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  

Preparation of a pH-Responsive Porous Materials Functionalized by Pyridine Groups via the Heck Reaction

作　　者：杨文艳[1] 刘鸿志[1,2] 

机构地区：[1]特种功能聚集体材料教育部重点实验室,山东大学化学与化工学院,济南250100 [2]特种功能高分子材料及相关技术教育部重点实验室,华东理工大学,上海200237

出　　处：《化学学报》2015年第6期623-628,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21274081)资助~~

摘　　要：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 mm Hg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526nm;在p H=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.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 29 Si MAS NMR, 13 C 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-1by t-plot method, the material also exhibited good CO2 uptake of 2.96 wt% at 273 K/760 mm Hg. 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 p H-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 p H values in the p H 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.

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 

分 类 号：O657.3[理学—分析化学] TQ422[理学—化学]