CN111484632B - 一种酸碱度传感器 - Google Patents

一种酸碱度传感器 Download PDF

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CN111484632B
CN111484632B CN202010331699.5A CN202010331699A CN111484632B CN 111484632 B CN111484632 B CN 111484632B CN 202010331699 A CN202010331699 A CN 202010331699A CN 111484632 B CN111484632 B CN 111484632B
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夏宏燕
胡丹
谢康
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Abstract

本发明属于水凝胶技术领域，尤其涉及一种酸碱度传感器。本发明提供了一种荧光可变色智能水凝胶的制备方法，将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，丙烯酰胺发生交联聚合反应并使荧光染料包裹于交联聚合反应生成的聚丙烯酰胺中，聚丙烯酰胺能够与荧光染料形成氢键避免荧光染料的泄露，荧光染料可感应pH发生荧光变化，得到的荧光可变色智能水凝胶随着酸碱性的不同而发生荧光变化，该荧光可变色智能水凝胶应用于酸碱度传感器中具有很大的应用前景。

Description

一种酸碱度传感器
技术领域
本发明属于水凝胶技术领域，尤其涉及一种酸碱度传感器。
背景技术
水凝胶是一种由亲水性聚合物在水中发生化学交联或物理交联后形成的具有三维网络结构的高分子软材料，它能被应用到很多领域，比如组织工程、药物释控、物质分离和机械器件等。目前，研究者们常以水凝胶作为基质，载以检测物质，用以特异性检测水凝胶周围环境的变化，进而实现水凝胶功能化。
但是，目前主要以热致变色或力致变色实现水凝胶变色功能，如何使水凝胶通过酸碱变色还有待于开发。
发明内容
有鉴于此，本发明提供了一种酸碱度传感器，该荧光可变色智能水凝胶可感应环境酸碱变化发生荧光变化，且荧光变化过程是可逆的。
本发明的具体技术方案如下：
一种荧光可变色智能水凝胶的制备方法，包括以下步骤：
将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，静置，丙烯酰胺发生交联聚合反应并使所述荧光染料包裹于所述交联聚合反应生成的聚丙烯酰胺中，得到荧光可变色智能水凝胶；
其中，所述荧光染料可感应pH发生荧光变化且能够与所述聚丙烯酰胺形成氢键。
本发明中，将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，丙烯酰胺发生交联聚合反应并使荧光染料包裹于交联聚合反应生成的聚丙烯酰胺中，聚丙烯酰胺含有大量的酰胺键，能够与荧光染料形成氢键避免荧光染料的泄露，荧光染料可感应pH发生荧光变化，得到的荧光可变色智能水凝胶随着酸碱性的不同而发生荧光变化，该荧光可变色智能水凝胶应用于酸碱度传感器中具有很大的应用前景。
本发明制备方法简单、操作方便快捷，且首次基于水凝胶体系来制备荧光可变色智能水凝胶，该荧光可变色智能水凝胶的荧光变化过程简便、快速，控制手段简单，荧光变化明显，肉眼可见。
优选的，所述荧光染料选自5(6)-羧基荧光素、8-羟基-1,3,6-芘三磺酸三钠、苯酚红、花菁染料Cy3或花菁染料Cy5，更优选为5(6)-羧基荧光素。
本发明中，5(6)-羧基荧光素和丙烯酰胺的结构式如下：
Figure 855358DEST_PATH_IMAGE001
5(6)-羧基荧光素；
Figure 834816DEST_PATH_IMAGE002
丙烯酰胺。
本发明中，采用丙烯酰胺，交联聚合反应生成的聚丙烯酰胺水凝胶具有良好的生物相容性和力学性能，透明性好、光导性能优良。本发明荧光可变色智能水凝胶可直接贴附于操作人员的皮肤上，便于操作人员快速知晓操作环境的酸碱度。
本发明中，荧光染料优选为5(6)-羧基荧光素，5(6)-羧基荧光素在碱性环境下荧光发生明显变化，接触酸性环境后其荧光状态可以逆回到初始状态，具有非常好的可逆性。本发明将5(6)-羧基荧光素掺杂进入聚丙烯酰胺水凝胶，通过对聚丙烯酰胺水凝胶进行酸碱处理达到视觉上的荧光变化，荧光变化具有效果明显，肉眼可见，变化过程可逆等特点，对酸碱度传感检测方面的研究应用提供了很大的发展空间。
优选的，所述荧光染料在所述丙烯酰胺水溶液的质量分数为3 wt‱~5 wt‱。
优选的，所述丙烯酰胺在所述丙烯酰胺水溶液的质量分数为40%~60%。
优选的，所述交联聚合反应的温度为10~38℃；
所述交联聚合反应的时间为10~60 min。
优选的，所述将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵之后，所述静置之前，还包括：
将溶有所述荧光染料的丙烯酰胺水溶液倒入模具中。
本发明中，荧光可变色智能水凝胶的制备方法具体包括以下步骤：
将5(6)-羧基荧光素溶于丙烯酰胺溶液，搅拌均匀后将溶液倒入实验用圆形或哑铃型模具中，放置60~150min，丙烯酰胺发生交联聚合反应得到聚丙烯酰胺并使5(6)-羧基荧光素包裹于聚丙烯酰胺中，得到荧光可变色智能水凝胶。
将把装有氨水的容器瓶置于工作的通风橱内，用镊子夹取荧光可变色智能水凝胶悬放在揭开瓶塞的容器瓶瓶口上方，均匀熏染一段时间，在442nm激发光的辐照下熏染后的荧光可变色智能水凝胶发出强烈的绿色荧光，原因在于5(6)-羧基荧光素在碱性环境下形成高度共轭结构，骨架有刚性，量子产率高，从而发出强绿色荧光；将氨水换成盐酸，夹取经氨水处理后的荧光可变色智能水凝胶悬放在容器瓶瓶口上方熏染，在442nm激发光辐照下经过酸熏染处理后的荧光可变色智能水凝胶基本无荧光反应，回到未处理时的状态。将经盐酸处理后的荧光可变色智能水凝胶再一次进行氨水熏染，442nm激发光辐照下得到发出强烈绿色荧光的荧光可变色智能水凝胶。本发明荧光可变色智能水凝胶可感应环境酸碱变化发生荧光变化，且荧光变化过程是可逆的。
本发明还提供了一种荧光可变色智能水凝胶，所述荧光可变色智能水凝胶由上述技术方案所述制备方法制得。
本发明荧光可变色智能水凝胶经碱处理后，在激光辐照下发出强烈的荧光，接着经酸处理，激光辐照下水凝胶恢复无明显荧光的状态，从而产生肉眼视觉上的荧光变化，且这种变化是可逆的。
本发明还提供了一种酸碱度传感器，包括上述技术方案所述荧光可变色智能水凝胶。
优选的，还包括激发光源；
所述激发光源的波长为420~460 nm。
优选的，所述激发光源的波长为442 nm。
综上所述，本发明提供了一种荧光可变色智能水凝胶的制备方法，包括以下步骤：将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，静置，丙烯酰胺发生交联聚合反应并使所述荧光染料包裹于所述交联聚合反应生成的聚丙烯酰胺中，得到荧光可变色智能水凝胶；其中，所述荧光染料可感应pH发生荧光变化且能够与所述聚丙烯酰胺形成氢键。本发明中，将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，丙烯酰胺发生交联聚合反应并使荧光染料包裹于交联聚合反应生成的聚丙烯酰胺中，聚丙烯酰胺能够与荧光染料形成氢键避免荧光染料的泄露，荧光染料可感应pH发生荧光变化，得到的荧光可变色智能水凝胶随着酸碱性的不同而发生荧光变化，该荧光可变色智能水凝胶应用于酸碱度传感器中具有很大的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本发明实施例1荧光可变色智能水凝胶的制备过程示意图；
图2为本发明实施例1荧光可变色智能水凝胶未处理、经碱处理和酸处理后的实物图，其中，第一排为在可见光下的实物图，第二排为在激发光下的实物图；
图3为本发明实施例1不同形状的荧光可变色智能水凝胶在激发光下的荧光变化实物图；
图4为本发明实施例1荧光可变色智能水凝胶的荧光变化原理图；
图5为本发明实施例1荧光可变色智能水凝胶的荧光光谱图。
具体实施方式
本发明提供了一种酸碱度传感器，该荧光可变色智能水凝胶可感应环境酸碱变化发生荧光变化，且荧光变化过程是可逆的。
下面将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，本领域普通技术人员在没有做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。
具体实施例中，丙烯酰胺购于天津市致远化学试剂有限公司，5(6)-羧基荧光素购于阿拉丁生化科技有限公司。
实施例1
请参阅图1，为本发明实施例1荧光可变色智能水凝胶的制备过程示意图。本实施例荧光可变色智能水凝胶的制备包括：将3g丙烯酰胺溶解于3mL去离子水得到丙烯酰胺溶液，再加入3mg的5(6)-羧基荧光素配置成掺杂荧光素的丙烯酰胺溶液，搅拌均匀后将溶液倒入实验用圆形或者哑铃型模具，室温下放置一天，在溶液变成凝胶状态后得到荧光可变色智能水凝胶，将荧光可变色智能水凝胶从模具中取出。
将制得的荧光可变色智能水凝胶进行碱处理和酸处理，请参阅图2，为本发明实施例1荧光可变色智能水凝胶未处理、经碱处理和酸处理后的实物图，其中，第一排为在可见光下的实物图，第二排为在激发光下的实物图。
（1）荧光可变色智能水凝胶碱处理
把装有氨水的容器瓶置于工作的通风橱内，用镊子夹取一块荧光可变色智能水凝胶悬放在揭开瓶塞的容器瓶瓶口上方，均匀熏染3分钟，在波长为442nm的激发光的辐照下经过氨水熏染处理后的荧光可变色智能水凝胶发出非常强烈的绿色荧光，原因在于5(6)-羧基荧光素在碱性环境下形成高度共轭结构，骨架有刚性，量子产率高，从而发出强绿色荧光。
（2）荧光可变色智能水凝胶酸处理
将（1）中的氨水换成盐酸，夹取另一块荧光可变色智能水凝胶悬放在瓶口上方均匀熏染3分钟，在波长为442nm的激发光的辐照下经过盐酸熏染处理后的荧光可变色智能水凝胶基本无荧光反应，处理前后无明显变化。
请参阅图3至图5，图3为本发明实施例1不同形状的荧光可变色智能水凝胶在激发光下的荧光变化实物图，图4为本发明实施例1荧光可变色智能水凝胶的荧光变化原理图，图5为本发明实施例1荧光可变色智能水凝胶的荧光光谱图。
将制得的荧光可变色智能水凝胶依次进行碱处理、酸处理和碱处理，先把荧光可变色智能水凝胶进行碱处理，在波长为442nm的激发光辐照下荧光可变色智能水凝胶发出非常强烈的绿色荧光；再进行酸处理，在442nm激发光辐照下荧光可变色智能水凝胶基本无荧光反应，基本回到未处理时的状态；再将荧光可变色智能水凝胶进行碱处理，在波长为442nm的激发光辐照下水凝胶发出非常强烈的绿色荧光，得到荧光可变色智能水凝胶荧光变化的过程，这种过程是可逆的。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (3)

1.一种酸碱度传感器，其特征在于，包括激发光源和荧光可变色智能水凝胶，所述激发光源的波长为420~460 nm，所述荧光可变色智能水凝胶的制备方法，包括以下步骤：
将3g丙烯酰胺溶解于3mL去离子水得到丙烯酰胺溶液，将3mg的荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵，室温下静置一天，丙烯酰胺发生交联聚合反应并使所述荧光染料包裹于所述交联聚合反应生成的聚丙烯酰胺中，得到荧光可变色智能水凝胶；
其中，所述荧光染料可感应pH发生荧光变化且能够与所述聚丙烯酰胺形成氢键；所述荧光染料为5(6)-羧基荧光素。
2.根据权利要求1所述的酸碱度传感器，其特征在于，所述将荧光染料溶于丙烯酰胺水溶液并加入过硫酸铵之后，所述静置之前，还包括：
将溶有所述荧光染料的丙烯酰胺水溶液倒入模具中。
3.根据权利要求1所述的酸碱度传感器，其特征在于，所述激发光源的波长为442 nm。
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