CN110055057B - 一种基于柱[5]芳烃的超分子聚合物凝胶及其合成和应用 - Google Patents

一种基于柱[5]芳烃的超分子聚合物凝胶及其合成和应用 Download PDF

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CN110055057B
CN110055057B CN201910410723.1A CN201910410723A CN110055057B CN 110055057 B CN110055057 B CN 110055057B CN 201910410723 A CN201910410723 A CN 201910410723A CN 110055057 B CN110055057 B CN 110055057B
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姚虹
周琦
王姣
阚晓彤
魏太保
张有明
林奇
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Abstract

本发明提供了一种基于柱[5]芳烃的超分子聚合物凝胶，是以硫代乙酰肼修饰的柱[5]芳烃为主体，2,2’‑(1,6‑己基)‑双苯并咪唑为客体，在DMSO‑H2O溶液中完全溶解自组装后冷却至室温形成具有青白色聚集诱导发射的有机凝胶，该凝胶与铁离子或铜离子发生配位后其聚集态荧光猝灭，实现了对这两种金属离子的高灵敏检测。同时，将该超分子聚合物凝胶晾干后得到的固体粉末也显示出很强的白色荧光，且该粉末可直接用于快速检测等酸性气体，为高性能固态气体传感器的发展及应用提供了一种可能。

Description

一种基于柱[5]芳烃的超分子聚合物凝胶及其合成和应用
技术领域
本发明涉及一种超分子聚合物凝胶，尤其涉及一种基于柱[5]芳烃的超分子聚合物凝胶；本发明同时还涉及该超分子聚合物凝胶作为荧光传感器分子在荧光识别金属离子及快速检测H2S等酸性气体的应用，属于荧光检测技术领域。
背景技术
超分子聚合物是超分子化学与聚合物化学相结合的结果，被定义为延伸到分子之外的聚合物系统。超分子聚合物通过各种非共价相互作用而连接，包括氢键，金属配位，π-π堆积和主客体相互作用，这些非共价键作用力不仅使它们具有优于传统共价键聚合物的优点，而且具有许多特有的性质。近年来，新的具有聚集诱导发射性能的超分子聚合物引起了大家的关注，尤其是在凝胶或固体荧光材料领域，这些材料被广泛用于荧光传感器，生物成像，药物输送及擦拭材料等。
为了解决人类所面对的健康问题和环境问题，离子的超灵敏检测及高性能的固态气体传感器的开发至今仍是一个热点问题。铁离子和铜离子是人体必需的微量元素，但这些离子的过量不但影响人体健康，而且也会对环境造成严重污染。H2S是一种弱酸性气体，作为人体中内源性气体的转运体可调节心血管，神经元和免疫系统，而H2S水平的异常可能导致唐氏综合症，动脉和肺动脉高压以及糖尿病。因此，对这些分析物的高灵敏度及简便的检测显得尤为重要。
柱芳烃具有构建荧光诱导发射性能的超分子聚合物的潜力，它们易于合成与修饰，能使不同的官能团连接到柱芳烃上以产生合适的相互作用位点，此外，柱芳烃的富电子空腔和柱状结构可以包结具有适当大小或电子密度的客体分子。柱芳烃不仅能与合适的阳离子相互作用，而且还能与许多中性分子结合，被修饰的柱芳烃甚至可以与阴离子客体结合。由于这些有趣的、独特的性质，许多基于柱芳烃的超分子聚合物为超分子化学开辟了新的道路。
发明内容
本发明的目的是提供一种基于柱[5]芳烃的超分子聚合物凝胶的制备方法；
本发明的另一目的是对上述基于柱[5]芳烃的超分子聚合物凝胶对金属阳离子及H2S等酸性气体的识别性能。
一、基于柱[5]芳烃的超分子聚合物凝胶
本发明的超分子聚合物凝胶，是以硫代乙酰肼修饰的柱[5]芳烃（MTP5）为主体，2,2’-(1,6-己基)-双苯并咪唑（HB）为客体，在DMSO-H2O溶液中完全溶解自组装后冷却至室温形成具有青白色聚集诱导发射的有机凝胶MTP5-HB。
主体分子硫代乙酰肼修饰的柱[5]芳烃（MTP5）的结构式如下：
Figure DEST_PATH_IMAGE001
MTP5的合成方法参见文献：Q. Lin, Y. Q. Fan, P. P. Mao. Pillar[5]arene-Based Supramolecular Organic Framework with Multi-Guest Detection andRecyclable Separation Properties. Chem. Eur. J. 2018, 24, 777-783。客体分子HB的结构式如下：
Figure 126934DEST_PATH_IMAGE002
HB的合成方法参见文献：J. Qian, Y, Zhang, X.Yin. The synthesis andstudy of bis(1-octylbenzimidazoi-2-yl)alkane oil-soluble corrosion inhibitor.Chemistry, 2012, 75, 88-91。
DMSO-H2O溶液中，H2O 的体积百分数为含水30~40%。
主客体分子MTP5与HB的摩尔比为1:1；主客体分子MTP5与HB在DMSO-H2O溶液中的最低浓度为50mg/ml。
二、有机凝胶CWP5-HB的荧光性能
实验表明，单独的CWP5和HB均不能自组装形成凝胶，但将CWP5和HB混合于DMSO-H2O的二元溶液中可形成具有青白色聚集诱导发射的MTP5-HB有机凝胶。其最低成凝胶浓度为50 mg/mL，转熔温度为83~85℃。将MTP5-HB有机凝胶晾干后所得固体粉末具有很强的白色荧光。
图1为MTP5-HB随温度下降的荧光发射光谱图。如图1所示，随着温度的降低，MTP5-HB从溶液转变成凝胶，并且在300~700 nm范围内的荧光强度逐渐增强最终趋于稳定，说明这种荧光是聚集诱导发射（AIE）。
图2为向MTP5中逐渐滴加HB的核磁滴定谱图。通过1H-NMR滴定证明了HB穿入了柱芳烃MTP5的空腔形成了主客体包结物。并通过ESI-MS谱图证明了MTP5与HB的摩尔配比为1:1（见图3）。
图4为MTP5-HB, MTP5-HB-Fe及MTP5-HB-Cu的XRD图。从XRD谱图看到，MTP5-HB,在2θ=22.26，26.75，31.47和20.21处有衍射峰，分别对应的d值为：3.99 Å，3.33 Å，2.84 Å和4.39 Å，这些数据表明在MTP5-HB有机凝胶中存氢键作用以及柱间的π-π堆积作用。
三、MTP5-HB凝胶对阳离子的响应性能
1、MTP5-HB凝胶对金属阳离子检测
向MTP5-HB凝胶中分别加入0.5当量的Ca2+，Mg2+，Pb2+，Ni2+，Co2+，Hg2+，Zn2+，Cd2+，Ag+，Cu2+，Cr3+，Al3+，Ba2+，La3+，Eu3+，Fe3+的水溶液（0.1M），发现，只有Fe3+和Cu2+的加入能使凝胶的荧光猝灭（图5），而其他金属离子的加入不会引起明显的凝胶荧光变化。同时，我们采用累积加样法逐渐向该凝胶中滴加Fe3+或Cu2+，发现MTP5-HB凝胶在478 nm处的荧光发射逐渐降低直到荧光淬灭（图6、图7），并通过对荧光滴定数据的处理以及应用3σ/s公式，计算出MTP5-HB凝胶对Fe3+和Cu2+的最低检测限分别为2.68 ×10-9 M和1.55 ×10-9M，实现了对Fe3 +和Cu2+的高灵敏度检测。
2、MTP5-HB干凝胶粉末对气体的检测
称取5 mg MTP5-HB干凝胶的固体粉末于载玻片上，再将该载玻片分别置于含有醋酸、盐酸、硫化氢、三甲胺、氨气的集气瓶中，放置几分钟后可观察到，置于醋酸、盐酸、硫化氢气体中的干凝胶固体粉末的荧光明显降低，而在碱性气体三甲胺、氨气中的固体粉末荧光没有发生变化。上述实验现象表明MTP5-HB干凝胶粉末能实现在固体状态下快速检测酸性气体。
附图说明
图1为MTP5-HB随温度下降的荧光发射光谱图。
图2为向MTP5中逐渐滴加HB的核磁滴定谱图。
图3为MTP5-HB的ESI-MS谱图。
图4为MTP5-HB, MTP5-HB-Fe3+及MTP5-HB-Cu2+的XRD图。
图5为MTP5-HB凝胶对金属离子的荧光响应谱图。
图6为Fe3+对MTP5-HB凝胶的荧光滴定谱图。
图7为Cu2+对MTP5-HB凝胶的荧光滴定谱图。
具体实施方式
下面通过具体实施对本发明中超分子聚集凝胶的制备、凝胶态识别金属离子及固态识别酸性气体的应用做进一步说明。
实施例1、MTP5-HB凝胶的制备
分别称取0.0086 g（9.6 × 10-6mol）MTP5和0.0014 g（4.8 × 10-6mol）HB于凝胶中，向其中加入200 µL DMSO-H2O（含水35%）溶液，充分加热使其完全溶解后静止冷却至室温，形成50 mg/mL的青白色荧光凝胶MTP5-HB。
实施例2、MTP5-HB凝胶对金属离子的识别
分别移取5 mg有机凝胶MTP5-HB于一系列点滴板中，分别加入10 µLCa2+，Mg2+，Pb2 +，Ni2+，Co2+，Hg2+，Zn2+，Cd2+，Ag+，Cu2+，Cr3+，Al3+，Ba2+，La3+，Eu3+，Fe3+的水溶液（0.1M）；若有机凝胶的荧光发生猝灭，则说明加入的可能是Fe3+或Cu2+，若有机凝胶荧光没有发生明显变化，则说明加入的是其他金属离子。
实施例3、MTP5-HB干凝胶粉末检测酸性气体
称取5 mg MTP5-HB干凝胶的固体粉末于一系列载玻片上，再将载玻片分别置于含有醋酸、盐酸、硫化氢、三甲胺、氨气的集气瓶中，放置后观察凝胶MTP5-HB的荧光变化。若MTP5-HB干凝胶粉末的荧光明显降低，则集气瓶中的气体是酸性气体（醋酸，盐酸，硫化氢气体），若MTP5-HB干凝胶粉末的荧光保持不变，则集气瓶中的气体是碱性气体（三甲胺或氨气）。

Claims (9)

1.一种基于柱[5]芳烃的超分子聚合物凝胶，是以硫代乙酰肼修饰的柱[5]芳烃为主体，2,2’-(1,4-丁基)-双苯并咪唑为客体，在DMSO-H2O溶液中自组装后形成的具有青白色聚集诱导发射的有机凝胶；
主体分子硫代乙酰肼修饰的柱[5]芳烃的结构式如下：
Figure DEST_PATH_IMAGE002
客体分子HB的结构式如下：
Figure DEST_PATH_IMAGE004
。
2.如权利要求1所述一种基于柱[5]芳烃的超分子聚合物凝胶的合成方法，是将主体硫代乙酰肼修饰的柱[5]芳烃和客体2,2’-(1,4-丁基)-双苯并咪唑充分加热溶解于DMSO-H2O溶液中，然后静止冷却至室温，即得超分子聚合物凝胶。
3.如权利要求2所述一种基于柱[5]芳烃的超分子聚合物凝胶的合成方法，其特征在于：DMSO-H2O溶液中，H2O 的体积百分数为含水30~40%。
4.如权利要求2所述一种基于柱[5]芳烃的超分子聚合物凝胶的合成方法，其特征在于：主客体分子MTP5与HB的摩尔比为1:1。
5.如权利要求2所述一种基于柱[5]芳烃的超分子聚合物凝胶的合成方法，其特征在于：主客体MTP5与HB在DMSO-H2O溶液中的最低浓度为50mg/ml。
6.如权利要求1所述一种基于柱[5]芳烃的超分子聚合物凝胶在荧光识别阳离子中的应用。
7.如权利要求6所述一种基于柱[5]芳烃的超分子聚合物凝胶在荧光识别阳离子中的应用，其特征在于：移取超分子聚合物凝胶于一系列点滴板中，分别加入Ca2+，Mg2+，Pb2+，Ni2 +，Co2+，Hg2+，Zn2+，Cd2+，Ag+，Cu2+，Cr3+，Al3+，Ba2+，La3+，Eu3+，Fe3+的水溶液，只有Fe3+、Cu2+的加入能使超分子聚合物凝胶的荧光发生猝灭。
8.如权利要求1所述一种基于柱[5]芳烃的超分子聚合物凝胶在识别酸性气体中的应用。
9.如权利要求8所述一种基于柱[5]芳烃的超分子聚合物凝胶在识别酸性气体中的应用，其特征在于：称取超分子聚合物干凝胶的固体粉末于一系列载玻片上，再将载玻片分别置于含有醋酸、盐酸、硫化氢、三甲胺、氨气的集气瓶中，放置后若干凝胶粉末的荧光明显降低，则集气瓶中的气体是酸性气体醋酸，盐酸，硫化氢气体，若干凝胶粉末的荧光保持不变，则说明集气瓶中的气体是碱性气体三甲胺、氨气。
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