CN108440441B - 一种aie荧光探针分子以及对对硝基苯胺、氟离子的检测方法 - Google Patents
一种aie荧光探针分子以及对对硝基苯胺、氟离子的检测方法 Download PDFInfo
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Abstract
本发明涉及一种AIE荧光探针分子以及对对硝基苯胺、氟离子的检测方法，解决了现有技术中荧光探针识别能力差和荧光猝灭严重的技术问题。本发明通过简单的合成手段以芘甲醛和绕丹宁为原料，吡啶做催化剂，获得了5‑芘亚甲基绕丹宁。该分子表现出良好的聚集诱导发光效应，是一种检测对硝基苯胺、氟离子的高灵敏性荧光探针分子。
Description
技术领域
本发明涉及聚集诱导发光效应和荧光探针领域，具体为一种AIE荧光探针分子以及对对硝基苯胺、氟离子的检测方法。
背景技术
聚集诱导发光效应(AIE)是2001年唐本忠院士课题组首先发现的,相对于传统的荧光生色团在高浓度下荧光会减弱甚至不发光现象，这类聚合物在聚集状态或固体薄膜下发光大大增强,这种由聚集所导致发光增强效应叫做“聚集诱导发光效应”。基于AIE现象的认识与研究，一系列的AIE物质被合成出来，并制成高效的发光器件和化学生物传感器。也正是如此，对于AIE现象机理的研究也广泛而深入的开展，目前提出的AIE机理包括分子内旋转受限(RIR)、分子内共平面、抑制光化学或光物理过程等.事实上，对于每一个分子而言，AIE现象的形成往往是几个原因共同作用的结果。这种反常的发光行为引起了国内外广大科研工作者的极大兴趣,关于AIE的机理及应用研究也越来越深入,具有AIE效应的发光材料在有机电致发光器件,化学传感器,生物荧光探针等领域已经表现出广阔的应用前景。
对硝基苯胺广泛应用于染料工业的人工合成化学物，是多种印染及医药化工品的中间体，也可用于分析试剂。但对硝基苯胺存在高毒性，吸入、皮肤接触及吞食有毒，且有累积效应，对水生生物有害，可能对水体环境产生长期不良影响。所以，设计、制备出一种合适的荧光探针是目前最紧要的研究。然而，对硝基苯胺对本发明中的荧光探针分子有明显的淬灭效应，本发明中分子是一种检测对硝基苯胺的有效荧光探针。
近几年，提出氟离子荧光探针分子结构有不少，例如：CN104449677A提出的一种2-(2-羟基苯基)苯并噻唑衍生物，CN104610955A制备的以2-(2-羟基苯基)苯并噻唑衍生物为母体结构的比率型荧光探针，CN105985291A一类萘酰亚胺类类化合物，其可作为氟离子比色荧光探针用于氟离子的检测和CN106632450A以水杨醛为原料，经与水合肼形成水杨醛吖嗪，再经硅保护而成氟离子荧光探针。但以5-芘亚甲基绕丹宁为基体结构的氟离子荧光探针分子至今没有发现。
发明内容
本发明的目的是提供一种AIE荧光探针分子以及对对硝基苯胺、氟离子的检测方法，本发明以芘甲醛和绕丹宁为原料，以吡啶做催化剂，获得了一种5-芘亚甲基绕丹宁，该分子表现出良好的聚集诱导发光效应，也是一种检测对硝基苯胺、氟离子的高灵敏性荧光探针分子。
本发明的上述技术目的是通过以下技术方案得以实现的：
一种AIE荧光探针分子，其特征在于：其化合物结构式为
优选地，R选自氢或醛基。
一种AIE荧光探针分子对对硝基苯胺的检测方法，其特征在于：其步骤如下：
先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的对硝基苯胺水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中对硝基苯的浓度，激发波长为300nm。
优选地，所述荧光探针分子溶液中水和丙酮或水和四氢呋喃的体积比为90:10～60:40；所述荧光探针分子溶液中的荧光探针分子的浓度为10-4mol/L。
优选地，所述荧光探针分子溶液中水和丙酮或水和四氢呋喃的体积比为80:20。
优选地，所述对硝基苯胺水溶液的浓度为0.003g/L～15g/L。
一种AIE荧光探针分子对氟离子的检测方法，其特征在于：其步骤如下：
先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的氟化钾水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中氟化钾的浓度，激发波长为300nm。
优选地，所述氟化钾水溶液中氟离子的浓度为0.01g/L～10g/L。
优选地，所述氟化钾水溶液中的钾离子、钠离子和氯离子的浓度分别为0.11g/L～10g/L。
本发明的有益效果是：
本发明将聚集诱导发光效应(AIE)引入荧光探针中，解决常规荧光探针分子需要良好水溶性的局限，该探针分子光稳定性强，荧光受环境影响小，且对于对硝基苯胺、氟离子也具有较高灵敏性和选择性，制备方法简便易行，在环境监测和生物体***中具有良好的应用前景。
附图说明
图1为本发明荧光探针分子在不同体积比水和丙酮混合溶剂化合物溶液(10-4M)荧光图谱(左)和对应的荧光强度变化曲线(右)(荧光激发波长为300nm)；
图2为本发明荧光探针分子在不同体积比水和丙酮混合溶剂化合物溶液(10-4M)实物图；
图3为本发明荧光探针分子在365nm紫外灯激发下、不同体积比水/丙酮混合溶剂化合物溶液(10-4M)实物图；
图4为本发明荧光探针分子对不同浓度的对硝基苯胺样品溶液(10-4M)的荧光光谱图(左)和对应的荧光强度条形图(右)(以300nm为荧光激发波长)；
图5为本发明荧光探针分子在365nm紫外灯下、不同浓度的对硝基苯胺样品溶液(10-4M)的实物图；
图6为本发明荧光探针分子对不同浓度的氟化钾样品溶液(10-4M)的荧光光谱图(左)和对应的荧光强度条形图(右)(以300nm为荧光激发波长)；
图7为本发明荧光探针分子在365nm紫外灯激发下、不同浓度的氟化钾样品溶液(10-4M)在365nm紫外灯下的激发图；
图8为本发明荧光探针分子对不同浓度的氯化钾样品溶液(10-4M)的荧光光谱图(左)和对应的荧光强度条形图(右)(以300nm为荧光激发波长)；
图9为本发明荧光探针分子在不同体积比水/四氢呋喃混合溶剂化合物溶液(10- 4M)荧光图谱(左)和对应的荧光强度变化曲线(右)(荧光激发波长为390nm)；
图10为本发明荧光探针分子对不同浓度的对硝基苯胺样品溶液(10-4M)的荧光光谱图(左)和对应的荧光强度条形图(右)(以390nm为荧光激发波长)；
图11为本发明可检测对硝基苯胺、氟离子的AIE荧光探针分子的结构式。
具体实施方式
本发明提供一种AIE荧光探针分子以及对对硝基苯胺、氟离子的检测方法；
实施例一：
1、荧光探针分子5-芘亚甲基绕丹宁的合成(R＝H)的制备方法包括以下步骤：
(1)将0.046g(0.2mmol)芘甲醛、0.0483g(0.3mmol)绕丹宁和3滴醋酸加入到50mL三口瓶中，用8mL无水乙醇溶解；
(2)加入3滴吡啶催化，80摄氏度回流反应3小时；
(3)冷却后，TLC检测反应完全，溶液显橙色，久置底部有橙红色晶体析出；
(4)减压蒸馏除去溶剂，以3:7:0.5的石油醚、二氯甲烷和甲醇为流动相,硅胶柱分离，得到橙红色粉末的目标产物5-芘亚甲基绕丹宁，产率约为76.2％。
橙红色粉末的目标产物的结构确认数据如下：1H NMR(500MHz,CDCl3)δ8.55–8.39(m,1H),8.35–7.94(m,7H),7.26(s,2H),4.39–4.19(m,2H),1.25(s,3H)；其以下分子结构式如下：
2、荧光探针分子聚集诱导发光(AIE)效应验证：
(1)对荧光探针分子5-芘亚甲基绕丹宁在水和丙酮不同体积比的荧光探究，将5-芘亚甲基绕丹宁以10-4M的浓度分散于10组水和丙酮混合溶剂(体积比0/100-90/10)中，以300nm为荧光激发波长，得到如图1所示的荧光光谱图；由图1可知，荧光光谱显示出明显的规律变化，随着水的不断增加，最大吸收峰在不移动的前提下，峰值逐渐增高，在水和丙酮比为80/20时达到最大。样品荧光强度从17.64a.u(0％)增加到878.9a.u(80％)，发光强度增加49倍。
(2)荧光探针分子5-芘亚甲基绕丹宁在水和丙酮比例分别为10/90、30/70、60/40和80/20的样品溶液如图2所示；在365nm紫外灯照射下，水和丙酮比例分别为20/80、40/60、80/20、90/10的样品溶液如图3所示，由图2可以明显看到，溶液由透明淡黄色到颜色加深最后到溶液浑浊，发生分子聚集现象，而图3的现象跟荧光光谱图相吻合，在80/20处荧光最强，验证了该荧光探针分子具有AIE效应。
3、荧光探针分子对于对硝基苯胺检测
(1)先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的对硝基苯胺水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中对硝基苯胺的浓度，激发波长为300nm；荧光探针分子溶液的浓度为10-4mol/L，水和丙酮或水和四氢呋喃的体积比为80:20；配置九组不同浓度的对硝基苯胺水溶液(浓度分别为0.03g/L、0.05g/L、0.1g/L、0.5g/L、1g/L、1.5g/L、2g/L、3g/L、15g/L)，用来参照比对，如图4所示，结果表明：随着对硝基苯胺的浓度增加，样品荧光强度急剧降低，从6223a.u.(0g/L)到51.29a.u.，减少了121倍。因此，该荧光分子对对硝基苯胺具有很好的检测性能。
(2)将浓度分别为0.5g/L、5g/L和10g/L与未加入对硝基苯胺的空白样品溶液进行紫外灯照射，如图5所述，可以明显看出：加入对硝基苯胺的样品溶液几乎变得澄清，纳米粒子的减少，荧光强度随之急剧降低，验证了对硝基苯胺对荧光探针分子有明显的淬灭现象，很好应用于对硝基苯胺的检测。
4、荧光探针分子对于氟离子的检测
(1)先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的氟化钾水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中氟化钾的浓度，激发波长为300nm；荧光探针分子溶液的浓度为10-4mol/L，水和丙酮或水和四氢呋喃的体积比为80:20；配置七组不同浓度的对硝基苯胺水溶液(浓度分别为0.03g/L、0.05g/L、0.1g/L、0.5g/L、1g/L、5g/L、10g/L)，用来参照比对，如图6所示，结果表明：随着加入氟化钾的样品溶液浓度的增大，发光强度降低，发生了荧光淬灭现象。
(2)取氟化钾1g/L、5g/L和10g/L与未加入氟化钾的空白样品溶液进行紫外灯照射，如图7所示，可以看到加入氟化钾的样品溶液，随着浓度的增大，发光强度降低，这与荧光图谱上的数据在理论上是一致。
(3)为了验证氟化钾中引起样品荧光猝灭的离子不是钾离子，而是氟离子，特此做了加入浓度0.1g/L、1g/L和10g/L氯化钾，采用激发波长为300nm，荧光光度计测试荧光强度，如图8所示，结果表明：钾离子对样品的荧光强度几乎没有影响，并且也没有明显的荧光猝灭现象；氟化钾水溶液中的钾离子、钠离子和氯离子的浓度分别为0.11g/L～10g/L。
实施例二
将R替换成氨基或者醛基，其余条件均与同实施例1相同，可以制得可检测氟离子的AIE荧光探针分子，结果与实施例1相似。
实施例三
1、荧光探针分子(R＝CHO)的制备方法，步骤如下：
(1)将实施例1中5-芘亚甲基绕丹宁1.4728g(4mmol)和N,N-二甲基酰胺6.2411g(85mmol)加入到100mL三口瓶中，在0℃冰浴下半小时内缓慢滴加3.2mLPOCl3，保持0℃冰浴反应1h，再升温至90-100℃回流反应约24h；
(2)待其冷却，TLC检测反应完全，溶液呈黑色；
(3)加入3mL冰水水解；再次冷却至室温，用浓Na2CO3溶液调节pH值至5-6，再用3×30mL甲苯萃取，取下层溶液；
(4)依次用浓Na2CO3溶液和去离子水洗涤，减压蒸馏除去溶剂，以3:2的石油醚和二氯甲烷为流动相，硅胶柱层析分离，得到目标产物，产率约为65％。
目标产物的结构确认数据如下：1H NMR(500MHz,CDCl3)δ8.96(s,1H),8.64–7.86(m,7H),7.26(s,2H),4.54–3.28(m,2H),1.40–1.27(m,3H)。
2、荧光探针分子(R＝CHO)聚集诱导发光(AIE)效应和对硝基苯胺检测的验证：
方法同实施例一中的第2、3点，区别在于取水和四氢呋喃混合溶液中，测试荧光光谱激发波长为390nm，分别得到如图9所示的荧光光谱图和如图10所示的对硝基苯胺检测。得到与实施例一的分子相似性质的结论。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。
Claims (8)
1.一种AIE荧光探针分子，其特征在于：其化合物结构式为，R选自醛基。
2.使用权利要求1的AIE荧光探针分子对对硝基苯胺的检测方法，其特征在于：其步骤如下：
先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的对硝基苯胺水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中对硝基苯的浓度，激发波长为300nm。
3.根据权利要求2所述的对对硝基苯胺的检测方法，其特征在于：所述荧光探针分子溶液中水和丙酮或水和四氢呋喃的体积比为90:10～60:40；所述荧光探针分子溶液中的荧光探针分子的浓度为10-4mol/L。
4.根据权利要求3所述的对硝基苯胺的检测方法，其特征在于：所述荧光探针分子溶液中水和丙酮或水和四氢呋喃的体积比为80:20。
5.根据权利要求2所述的对对硝基苯胺的检测方法，其特征在于：所述对硝基苯胺水溶液的浓度为0.003g/L～15g/L。
6.使用权利要求1的AIE荧光探针分子对氟离子的检测方法，其特征在于：其步骤如下：
先将荧光探针分子溶于水和丙酮或水和四氢呋喃溶液中，得到具有AIE效应的荧光探针分子溶液，再将荧光探针分子溶液与待测的氟化钾水溶液混合，得到混合溶液，通过混合溶液中探针分子荧光光谱强度变化，检测待测水溶液中氟化钾的浓度，激发波长为300nm。
7.根据权利要求6所述的对氟离子的检测方法，其特征在于：所述氟化钾水溶液中氟离子的浓度为0.01g/L～10g/L。
8.根据权利要求6所述的对氟离子的检测方法，其特征在于：所述氟化钾水溶液中的钾离子、钠离子和氯离子的浓度分别为0.11g/L～10g/L。
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