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化学进展 2019, Vol. 31 Issue (11): 1509-1527 DOI: 10.7536/PC190734 前一篇   后一篇

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爆炸物检测用荧光聚合物材料

吴晓甫, 童辉**(), 王利祥**()   

  1. 中国科学院长春应用化学研究所 高分子物理与化学国家重点实验室 长春 130022
  • 收稿日期:2019-07-25 出版日期:2019-11-15 发布日期:2019-10-23
  • 通讯作者: 童辉, 王利祥
  • 基金资助:
    国家自然科学基金项目(51833009); 国家自然科学基金项目(21574131); 国家自然科学基金项目(91333205); 国家自然科学基金项目(21674111); 国家自然科学基金项目(21322403)
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Fluorescent Polymer Materials for Detection of Explosives

Xiaofu Wu, Hui Tong**(), Lixiang Wang**()   

  1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:2019-07-25 Online:2019-11-15 Published:2019-10-23
  • Contact: Hui Tong, Lixiang Wang
  • About author:
    ** E-mail: (Hui Tong);
    (Lixiang Wang)
  • Supported by:
    National Natural Science Foundation of China(51833009); National Natural Science Foundation of China(21574131); National Natural Science Foundation of China(91333205); National Natural Science Foundation of China(21674111); National Natural Science Foundation of China(21322403)

作为荧光传感材料,荧光聚合物不仅具有传感单元多、荧光亮度高、光稳定性好等特点,而且方便制备荧光传感薄膜,易于实现器件化,在爆炸物荧光检测中得到了广泛的研究与应用。近年来,随着荧光聚合物从传统的线型结构向支化和多孔网络结构的拓展,以及各种功能单元的引入,大量的新型荧光聚合物有效地提升了爆炸物检测的灵敏度、选择性和响应速度等性能。本综述从线型聚合物、支化聚合物、多孔聚合物三类体系出发,总结和评述了用于爆炸物荧光检测的线型共轭与非共轭聚合物、树枝状分子与超支化聚合物、无定形与结晶型多孔聚合物等典型体系的分子结构设计策略、功能特点以及传感性能,并展望了荧光聚合物未来在爆炸物检测应用中所面临的机遇和挑战。

关键词： 荧光聚合物, 爆炸物, 荧光检测, 线型聚合物, 树枝状分子, 超支化聚合物, 多孔有机聚合物

As fluorescent sensing materials, fluorescent polymers not only have many sensing units, high brightness and good light stability, but also facilitate the fabrication of fluorescent sensing films, which are easy to implement devices. Therefore, fluorescent polymers have been widely studied and applied in fluorescence detection of explosives. In recent years, a large number of fluorescent polymers with various functional units have been developed, and their structures have evolved from common linear structures to branched and porous network structures, which have effectively improved the sensitivity, selectivity and response rate of explosive detection. This review is aimed to summarize the research progress on fluorescent polymers used for detection of explosives, including linear polymers, branched polymers and porous polymers. The emphasis of this review is especially focused on the structure design strategies, functional characteristics and sensing performances of typical linear conjugated and non-conjugated polymers, dendrimers and hyperbranched polymers and amorphous and crystalline porous polymers. Finally, the future opportunities and challenges of fluorescent polymers in application of explosive detection are presented.

Key words: fluorescent polymers, explosives, fluorescence detection, linear polymers, dendrimers, hyperbranched polymers, porous organic polymers
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图1 主链含五蝶烯单元和稠环芳烃的共轭聚合物[14, 17~20]
Fig. 1 Conjugated polymers with pentiptycene and polycyclic polycyclic aromatic hydrocarbons in the backbones[14, 17~20]
图2 主链含AIE单元的共轭聚合物[21, 22, 28]
Fig. 2 Conjugated polymers containing aggregation-induced emission(AIE) units in the backbones[21, 22, 28]
图3 具有大位阻侧链的共轭聚合物[29,30,31,32,33]
Fig. 3 Conjugated polymers with bulky side chains[29,30,31,32,33]
图4 具有杯[4]芳烃侧链的共轭聚合物[34,35]
Fig. 4 Conjugated polymers with calix[4]arene as side chains[34,35]
图5 侧链带有离子基团的水溶性共轭聚合物[36,38,39]
Fig. 5 Conjugated polymers with ionic side chains[36,38,39]
图6 侧链具有荧光团的非共轭聚合物[40,45]
Fig. 6 Nonconjugated polymers with fluorophores in side chains[40,45]
图7 主链具有荧光团及无荧光团的非共轭聚合物[46,47,48,49,50,51]
Fig. 7 Nonconjugated polymers with fluorophores in backbones and without fluorophores[46,47,48,49,50,51]
图8 基于齐聚芴树枝和噻吩-苯树枝的共轭树枝状分子[53, 55~57]
Fig. 8 Conjugated dendrimers based on fluorene dendrons and thiophene-benezene dendrons[53, 55~57]
图9 基于咔唑树枝的共轭型树枝状分子[59. 60]
Fig. 9 Conjugated dendrimers based on carbazole dendrons[59. 60]
图10 含荧光团的非共轭树枝状分子[61. 62]
Fig. 10 Nonconjugated dendrimers containing fluorophores[61. 62]
图11 无荧光团的非共轭树枝状分子[64. 65]
Fig. 11 Nonconjugated dendrimers without fluorophores[64. 65]
图12 基于噻咯单元的AIE型超支化聚合物[68. 69]
Fig. 12 AIE-type hyperbranched polymers based on silole units[68. 69]
图13 基于四苯基乙烯单元的AIE型超支化聚合物[70, 71,74,76]
Fig. 13 AIE-type hyperbranched polymers based on tetraphenylethylene units[70, 71, 74, 76]
图14 非AIE型荧光超支化共轭聚合物[77,78,79,80]
Fig. 14 NonAIE-type fluorescent hyperbranched polymers[77,78,79,80]
图15 荧光超支化共轭聚合物纳米粒子[81,82,83,84]
Fig. 15 Fluorescent hyperbranched conjugated polymer nanoparticles[81,82,83,84]
图16 非共轭的荧光超支化聚合物[85,86,87,88]
Fig. 16 Fluorescent hyperbranched nonconjugated polymers[85,86,87,88]
图17 Yamamoto偶联反应制备的共轭多孔聚合物[97,98,99]
Fig. 17 Conjugated porous polymers prepared by Yamamoto coupling reaction[97,98,99]
图18 Heck偶联聚合制备的共轭多孔聚合物[100,101]
Fig. 18 Conjugated porous polymers prepared by Heck coupling reaction[100,101]
图19 Friedel-Crafts偶联反应制备的共轭多孔聚合物[102,103,104]
Fig. 19 Conjugated porous polymers prepared by Friedel-Crafts coupling reaction[102,103,104]
图20 氧化偶联反应制备的共轭多孔聚合物[105, 106]
Fig. 20 Conjugated porous polymers prepared by oxidation coupling reaction[105, 106]
图21 细乳液Suzuki偶联反应制备的可溶液加工的共轭多孔聚合物纳米粒子[108, 109]
Fig. 21 Solution-processable conjugated porous polymer nanoparticles prepared by Suzuki coupling reaction in miniemulsion[108, 109]
图22 在烯丙基硅烷修饰的SiO2基底上进行烯烃复分解反应制备的共轭多孔聚合物薄膜[112]
Fig. 22 Conjugated porous polymer films prepared by olefin metathesis reaction on alylsilane-functionalized SiO2 substrates[112]
图23 Sonogashira偶联反应制备的共轭多孔聚合物[111, 113, 114]
Fig. 23 Conjugated porous polymers prepared by Sonogashira coupling reaction[111, 113, 114]
图24 电化学聚合反应制备的共轭多孔聚合物[115. 116]
Fig. 24 Conjugated porous polymers prepared by electrochemical polymerization[115. 116]
图25 非共轭多孔聚合物[118,119,120]
Fig. 25 Nonconjugated porous polymers[118,119,120]
图26 硼酸缩合反应制备的三维结晶多孔聚合物材料[123, 124]
Fig. 26 Three demensional crystalline porous polymers prepared by boronic acid condensation reaction[123, 124]
图27 席夫碱缩合反应制备的COFs材料[125,126,127,128]
Fig. 27 Covalent organic frameworks(COFs) prepared by Schiff-base condensation reaction[125,126,127,128]
图28 酰亚胺化反应和Michael加成-消除反应制备的COFs[129, 130]
Fig. 28 COFs prepared by imidization reaction and Michael addition-elimination reaction[129, 130]
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摘要

爆炸物检测用荧光聚合物材料