CN113248456B - 一种双重pH响应的聚集诱导发红光材料的制备及应用 - Google Patents
一种双重pH响应的聚集诱导发红光材料的制备及应用 Download PDFInfo
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Abstract
一种双重pH响应的聚集诱导发红光材料的制备及应用方法。所述发红光材料是由4‑(二乙氨基)水杨醛与4‑氨基‑2,1,3‑苯并噻二唑通过席夫碱反应制备而成。发红光材料基于扭曲的分子内电荷转移、分子内运动受限和激发态分子内质子转移协同作用的基础上，在聚集态下具有明亮的红色荧光，具有良好的聚集诱导发光性能。由于整合了两个pH响应基元，发红光材料在逐渐酸化过程中，伴随着荧光颜色从红色到黄绿色再到荧光淬灭的变化，同时在高水含量下的棒状分子组装体先转变为微球，再在较高酸度下微球被破坏。其次，二乙胺基的质子化在二氧化碳可视化检测和防伪、信息加密方面也具有应用价值。本发明制备工艺简单，制备成本较低，产率较高。
Description
技术领域
本发明涉及有机发光材料及防伪和加密材料技术领域，尤其涉及一种双重pH响应的聚集诱导发红光材料的制备和应用。
背景技术
由于快速响应、检测方便、对比度高、成本低的特点，刺激响应荧光材料在成像、防伪、图案制作和传感器等方面都显示出巨大的潜力。然而，大多数传统有机发光剂都会遭遇聚集淬灭效应，即荧光在高浓度溶液或聚集状态下会减弱甚至熄灭，这大大限制了它们的实际使用，因为大多数应用场景都处于固态状态。与聚集淬灭效应相反的现象称为聚集诱导发光，它是在稀释溶液中几乎无发射，而在聚集态发射强荧光。聚集诱导发光荧光团由于完美解决了实际应用中遇到的聚集淬灭效应的困境，掀起了科研界的研究热潮。聚集诱导发光材料可以为构建具有各种刺激反应性的荧光材料提供理想的平台。尤其是具有pH响应的聚集诱导发光材料受到越来越多的关注，因为pH值与环境和生命都息息相关。然而，由于缺乏具体的分子设计指南，大多数报道的pH响应性聚集诱导发光材料只有一种响应位点或者具有单一功能，这不利于多功能聚集诱导发光荧光材料的开发。此外，具有长波长发射的聚集诱导发光材料因其可以避免与基质自身荧光的光谱重叠，最大限度地减少对样品的光损伤而具有很大的需求和实际应用价值。由于聚集诱导发光材料具有有序的微观结构和独特的功能，因此可调谐的自组装形态转变对于聚集诱导发光材料更为理想。因此，具有多pH响应位点、长波长发射和可控自组装形貌的多功能聚集诱导发光材料的开发是十分必要的。
发明内容
有鉴于此，本发明提供了一种双重pH响应的聚集诱导红光材料的制备和应用，能够在酸化过程中表现出两种不同的荧光变化，同时伴随着自组装形貌的变化，并且可用于CO2可视化检测、防伪及加密领域。
一种双重pH响应的聚集诱导发红光材料的制备方法，其特征在于，制备步骤如下：
聚集诱导发红光材料的制备：将4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑加入到乙醇溶液中搅拌，接着加入几滴酸催化反应；反应完成后得到混合溶液，将混合溶液离心以沉淀产物，分离，干燥，得到聚集诱导发红光材料。
进一步地，所述4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑的摩尔比为1:1，所述乙醇溶液中无水乙醇、去离子水的体积比为4:1，所述反应温度为80-90℃，所述反应时间为6-8h；所述分离为离心沉淀分离，并选用去离子水和乙醇进行洗涤；所述反应为席夫碱反应，需在弱酸催化的环境下进行。所述酸为冰醋酸。
进一步地，通过二乙胺基水杨醛供体结构和苯并噻二唑受体结构的引入，基于扭曲的分子内电荷转移、分子内运动的受限和激发态分子内质子转移的协同效应，所制备的材料在聚集态具有明亮且长波长的荧光，即表现出优异的聚集诱导发红光性质。
进一步地，所述聚集诱导发红光材料在逐渐酸化过程中显示双重响应，在酸化至pH为3时，由于二乙胺基的质子化材料的发射由红色转变为黄绿色；继续酸化至pH为1时，由于席夫碱结构的破坏黄绿色荧光淬灭。
进一步地，所述聚集诱导发红光材料在高水含量不良溶剂环境中在氢键和疏水作用协同作用下有序堆积和排列，自组装为纳米棒状结构；在pH 4下二乙氨基质子化后，棒状结构转变成粒径约为400nm的微球；进一步酸化至pH 1，席夫碱键的水解导致微球的破坏，产生更小的颗粒。
如上所述方法制备的聚集诱导发红光材料的应用，其特征在于：所述具有双重pH响应的聚集诱导发红光材料可应用于CO2的可视化检测荧光材料、防伪材料或双重加密材料。(这一点为防伪应用)
所述聚集诱导发红光材料在CO2鼓泡过程中逐渐质子化，减弱了给电子能力，聚集诱导发红光材料的紫外吸收光谱和荧光都会发生变化，由红色荧光变为黄绿色荧光。在日光下聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的红色悬浮液会逐渐便清澈。通过调控CO2的通气速率可以控制该聚集诱导发红光材料质子化的快慢，进一步调控荧光变化的快慢，即可以通过紫外吸收光谱、荧光变化的快慢，定量检测CO2。也可通过在日光下悬浮液变澄清的速率对CO2进行定量检测。
由于所述聚集诱导发红光材料含有pH响应的二乙胺基基团，其显示可逆的质子化-去质子化过程，荧光颜色通过用HCl和NaOH溶液将pH值分别调节为4和10实现在红色发射和绿色发射之间可逆切换多次。通过酸碱调节实现该聚集诱导发光材料的荧光可逆切换可用于产品防伪领域。
其原理是：所述具有聚集诱导发红光材料不仅具有二乙胺基基团可逆的质子化-去质子化过程，其结构中的席夫碱键在强酸条件下会发生水解，破坏发光结构，导致荧光淬灭。双重pH响应过程中不同的荧光变化可以用于双重加密系统。选用在日光下颜色相近的非荧光染料，以及颜色相近、荧光相近的没有pH响应的荧光材料与所述聚集诱导发红光材料协同构建双重加密系统：一重加密信息在紫外灯下显示；二重加密信息需要在弱酸条件下使二乙胺基质子化后可显示出来。在读取二重加密信息后，用强酸处理，由于席夫碱键的水解，二重信息在紫外线和日光下均不可见，从而进一步防止了信息披露。(这一点为双重加密应用)
一种如上所述方法制备的具有双重pH响应的聚集诱导发红光材料的应用方法，具体制备步骤为：
1.将4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑加入到乙醇中，接着加入几滴冰醋酸催化反应，80-90℃冷凝回流6-8h；反应完成后得到混合溶液，将混合溶液离心以沉淀产物，分离，用乙醇和去离子水洗涤三次，干燥，得到聚集诱导发红光材料。
2.以乙醇为该聚集诱导发红光材料的良溶剂，以水为不良溶剂，配制不同水含量的同浓度的聚集诱导发红光材料的乙醇和水混合物溶液，用荧光光谱仪测量不同水含量下的荧光图谱，绘制荧光谱图，并且绘制荧光强度随水含量变化的线性曲线。
3.配制不同pH值的同浓度聚集诱导发红光材料溶液，用紫外吸收光谱仪和荧光光谱仪测量不同pH下的吸收光谱和荧光谱图，绘制谱图。
4.用稀释的盐酸溶液和氢氧化钠溶液循环调控该聚集诱导发红光材料在90％水含量下的pH为4和10，分别测量它们的荧光谱图。
5.将滤纸浸渍在该聚集诱导发红光材料的水含量为90％的乙醇/水混合液中，干燥后观察其荧光；用乙酸蒸汽、盐酸蒸汽分别熏蒸该滤纸，观察熏蒸前后荧光变化。用热三乙胺蒸汽熏蒸经乙酸蒸汽熏蒸过的滤纸，观察其荧光变化。
6.通过透射电镜观察该聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的形貌。然后依次将其酸化至pH为4和1，通过透射电镜观察该聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的形貌。
7.向该聚集诱导发红光材料的水含量为90％的乙醇/水混合液中通入CO2，检测其紫外吸收和荧光变化。
8.将该聚集诱导发红光材料的溶液沉积于滤纸上构建防伪和双重加密系统给。
本发明红光材料基于扭曲的分子内电荷转移、分子内运动受限和激发态分子内质子转移协同作用的基础上，在聚集态下具有明亮的红色荧光，具有良好的聚集诱导发光性能。由于整合了两个pH响应单元，红光材料在逐渐酸化过程中，伴随着荧光颜色从红色到黄绿色再到荧光淬灭的变化，同时在高水含量下的棒状分子组装体先转变为微球，再在较高酸度下微球被破坏。其次，二乙胺基的质子化在二氧化碳可视化检测和防伪、信息加密方面也具有应用价值。
本发明优点是：通过4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑进行席夫碱反应，生成该聚集诱导发红光材料，且该聚集诱导发红光材料的制备工艺简单，制备成本较低，产率较高。不仅具有双重pH响应性能和聚集诱导发光性能，还具有可调的形貌转变和CO2响应特性；另外，该聚集诱导发红光材料在防伪和加密领域拥有良好的应用前景。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1为本发明实施例提供的具有双重pH响应的聚集诱导发红光材料的制备方法的步骤示意图；
图2是聚集诱导发红光材料在具有不同水含量的乙醇/水混合液中的荧光光谱。
图3是聚集诱导发红光材料在具有不同水含量的乙醇/水混合液中的最高荧光强度随水含量变化的线性关系图。
图4是聚集诱导发红光材料在具有不同pH值的90％水含量乙醇/水混合液中的紫外-可见吸收和荧光光谱。
图5是聚集诱导发红光材料在具有不同水含量的乙醇/水混合液中的荧光强度在碱性条件(pH 10.0，开启)和酸性条件(pH 4.0，关闭)之间的可逆切换图。
图6是在日光和紫外光照射下，用乙酸(AcOH)蒸汽、盐酸(HCl)蒸汽或热三乙胺(TEA)蒸汽冒烟前后，浸渍有乙醇/水混合物的聚集诱导发红光材料的滤纸的照片。
图7是90％水含量下乙醇/水混合物中该聚集诱导发红光材料的透射电镜图片(从左至右分别是在pH 6.5，pH 4，pH 1条件下)。
图8是连续CO2刺激(18mL/min)不同时间和用NaOH溶液调节至pH 10后在90％水含量下乙醇/水混合物中该聚集诱导发红光材料的紫外-可见吸收和荧光光谱。
图9是连续CO2刺激(18mL/min)不同时间和用NaOH溶液调节至pH 10后在90％水含量下乙醇/水混合物中该聚集诱导发红光材料在日光和紫外灯下的照片。图10是本发明实施例提供的具有双重pH响应的聚集诱导发红光材料制备的防伪模型照片。
图11是本发明实施例提供的具有双重pH响应的聚集诱导发红光材料制备的双重加密模型照片。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
1.图1为本发明实施例提供的具有双重pH响应的聚集诱导发红光材料的制备方法的步骤示意图。制备具有双重pH响应的聚集诱导发红光材料，制备步骤如下：
4-(二乙氨基)水杨醛(193mg)与4-氨基-2,1,3-苯并噻二唑(151mg)以1：1的摩尔投料比加入到反应瓶中，再加入15mL乙醇，滴加两滴冰醋酸做催化剂，将该体系于80-90℃冷凝回流6-8h，反应结束后离心处理，用去离子水洗涤三次后，烘干即得具有双重pH响应的聚集诱导发红光材料。产率为90％。
2.将该具有双重pH响应的聚集诱导发红光材料溶解于乙醇中，配制含有不同水含量(0-90％水含量)的同浓度的乙醇/水混合溶液。采用荧光光谱仪测量不同水含量对应体系的荧光光谱(见图2)，并绘制其不同水含量下对应体系的最高荧光强度随水含量变化的线性曲线(见图3)。荧光强度随着水含量的增加显著增强。
3.双重pH响应的测试
(1)测量具有不同pH值的90％水含量乙醇/水混合液中该聚集诱导发红光材料的紫外-可见吸收和荧光光谱(见图4)。该红光材料在弱碱、中性和弱酸条件下荧光开启，在强碱和强酸条件下荧光关闭。该具有双重pH响应的聚集诱导发红光材料在pH 4和9之间荧光可以循环可逆关闭和开启(见图5)。
(2)观察浸渍有乙醇/水混合物的聚集诱导发红光材料的滤纸的荧光照片，再依次用醋酸和盐酸蒸汽熏蒸滤纸观察荧光变化。浸渍有乙醇/水混合物的聚集诱导发红光材料的滤纸在紫外灯下发射红色荧光，经醋酸蒸汽熏蒸后，由于二乙胺基的质子化红色荧光转变为黄绿色荧光，且经三乙胺蒸汽熏蒸后黄绿色荧光可以恢复到原始的红色荧光。但在经盐酸蒸汽熏蒸后，由于席夫碱键的断裂，荧光淬灭且不可逆(见图6)。
4.形貌调控的测试
图7是90％水含量下乙醇/水混合物中该聚集诱导发红光材料的透射电镜图片，在疏水作用和氢键作用的协同作用下自组装成棒状结构。在pH为4时，由于二乙氨基的疏水-亲水转变促进了超分子自组装驱动力的变化，棒状结构转变为粒径约400nm的微球。随着系统进一步酸化至pH为1，该聚集诱导发红光材料结构中席夫碱键的水解导致微球的破坏，产生更小的颗粒。
5.CO2检测的测试
由于二乙氨基的质子化会被CO2溶剂化导致的pH值降低触发，因此研究了该聚集诱导发红光材料的CO2响应性。测量CO2通气过程中90％水含量乙醇/水混合液中该聚集诱导发红光材料的紫外-可见吸收和荧光光谱(见图8)。在CO2鼓气10min后，红色荧光变成了一种荧光较弱的淡黄色、相对透明的液体。用CO2处理30min后，悬浮液变得透明，荧光熄灭。再用NaOH溶液将pH值调整为10后，体系恢复浑浊，荧光恢复(见图9)。
6.本发明提供的具有双重pH响应的聚集诱导发红光材料的防伪和双重加密应用：
图10为应用双重pH响应的聚集诱导发红光材料制备的防伪模型照片，字符“AIE”是用该聚集诱导发红光材料制备的墨水书写的，呈黄棕色，发出红色荧光。在用10-3M HCl的酸性笔处理后变为黄色，并显示出明亮的黄绿色荧光。此外，当用10-3M NaOH笔重写时，字符可以恢复到原来的状态，并发出红光。
除了用于防伪的可逆荧光书写之外，该聚集诱导发红光材料还具有用于双重加密应用的潜力。字母“A、F、G”、“B、D、E”和“C”分别用偶氮苯衍生物墨水、该聚集诱导发红光材料墨水和吩噻嗪衍生物墨水书写。在日光照射下，只显示一系列颜色相似的黄色信息。“B，C，D，E”在紫外光照射下发出明亮的荧光，而“A，F，G”是非荧光的。加密信息“B，D，E”经10-3MHCl酸性笔处理后，呈现出明显的由红到黄绿色的荧光颜色变化。加密信息“B，D，E”在用10- 1M HCl处理后会被破坏，在紫外线和日光下是看不见的，进一步阻止信息泄露(见图11)。由该图可以看出该聚集诱导发红光材料在防伪和加密领域将拥有巨大的应用前景。
Claims (8)
1.一种双重pH响应的聚集诱导发红光材料的制备方法，其特征在于，
将4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑加入到乙醇去离子水溶液中搅拌，接着加入几滴弱酸催化剂催化反应；反应完成后得到混合溶液，将混合溶液分离，干燥，得到聚集诱导发红光材料。
2.根据权利要求1所述具有双重pH响应的聚集诱导发红光材料的制备方法，其特征在于：所述4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑的摩尔比为1:1，所述乙醇溶液中无水乙醇、去离子水的体积比为4:1，所述反应温度为80-90℃，所述反应时间为6-8h；所述分离为离心沉淀分离，并选用去离子水和乙醇进行洗涤；所述反应为席夫碱反应，需在弱酸催化的环境下进行。
3.根据权利要求1或2所述具有双重pH响应的聚集诱导发红光材料的制备方法，其特征在于：通过二乙胺基水杨醛供体结构和苯并噻二唑受体结构的引入，基于扭曲的分子内电荷转移、分子内运动的受限和激发态分子内质子转移的协同效应，所制备的材料在聚集态具有明亮且长波长的荧光，即表现出优异的聚集诱导发红光性质。
4.根据权利要求1或2所述具有双重pH响应的聚集诱导发红光材料的制备方法，其特征在于：所述聚集诱导发红光材料在逐渐酸化过程中显示双重响应，在酸化至pH为3时，由于二乙胺基的质子化材料的发射由红色转变为黄绿色；继续酸化至pH为1时，由于席夫碱结构的破坏黄绿色荧光淬灭。
5.根据权利要求1所述具有双重pH响应的聚集诱导发红光材料的制备方法，其特征在于：所述聚集诱导发红光材料在高水含量不良溶剂环境中在氢键和疏水相互作用协同作用下有序堆积和排列，自组装为纳米棒状结构；在pH 4下二乙氨基质子化后，棒状结构转变成粒径为400nm的微球；进一步酸化至pH 1，席夫碱键的水解导致微球的破坏，产生更小的颗粒。
6.一种如权利要求1所述方法制备的具有双重pH响应的聚集诱导发红光材料的应用方法，其特征在于具体步骤为：
1).将4-(二乙氨基)水杨醛与4-氨基-2,1,3-苯并噻二唑加入到乙醇中，接着加入几滴冰醋酸催化反应，80-90℃冷凝回流6-8h；反应完成后得到混合溶液，将混合溶液离心以沉淀产物，分离，用乙醇和去离子水洗涤三次，干燥，得到聚集诱导发红光材料；
2).以乙醇为该聚集诱导发红光材料的良溶剂，以水为不良溶剂，配制不同水含量的同浓度的聚集诱导发红光材料的乙醇和水混合物溶液，用荧光光谱仪测量不同水含量下的荧光图谱，绘制荧光谱图，并且绘制荧光强度随水含量变化的线性曲线；
3).配制不同pH值的同浓度聚集诱导发红光材料，用紫外吸收光谱仪和荧光光谱仪测量不同pH下的吸收光谱和荧光谱图，绘制谱图；
4).用稀释的盐酸溶液和氢氧化钠循环调控该聚集诱导发红光材料在90％水含量下的pH为4和10，分别测量它们的荧光谱图；
5).将滤纸浸渍在该聚集诱导发红光材料的水含量为90％的乙醇/水混合液中，干燥后观察其荧光；用乙酸蒸汽、盐酸蒸汽分别熏蒸该滤纸，观察熏蒸前后荧光变化；用热三乙胺蒸汽熏蒸经乙酸蒸汽熏蒸过的滤纸，观察其荧光变化；
6).通过透射电镜观察该聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的形貌，然后依次将其酸化至pH为4和1，通过透射电镜观察该聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的形貌；
7).向该聚集诱导发红光材料的水含量为90％的乙醇/水混合液中通入CO2，检测其荧光变化。
7.根据权利要求1所述方法制备的聚集诱导发红光材料的应用，其特征在于：所述聚集诱导发红光材料可用于CO2的可视化检测，所述聚集诱导发红光材料在CO2鼓泡过程中逐渐质子化，削弱了给电子能力，聚集诱导发红光材料的紫外吸收光谱会发生变化，荧光也由红色变为黄绿色，在日光下聚集诱导发红光材料在水含量为90％的乙醇/水混合液中的红色悬浮液会逐渐便清澈；
通过调控CO2的通气速率可以控制该聚集诱导发红光材料质子化的快慢，进一步调控荧光变化的快慢，即通过紫外吸收光谱、荧光变化的快慢，定量检测CO2；或通过在日光下悬浮液变澄清的速率对CO2进行定量检测。
8.根据权利要求1所述方法制备的聚集诱导发红光材料的应用，其特征在于：所述具有双重pH响应的聚集诱导发红光材料可应用于防伪材料和双重加密材料；由于所述聚集诱导发红光材料含有pH响应的二乙胺基基团，其显示可逆的质子化-去质子化过程，荧光颜色通过用HCl和NaOH溶液将pH值分别调节为4和10实现在红色发射和绿色发射之间可逆切换多次；通过酸碱调节实现该聚集诱导发光材料的荧光可逆切换可用于产品防伪领域；
其原理是：所述具有聚集诱导发红光材料不仅具有二乙胺基基团可逆的质子化-去质子化过程，其结构中的席夫碱键在强酸条件下会发生水解，破坏发光结构，导致荧光淬灭；双重pH响应过程中不同的荧光变化可以用于双重加密系统，选用在日光下颜色相近的非荧光染料、以及颜色相近、荧光相近的没有pH响应的荧光材料与所述聚集诱导发红光材料协同构建双重加密系统：一重加密信息在紫外灯下显示；二重加密信息需要在弱酸条件下使二乙胺基质子化后可显示出来；在读取二重加密信息后，用强酸处理，由于席夫碱键的水解，二重加密信息在紫外线和日光下均不可见，从而进一步防止了信息披露。
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