
其中所述步骤（1）中，甲苯和无水乙醇的体积比为8:1，优选二氯甲烷对其有机相进行萃取除去水样。
其中所述步骤（2）中，TPE-Ac与4-溴二苯甲酮的摩尔比为1: 1.25，优选10%碳酸钾水溶液对反应进行猝灭。
其中所述步骤（3）中，TPE-Br与双（频哪醇）二硼的摩尔比为1:2.5，催化剂优选Pd(dppf)Cl2，摩尔用量为反应原料的2%-5%。
上述的荧光探针主要用于检测纯水环境中的次氯酸盐。
其中所述的检测方法为荧光猝灭。
本发明的有益效果如下：
1、本发明是基于四苯乙烯硼酸酯衍生物的新型次氯酸盐荧光探针，能够通过荧光的变化实现对水体系中次氯酸盐的检测；探针溶液本身为亮绿色荧光，加入次氯酸盐后，变为无色，现象明显，易于观察；同时，相对于其他的阴离子，该探针对次氯酸盐具有较好的选择性。
2、本发明的操作步骤简单，对环境要求较低，产品易于提纯，产率高。
附图说明
图1为本发明荧光探针在不同溶剂中荧光光谱曲线变化，荧光探针浓度均为10 μM；
图2为本发明探针随水含量变化而变化的荧光光谱图，探针浓度为10 μM；
图3为本发明探针随次氯酸盐浓度变化而变化的荧光光谱图，探针浓度为10 μM；
图4为本发明探针加入不同阴离子之后510 nm处荧光强度变化的对比图；
图5为本发明探针加入饱和当量识别离子后随时间变化的荧光强度变化的对比图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明，但不局限于此。在以下具体实例中所用的原料，如无特意说明，均为常规市购产品。
实施例1
制备新型四苯乙烯衍生物的次氯酸盐荧光探针
(1) 将4-（二苯胺基）苯硼酸（2.89 g，10 mmol）﹑苯甲酰溴（1.85 g，10 mmol）加入到16 mL甲苯和2 mL无水乙醇中。在N2保护条件下，加入四（三苯磷）钯（218 mg，0.18mmol）和碳酸钾（2M，50 mL）回流20 h（120℃），将溶液冷却至室温。二氯甲烷萃取3遍，得到的有机层用水洗涤3次，无水硫酸镁除去多余水分，过滤，除去溶剂，利用硅胶色谱柱分离法对其进行提纯得到的固体即为TPE-Ac。
合成路线如下图所示:
(2)取4-溴二苯甲酮（3.26 g，12.5 mmol）、TPE-Ac（3.49 g，10 mmol）、锌粉（3.92g，60 mmol），倒入60 mL 四氢呋喃中。在0℃氩气保护下滴加四氯化钛（3.32 mL，30 mmol）。将混合物温热至25℃，在75℃下回流过夜。然后将反应用10%碳酸钾水溶液淬灭，并用二氯甲烷萃取。有机层用去离子水洗涤，并用无水硫酸镁干燥。过滤，将该溶液真空浓缩并通过柱色谱法纯化，得到呈固体产物TPE-Br。
合成路线如下图所示：
(3)将TPE-Br（1.15 g，2 mmol）、双（频哪醇）二硼（1.27 g，5 mmol）、乙酸钾（KOAc，1.37 g，14 mmol）以及Pd(dppf)Cl2（0.08 g，0.1 mmol）加入30 mL的无水DMF中。在氮气保护下保持85℃反应24 h，将溶液冷却至室温。用二氯甲烷萃取3遍，得到的有机层用水洗涤3次，用无水硫酸镁除去多余水分，过滤，除去溶剂，用硅胶色谱法对其进行纯化处理，得到橙色固体即为最终产物TPE-Bpin。1H NMR (400 MHz, CDCl3) δ (ppm): 1.30-1.35 (m,12H), 6.77 (d, J = 8.4 Hz, 2H), 6.85 (dd, J = 8.8, 2.4 Hz, 2H), 6.99-7.09 (m,18H), 7.20-7.23 (m, 4H), 7.52 (d, J = 6.4 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H).
合成路线如下图所示：
实施例2
新型次氯酸盐荧光探针溶质化显色现象探究
在正己烷，甲苯，四氢呋喃，丙酮，乙腈，二甲基亚砜，甲醇，水中加入初始浓度为1mM荧光探针，使得溶液中荧光探针浓度为10 μM。对其做在不同极性溶剂中的荧光光谱变化曲线。如图1示，随着溶剂极性的增加，其荧光峰出现了明显红移，并且在水中表现出了明显的荧光增强现象。
实施例3
新型次氯酸盐荧光探针聚集诱导发光现象探究
在甲醇-水混合体系中加入初始浓度为1 mM荧光探针，使得溶液中荧光探针浓度为10 μM。对其做在不同含量甲醇-水中的荧光光谱变化曲线。如图2所示，随着水含量的增加，其荧光峰出现了明显红移，在水含量为40%时出现明显荧光增强现象，并且在水含量为100%时明显的荧光强度达到最高。结果表明，探针具有显著的聚集诱导发光效应。
实施例4
制备的次氯酸盐荧光探针的识别效果探究
在PBS缓冲液中，加入初始浓度为1 mM荧光探针，使得溶液中荧光探针浓度为10 μM。然后，依次加入0 μM、2 μM、4 μM、6 μM、8 μM、10 μM、12 μM、14 μM、16 μM、18 μM、20 μM不同浓度的次氯酸盐溶液，用荧光光谱仪测试不同次氯酸盐浓度条件下的荧光光谱。化合物的荧光光谱变化如图3所示，化合物在510 nm处的荧光峰值随着次氯酸盐的增加显著降低。并且，当次氯酸盐加入到20 μM 时，达到饱和，荧光强度不再降低。这说明荧光探针对次氯酸盐的灵敏性较好。
实施例5
制备的次氯酸盐荧光探针的竞争选择性效果探究
如实施例4所述，在同样测试条件下，向溶液中加入常见的阴离子，(1): F-, (2):Cl-, (3): Br-, (4): I-, (5): S2-, (6): SCN-, (7): HSO3 -, (8): SO4 2-, (9): CN-,(10): CO3 2-, (11): PO4 3-, (12): NO2 -, (13): ClO-。阴离子的浓度均为20 μM，测试其荧光光谱。结果如图4所示。显示，该探针对次氯酸盐具有较好的选择性。
实施例6
制备的次氯酸盐荧光探针的时间依赖性效果探究
化合物在pH为7.4的缓冲液中，加入初始浓度为1 mM荧光探针，使得溶液中荧光探针浓度为10 μM。然后，加入次氯酸盐，使次氯酸盐在混合液中的浓度达到20 μM，之后用荧光光谱仪测试不同时长下的荧光光谱，如图5所示。可以发现荧光强度在最初几秒内急速下降，1分钟左右荧光强度趋于稳定。说明探针与次氯酸盐可以迅速响应，具有较快的反应速度。
Claims (7)
1.一种四苯乙烯衍生物荧光探针，其特征在于，探针分子式为C44H40BNO2，如式(I)所示的结构：
2.一种权利要求1所述的四苯乙烯衍生物荧光探针的制备方法，其特征在于，采用以下步骤：
(1)将4-(二苯胺基)苯硼酸、苯甲酰溴溶于体积比为8:1的甲苯和无水乙醇中，N2保护下，加入四(三苯磷)钯和碳酸钾回流20h，二氯甲烷萃取，干燥后得到固体粉末为化合物TPE-Ac，其结构式如下：
(2)将4-溴二苯甲酮与TPE-Ac、锌粉溶于四氢呋喃中，0℃氩气保护下滴加四氯化钛在75℃下回流过夜；然后将反应用10％碳酸钾水溶液淬灭，萃取干燥后利用硅胶色谱柱状分离法对其进行提纯处理，得到固体产物即为TPE-Br，其结构式如下：
(3)将固体粉末TPE-Br与双(频哪醇)二硼、乙酸钾溶于无水N,N-二甲基甲酰胺，二氯[1,1'-二(二苯基膦)二茂铁]钯作为催化剂，在氮气保护下，在85℃的条件下反应24h，萃取干燥后利用硅胶色谱柱状分离法对其进行提纯处理，得到一种固体即为TPE-Bpin，其结构式如下：
3.根据权利要求2所述的四苯乙烯衍生物荧光探针的制备方法，所述步骤(2)中，TPE-Ac与4-溴二苯甲酮的摩尔比为1:1.25。
4.根据权利要求2所述的四苯乙烯衍生物荧光探针的制备方法，所述步骤(3)中，TPE-Br与双(频哪醇)二硼的摩尔比为1:2.5。
5.根据权利要求2所述的四苯乙烯衍生物荧光探针的制备方法，所述步骤(3)中，催化剂二氯[1,1'-二(二苯基膦)二茂铁]钯的摩尔用量为反应原料的2％-5％。
6.一种权利要求1所述的四苯乙烯衍生物荧光探针的应用，其特征在于，用于检测纯水环境中的次氯酸盐。
7.根据权利要求6所述的四苯乙烯衍生物荧光探针的应用，其特征在于，所述的检测方法为荧光猝灭型。
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