CN109320454B - 一种双组分超分子有机凝胶及其金属凝胶的制备和应用 - Google Patents

一种双组分超分子有机凝胶及其金属凝胶的制备和应用 Download PDF

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CN109320454B
CN109320454B CN201811443350.XA CN201811443350A CN109320454B CN 109320454 B CN109320454 B CN 109320454B CN 201811443350 A CN201811443350 A CN 201811443350A CN 109320454 B CN109320454 B CN 109320454B
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林奇
杨海龙
孙小文
唐忠娣
张有明
魏太保
姚虹
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Northwest Normal University
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Abstract

本发明公开了一种双组分超分子有机凝胶因子，是将含西弗碱功能化的萘二甲酰亚胺与4‑氨基吡啶功能化的均苯三甲酰氯，在加热下充分溶解到DMSO‑H2O中，得透明溶液；冷却至室温，形成稳定的具有橘黄色聚集态荧光的双组分超分子有机凝胶MQ。向MQ中分别加入一系列阳离子溶液，只有Fe3+的加入使其荧光猝灭，因此MQ能专一选择性荧光识别Fe3+。将双组分超分子有机凝胶与六水合高氯酸铁加热溶解于DMSO‑H2O中，冷却后形成金属凝胶，当向金属凝胶中分别加入一系列阴离子，只有H2PO4 ‑的加入能使金属凝胶的荧光打开，且荧光由黑色变为橘黄色，从而实现了对H2PO4 ‑的超灵敏检测。

Description

一种双组分超分子有机凝胶及其金属凝胶的制备和应用
技术领域
本发明涉及一种由西弗碱功能化的萘二甲酰亚胺与4-氨基吡啶功能化的均苯三甲酰氯凝胶因子通过氢键、π-π作用形成具有强荧光的双组份超分子有机凝胶；本发明同时还涉及基于该超分子有机凝胶的金属凝胶在选择性荧光识Fe3+、H2PO4 -的应用，属于超分子有机凝胶领域。
背景技术
超分子有机凝胶是一种低分子量的有机化合物（凝胶因子）在有机溶剂中通过氢键、范德华力、π-π堆积作用及亲水-疏水作用等分子间弱相互作用自组装形成的超分子（软）材料。这种材料同时具有固体材料和液体材料特有的优点：超分子有机凝胶分子保持自己的化学性质，可以进行其在溶液中的一些反应，同时该凝胶材料又具有类似于固体的稳定，如易于保存等优点，因此，在超分子软材料领域具有广泛的应用。
最近几年，为金属离子在环境中寻找超灵敏检测分离的离子响应材料已经变得十分重要。到目前为止，有多种方法用来检测不同离子在环境中的存在，如原子吸收光谱法、荧光分析法等。但是这些方法操作起来比较复杂，而且设备价格昂贵，不宜大量投入实际应用中。因此，研究新的方法以实现在环境中有效地检测且分离不同离子仍然是一个具有挑战性的问题。具有刺激响应的超分子有机凝胶作为一种新兴的功能和智能材料，由于它本身具有的特殊性质和很好的应用前景，已经越来越被人们的关注。
Fe3+在细胞水平的许多生化过程中起着关键的作用，人体中缺少Fe3+会导致贫血、肝损伤、帕金森病和癌症等疾病，同时，Fe3+由于具有顺磁性的本质，导致它成为一种荧光猝灭剂，这就使人们很难研究出一种连续可逆的荧光传感器来检测分离Fe3+。H2PO4 -不仅在各种环境和生物学的应用中起着至关重要的作用，而且在信息传输和能量储存方面也扮演着重要的角色。
发明内容
本发明的目的是提供一种由含西弗碱功能化的萘二甲酰亚胺与4-氨基吡啶功能化的均苯三甲酰氯凝胶因子通过氢键、π-π作用形成具有强荧光的双组份超分子有机凝胶及其制备方法；
本发明的另一目的是提供一种该双组分超分子有机凝胶在单一选择性荧光识别铁离子（Fe3+）和连续识别磷酸二氢根（H2PO4 -）的应用。
一、双组分超分子有机凝胶
本发明的双组分超分子有机凝胶，是将含西弗碱功能化的萘二甲酰亚胺凝胶因子（标记为M）与4-氨基吡啶功能化的均苯三甲酰氯凝胶因子（标记为Q），在加热下按30~35mg/mL的质量体积比充分溶解到DMSO-H2O中得到透明溶液；冷却至室温形成稳定的双组分超分子有机凝胶（标记为MQ）。DMSO-H2O中，DMSO与H2O的体积比为3:1~1:1。
其中，西弗碱功能化的萘二甲酰亚胺的结构式为：
Figure DEST_PATH_IMAGE001
4-氨基吡啶功能化的均苯三甲酰氯的结构式为：
Figure 114956DEST_PATH_IMAGE002
MQ的结构式为：
Figure 100002_DEST_PATH_IMAGE003
实验表明，该双组分超分子有机凝胶MQ具有良好的稳定性，放置一周后双组分超分子有机凝胶MQ的形态保持不变。双组分超分子有机凝胶MQ的转溶温度为75~80℃。
图1为MQ在成凝胶过程中荧光强度随温度的变化（λex=415 nm）；图1的结果显示，双组分超分子有机凝胶MQ在溶胶状态下荧光较弱（MQ-Sol）；随着温度的降低，溶胶转化成凝胶，并产生强烈的橘黄色的聚集态荧光（MQ-Gel）。
二、双组分超分子有机凝胶MQ对阳离子的识别实验
1、MQ对Fe3+的荧光响应
在白色点滴板上分别取13份少量（约0.02g）的双组分超分子有机凝胶MQ，分别在这些双组分超分子有机凝胶上加入20μL的不同阳离子（C =0.1moL/L，Mg2+，Ca2+，Cr3+，Fe3+，Co2+，Ni2+，Cu2+，Zn2+，Ag+，Cd2+，Hg2+，Pb2+）的水溶液。然后在紫外灯下观察该双组分超分子有机凝胶的荧光变化。结果显示，超分子有机凝胶MQ在遇到Fe3+水溶液时荧光猝灭，而在遇到含其他阳离子的水溶液时，超分子有机凝胶MQ的荧光未猝灭且颜色不变（如图2所示）。因此，该双组分超分子有机凝胶MQ能专一选择性荧光识别Fe3+。同时，当在双组分超分子有机凝胶MQ中加入含Fe3+的固体待测样品时，它可以直接溶解待测样品而实现对铁离子的检测，这将简化样品的检测过程。因此，该材料的使用将大大简化铁离子的检测方法并降低检测成本。
2、双组分超分子有机凝胶MQ对Fe3+的荧光滴定实验
在微量荧光比色池中配制一份体积为250μL（凝胶浓度为30mg/mL）的双组分超分子有机凝胶MQ，向MQ中加入不同当量Fe3+的水溶液（C =0.1moL/L），测双组分超分子有机凝胶荧光强度的变化。随着Fe3+的逐渐加入，530nm处的荧光逐渐减弱并最终趋于稳定（如图3所示）；并且MQ对Fe3+的荧光光谱检测限为6.10×10-8M（如图4所示）。该检测限很低，达到了超灵敏检测的水平。说明MQ在环境中可以超灵敏检测Fe3+。
三、双组分超分子金属有机凝胶对磷酸二氢根的识别实验
1、双组分超分子金属有机凝胶的制备
将双组分超分子有机凝胶MQ与六水合高氯酸铁（超分子有机凝胶MQ与六水合高氯酸铁的摩尔比为1:1.5）一同加热溶解于DMSO-H2O中，冷却至室温后，形成了稳定的超分子金属有机凝胶，标记为MQ+Fe3+。DMSO-H2O中，DMSO与H2O的体积比为3:1~2:1。。双组分超分子有机凝胶MQ与六水合高氯酸铁按30~35mg/mL的质量体积比溶解于DMSO-H2O中。实验表明，该超分子金属有机凝胶MQ+Fe3+具有良好的稳定性，放置一周后其形态保持不变。
2、双组分超分子金属有机凝胶（MQ+Fe3+）对磷酸二氢根的识别实验
MQ+Fe3+对H2PO4 -的荧光响应实验：在白色点滴板上分别取14份少量（约0.02g）的双组分超分子金属有机凝胶MQ+Fe3+，然后在其基础之上分别加入20μL的各种阴离子（F-，Cl-，Br-，I-，N3 -，S2-，OH-，CN-， SCN-，H2PO4 -，AcO-，HSO4 -，ClO4 -，C=0.1mol/L），然后在紫外灯下观察该双组分超分子金属有机凝胶的荧光变化。结果发现，该超分子金属有机凝胶MQ+Fe3+只有在遇到H2PO4 -水溶液时荧光打开，在415nm的激发波下，荧光颜色由黑色为橘黄色，表明Fe3+被H2PO4 -竞争络合掉，从而使得超分子有机凝胶MQ+Fe3+的荧光颜色由黑色为橘黄色（如图5所示）。因此，该超分子金属有机凝胶MQ+Fe3+在水溶液中能荧光识别H2PO4 -。
MQ+Fe3+对H2PO4 -的滴定实验
在微量荧光比色池中配制一份体积为250μL（凝胶浓度为30mg/mL）的MQ+Fe3+，向其中加入不同当量H2PO4 -的水溶液（C=0.1moL/L），测双组分超分子有机凝胶荧光强度的变化。随着H2PO4 -的逐渐加入，530nm处的荧光逐渐增强并最后趋于稳定，并且MQ+Fe3+对H2PO4 -的荧光光谱检测限为1.56×10-7M（见图6、图7），说明MQ+Fe3+在环境中可以超灵敏检测H2PO4 -。
四、MQ对Fe3+和H2PO4 -的连续性识别机理
对于MQ对Fe3+和H2PO4 -的连续性识别机理，我们通过IR、XRD、SEM等进行了研究。IR表明（图8），M形成MQ后，-NH2、-NH、-C=O伸缩振动峰向低波数方向移动，说明有氢键作用。XRD表明（图9），2𝜽=23.434℃，d=3.794Å，说明存在π-π作用。SEM表明（图10），RQ形貌呈现螺旋状。IR表明，当向MQ中加入Fe3+会导致-NH2、-NH、-C=O伸缩振动峰向低波数移动（图11）；XRD表明（图12），π-π作用减弱。SEM表明（图13），MQ+ Fe3+形貌呈现块状，进一步说明，Fe3+在其中发生配位、形成阳离子π作用。IR表明，再向MQ+Fe3+中加入H2PO4 -会导致-NH2、-NH、-C=O伸缩振动峰移向低波数的位置；在XRD中，2𝜽=23.142℃，d=3.840Å，说明存在π-π作用再次出现；在MQ+Fe3+中加入H2PO4 -形貌又呈现螺旋状（如图14所示）。
综上所述，双组分超分子有机凝胶MQ超灵敏识别过程是通过新型的配位作用与阳离子π竞争实现的。当向MQ中加入Fe3+，由于Fe3+能与MQ产生阳离子π作用、配位作用；导致MQ的荧光猝灭；当向荧光猝灭的双组分超分子金属有机凝胶MQ+Fe3+中加入H2PO4 -时，由于H2PO4 -与Fe3+络合使MQ之间的螺旋结构再次恢复，导致荧光回到原来的现象，从而实现了对Fe3+和H2PO4 -连续可逆超灵敏检测。
附图说明
图1为MQ在成凝胶过程中荧光强度随温度的变化(λex=415 nm)；
图2为MQ对阳离子的全扫描图；
图3为MQ对Fe3+的荧光滴定(λex=415nm)；
图4为 MQ对Fe3+的拟合曲线；
图5为MQ+Fe3+对H2PO4 -的阴离子的全扫描图；
图6为MQ+Fe3+对H2PO4 -的荧光滴定(λex=415 nm)；
图7为MQ+Fe3+对H2PO4 -的拟合曲线；
图8为M、Q、MQ的红外光谱图；
图9为M、Q、MQ的XRD图；
图10为MQ的SEM图；
图11为MQ、MQ+Fe3+、MQ+Fe3++H2PO4 -的红外光谱图；
图12为MQ、MQ+Fe3+、MQ+Fe3++H2PO4 -的XRD图；
图13为MQ+Fe3+的SEM图；
图14为MQ+Fe3++H2PO4 -的SEM图。
具体实施方式
下面通过具体实施例对本发明双组分超分子有机凝胶因子MQ的合成，以及单一性选择识别Fe3+与H2PO4 -的方法作进一步说明。
实施例1、双组分超分子有机凝胶MQ的合成
（1）基于西弗碱功能化的萘二甲酰亚胺凝胶因子M的合成：向100mL圆底烧瓶中分别加入对苯二胺（1.08 g，10~10.5mmol），1,8-萘二甲酸酐（1.98g，10~10.5mmol）和100 mL乙醇，在80 ℃加热回流搅拌24h。反应结束后抽滤，用热的乙醇淋洗，抽滤烘干，得到黄色粉末中间体；然后，100mL圆底烧瓶中分别取黄色粉末中间体（1.45g，5~5.5mmol）、2-羟基萘甲醛（0.88g，5~5.5mmol）、1.5mL的冰CH3COOH和60mL乙醇，在80℃加热回流搅拌24h，反应结束后抽滤，用热的乙醇淋洗，抽滤烘干，得到黄色粉末M，产率为：90%；
（2）4-氨基吡啶功能化的均苯三甲酰氯凝胶因子Q的合成：向100 mL圆底烧瓶中加入4-氨基吡啶（0.75 g，8.0~8.05mmol）与CHCl3（40 mL），在恒压漏斗中加入均苯三甲酰氯（0.52 g，5.0 ~5.05mmol）与CHCl3（40 mL），使其慢慢滴入圆底烧瓶内，过夜；抽滤得到白色固体Q，产率为：80%；
（3）双组分超分子有机凝胶（MQ）的合成：称取MQ（0.005g），加入到100μL的DMSO与60μL的H2O中，在加热下使其充分溶解，得透明溶液；冷却至室温时，溶液形成稳定的双组分超分子有机凝胶MQ。MQ在溶胶状态下荧光较弱（MQ-Sol）；随着温度的降低，溶胶转化成凝胶，并产生强烈的橘黄色的聚集态荧光（MQ-Gel）。
实施例2、MQ识别实验Fe3+
在白色点滴板上分别取13份少量（约0.02g）的有机凝胶MQ，分别在其上加入20μL的不同阳离子（C=0.1moL/L，Mg2+，Ca2+，Cr3+，Fe3+，Co2+，Ni2+，Cu2+，Zn2+，Ag+，Cd2+，Hg2+，Pb2+）的水溶液。在紫外灯下观察其荧光颜色变化，如果有机凝胶MQ的荧光颜色由橘黄色变为黑色，则说明加入的是Fe3+溶液，若MQ的荧光颜色不变，则说明加入的是其他阳离子的水溶液。
实施例3、双组分超分子金属有机凝胶（MQ+Fe3+）的制备及识别H2PO4 -
先称取双组分超分子金属有机凝胶MQ（0.005g），再称取六水合高氯酸铁（0.0158g）一同加入到100μL的DMSO与60μL的H2O中，加热使其溶解，冷却至室温后，形成了稳定的双组分超分子金属有机凝胶（MQ+Fe3+）。
在上述黑色的超分子金属有机凝胶MQ-Fe3+中，分别加入20μL的各种阴离子（F-，Cl-，Br-，I-，N3 -，S2-，OH-，CN-， SCN-，H2PO4 -，AcO-，HSO4 -，ClO4 -,C=0.1mol/L），若超分子金属有机凝胶MQ-Fe3+的荧光打开，且荧光由黑色变为橘黄色，说明加入的是H2PO4 -的水溶液；若发现双组分超分子金属有机凝胶的荧光未打开，说明加入的不是H2PO4 -的水溶液。

Claims (9)

1.一种双组分超分子有机凝胶，其结构式如下：
Figure 632702DEST_PATH_IMAGE002
。
2.如权利要求1所述一种双组分超分子有机凝胶的合成，是将含西弗碱功能化的萘二甲酰亚胺与4-氨基吡啶功能化的均苯三甲酰氯，在加热下充分溶解到DMSO-H2O中，得透明溶液；冷却至室温，形成稳定的具有橘黄色聚集态荧光的双组分超分子有机凝胶；西弗碱功能化的萘二甲酰亚胺的结构式为：
Figure DEST_PATH_IMAGE003
4-氨基吡啶功能化的均苯三甲酰氯的结构式为：
Figure 720482DEST_PATH_IMAGE004
。
3.如权利要求2所述一种双组分超分子有机凝胶的合成，其特征在于：西弗碱功能化的萘二甲酰亚胺与4-氨基吡啶功能化的均苯三甲酰氯的摩尔比为3:1。
4.如权利要求2所述一种双组分超分子有机凝胶的合成，其特征在于：DMSO-H2O中，DMSO与H2O的体积比为3:1~2:1。
5.如权利要求2所述一种双组分超分子有机凝胶的合成，其特征在于：西弗碱功能化的萘二甲酰亚胺与4-氨基吡啶功能化的均苯三甲酰氯按30~35mg/mL的质量体积比溶解于DMSO-H2O中。
6.如权利要求1所述一种双组分超分子有机凝胶在单一选择性荧光识别Fe3+中的应用，其特征在于：在双组分超分子有机凝胶上分别加入Fe3+，Hg2+，Ag+，Ca2+，Cu2+，Co2+，Ni2+，Cd2+，Pb2+，Zn2+，Cr3+，Mg2+的水溶液，只有Fe3+的加入能使双组分超分子有机凝胶的荧光猝灭，而其他阳离子的加入均不能使双组分超分子有机凝胶的荧光发生变化；所述应用是以非疾病诊断或治疗为目的。
7.一种基于如权利要求1所述双组分超分子有机凝胶的超分子金属有机凝胶，是将权利要求1所述双组分超分子有机凝胶与六水合高氯酸铁以1:1~1:2的摩尔比，加热溶解于DMSO-H2O中，冷却至室温后，形成了稳定的金属双组分超分子有机凝胶。
8.如权利要求7所述超分子金属有机凝胶，其特征在于：DMSO-H2O中，DMSO与H2O的体积比为3:1~2:1；双组分超分子有机凝胶与六水合高氯酸铁按30~35mg/mL的质量体积比溶解于DMSO-H2O中。
9.如权利要求8所述超分子有机金属凝胶在检测H2PO4 -的应用，其特征在于：分别在超分子金属有机凝胶上加入F-，Cl-，Br-，I-，N3 -，S2-，OH-，CN-， SCN-，H2PO4 -，AcO-，HSO4 -，ClO4 -的水溶液，只有H2PO4 -的加入能使超分子金属有机凝胶的荧光打开，且荧光由黑色变为橘黄色；所述应用是以非疾病诊断或治疗为目的。
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