通过Heck偶联反应制备具有pH响应的吡啶基团功能化的多孔材料
收稿日期: 2015-01-19
网络出版日期: 2015-03-04
基金资助
项目受国家自然科学基金(No. 21274081)资助.
Preparation of a pH-Responsive Porous Materials Functionalized by Pyridine Groups via the Heck Reaction
Received date: 2015-01-19
Online published: 2015-03-04
Supported by
Project supported by the National Natural Science Foundation of China (No. 21274081).
四(4-苯乙烯基)硅烷(TVBS)和溴代二苯乙烯基吡啶(Br-DSP)通过Heck偶联反应构筑以共价键连接的具有pH响应的新型多孔材料. 材料具有良好的孔性能和热稳定性能, 其比表面积为467 m2·g-1, 孔体积为0.41 cm3·g-1. 所得的多孔材料在273 K/760 mmHg条件下的CO2吸附量为2.96 wt%. 二苯乙烯基吡啶(DSP)单元的引入, 使多孔材料具有优异的荧光性能, 其中N原子作为质子化中心, 使材料具有pH响应性. 在固体状态下, 材料的荧光最大发射波长在526 nm; 在pH＝1.00～4.50范围内, 材料的荧光最大发射波长和相应的pH值成线性关系, 表明该材料可用于酸性溶液的精确地快速检测.
关键词： 多孔材料; pH响应性; 荧光性能; 溴代二苯乙烯基吡啶; 四(4-苯乙烯基)硅烷
杨文艳 , 刘鸿志 . 通过Heck偶联反应制备具有pH响应的吡啶基团功能化的多孔材料[J]. 化学学报, 2015 , 73(6) : 623 -628 . DOI: 10.6023/A15010054
A novel covalent-linked pH-responsive porous polymer (CPP) was prepared successfully using the tetrahedron tetrakis(4-vinylbenzyl)silane and brominated distyrylpyridine (Br-DSP) as the building blocks via the Heck coupling reaction. The structure of the resulting material was characterized by FTIR, solid-state 29Si MAS NMR, 13C CP/MAS NMR and elemental analysis. The material possessed good porosity, the porosity parameters were evaluated by nitrogen adsorption and desorption measurement, thereinto, pore-size distribution (PSD) was characterized by nonlocal density functional theory (NL-DFT). The Brunauer-Emmett-Tellerspecific surface area of CPP was 467 m2·g-1 and total pore volume of 0.41 cm3·g-1 by t-plot method, the material also exhibited good CO2 uptake of 2.96 wt% at 273 K/760 mmHg. The powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM) measurements were used to investigate the porous polymer. CPP exhibited high thermal stability with decomposition temperature at 462 ℃ (10 wt%) by thermogravimetric analysis (TGA). By the introduction of the conjugated structures of distyrylpyridine groups, the porous polymer showed luminescence with the maximum emission at ca. 526 nm in the solid state. Additionally, CPP exhibited an excellent pH-responsive property due to the protonated nitrogen centers of pyridine groups in the porous structure, a linear relation was established between the maximum luminescent emission wavelengths (λem) of the porous polymer in buffer solutions and the corresponding pH values in the pH range from 1.00 to 4.50, the correlation coefficient of the straight line was 0.992. Therefore, this porous material can be utilized as an promising fluorescent probe in the rapid test systems.
[1] Morris, R. E.; Wheatley, P. S. Angew. Chem., Int. Ed. 2008, 47, 4699.
[2] McKeown, N. B.; Budd, P. M. Chem. Soc. Rev. 2006, 35, 675.
[3] Wu, D.; Xu, F.; Sun, R.; Fu, R.; He, H.; Matyjaszewski, K. Chem. Rev. 2012, 112, 3959.
[4] Soler-Illia, G.; Sanchez, C.; Lebeau, B.; Patarin, J. Chem. Rev. 2002, 102, 4093.
[5] (a) Patra, A.; Scherf, U. Chem. Eur. J. 2012, 18, 10074.
(b) Xu, Y.; Jin, S.; Xu, H.; Nagai, A.; Jiang, D. Chem. Soc. Rev. 2013, 42, 8012.
[6] (a) Weber, J.; Thomas, A. J. Am. Chem. Soc. 2008, 130, 6334.
(b) Chen, L.; Honsho, Y.; Seki, S.; Jiang, D. L. J. Am. Chem. Soc. 2010, 132, 6742.
(c) Jiang, J. X.; Trewin, A.; Adams, D. J.; Cooper, A. I. Chem. Sci. 2011, 2, 1777.
(d) Liu, X. M.; Xu, Y. H.; Jiang, D. L. J. Am. Chem. Soc. 2012, 134, 8738.
(e) Wang, D.; Li, L.; Yang, W.; Zuo, Y.; Feng, S.; Liu, H. RSC Adv. 2014, 4, 59877.
[7] (a) Jiang, X.; Yin, J.; Murakami, Y.; Kaji, M. J. Photopolym. Sci. Technol. 2009, 22, 351.
(b) Pivovarenko, V. G.; Grygorovych, A. V.; Valuk, V. F.; Doroshenko, A. O. J. Fluoresc. 2003, 13, 479.
(c) Yang, W.; Jiang, X.; Liu, H. RSC Adv. 2015, 5, 12800.
(d) Grygorovych, O. V.; Moskalenko, S. M.; Marekha, B. A.; Doroshenko, A. O. J. Fluoresc. 2010, 20, 115.
[8] (a) Yuan, D.; Lu, W.; Zhao, D.; Zhou, H. C. Adv. Mater. 2011, 23, 3723.
(b) Holst, J. R.; Stöckel, E.; Adams, D. J.; Cooper, A. I. Macromolecules 2010, 43, 8531.
(c) Ben, T.; Ren, H.; Ma, S.; Cao, D.; Lan, J.; Jing, X.; Wang, W.; Xu, J.; Deng, F.; Simmons, J. M.; Qiu, S.; Zhu, G. Angew. Chem., Int. Ed. 2009, 48, 9457.
[9] (a) Wang, D.; Yang, W.; Li, L.; Zhao, X.; Feng, S.; Liu, H. J. Mater. Chem. 2013, 1, 13549.
(b) Yang, W.; Wang, D.; Li, L.; Liu, H. Eur. J. Inorg. Chem. 2014, 2976.
(c) Sengupta, P.; Zhang, H.; Son, D. Y. Inorg. Chem. 2004, 43, 1828.
[10] (a) Wang, D.; Xue, L.; Li, L.; Deng, B.; Feng, S.; Liu, H.; Zhao, X. Macromol. Rapid Commun. 2013, 34, 861.
(b) Wu, Y.; Wang, D.; Li, L.; Yang, W.; Feng, S.; Liu, H. J. Mater. Chem. 2014, 2, 2160.
[11] (a) Zhao, Y.; Cheng, Q.; Zhou, D.; Wang, T.; Han, B. J. Mater. Chem. 2012, 22, 11509.
(b) Feng, L.; Chen, Q.; Zhu, J.; Liu, D.; Zhao, Y.; Han, B. Polym. Chem. 2014, 5, 3081.
(c) Chen, Q.; Luo, M.; Hammershøj, P.; Zhou, D.; Han, Y.; Laursen, B. W.; Yan, C.; Han, B. J. Am. Chem. Soc. 2012, 134, 6084.
(d) Wang, W.; Yan, Z.; Yuan, Y.; Sun, F.; Zhao, M.; Ren, H.; Zhun, G. Acta Chim. Sinica 2014, 72, 557. (王维, 闫卓君, 元野, 孙福兴, 赵明, 任浩, 朱广山, 化学学报, 2014, 72, 557.)
[12] (a) Kobayashi, F.; Ikeura, H.; Odake, S.; Tanimoto, S.; Hayata, Y. LWT-Food Sci. Technol. 2012, 48, 330.
(b) Chen, Y.-C.; Xie, R.; Chu, L.-Y. J. Membr. Sci. 2013, 442, 206.
[13] Zhang, H.; Bai, S.; Sun, J.; Han, J.; Guo, Y. Mater. Res. Bull. 2014, 53, 266.
[14] (a) Lindqvist, J.; Nyström, D.; Östmark, E.; Antoni, P.; Carlmark, A.; Johansson, M.; Hult, A.; Malmström, E. Biomacromolecules 2008, 9, 2139.
(b) Liu, S.; Wang, L.; Liu, B.; Song, Y. Polymer 2013, 54, 3065.
[15] Yameen, B.; Ali, M.; Neumann, R.; Ensinger, W.; Knoll, W.; Azzaroni, O. Nano Lett. 2009, 9, 2788.
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