聚集诱导发光超分子聚合物的光物理性能研究  

Photophysical Properties of Supramolecular Polymeric Nanoparticles with Aggregation-induced Emission

作　　者：黄媛媛[1,2] 高建峰[1] 彭慧晴 吴骊珠[2] 佟振合[2] 陈玉哲[2] 杨清正[3] Yuan-yuan Huang Jian-feng Gao Hui-qing Peng Li-zhu Wu Chen-ho Tung Yu-zhe Chen Qing-zheng Yang(Department of Chemistry, North University of China, Taiyuan 030051 College of Chemistry, Beo＇ing Normal University, Beo＇ing 100875 Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190)

机构地区：[1]中北大学理学院,太原030051 [2]中国科学院理化技术研究所光化学转换与功能材料重点实验室,北京100190 [3]北京师范大学化学学院,北京100875

出　　处：《高分子学报》2017年第1期112-120,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21474124,21272243;21525206);国家重点基础研究发展计划(973计划,项目号2013CB933800)资助项目

摘　　要：将一种含具有聚集诱导发光性能(AIE)的四苯乙烯的2-脲基-4[1H]-嘧啶酮衍生物(TPE-bis UPy)在氯仿中通过四重氢键作用组装形成的超分子聚合物,再以十六烷基三甲基溴化铵(CTAB)为表面活性剂利用微乳法制备了基于超分子聚合物的纳米球.这种纳米球的形貌通过SEM进行了表征,具有规整的形貌与尺寸.相比在溶液里,该超分子聚合物纳米球的荧光显著增强.通过改变单体的浓度得到了3种不同粒径的超分子聚合物纳米球,DLS表征其粒径分别为46、66和91 nm.将这3种不同粒径的TPE-bis UPy超分子聚合物纳米小球与带负电的曙红(EY)进行组装,由于静电相互作用曙红吸附在纳米球表面,拉近了TPE-bis UPy和曙红之间的距离,使得在组装体内TPE-bis UPy可以有效地将激发能传递给曙红分子,该体系的发光颜色从蓝色荧光变为黄绿色荧光,其能量传递效率分别为62%、55%和39%,洗去表面活性剂CTAB后静电作用减弱,能量传递效率显著降低,分别为46%、36%和33%.研究表明,TPE-bis UPy超分子聚合物纳米小球与曙红的组装体系内,静电作用越强能量传递效率越高;超分子聚合物纳米球粒径越小,能量传递效率越高;并且通过这种组装可以调控体系的发光颜色,能量传递也可以通过体系的发光颜色变化观察到.Tetraphenylethylene functionalized with 2-Ureido-4[1H]-pyrimidinone （TPE-bisUPy）, was synthesized and applied to build supramolecular polymers in CHC13. Nanoparticles of supramolecular polymer from TPE-bisUPy was prepared by using the miniemulsion method with cetyltrimethyl ammonium bromide （CTAB） as surfactant. These nanoparticles were characterized by SEM and DLS, confirming their uniform shape and size. The fluorescence of the nanoparticles significantly enhanced compared with that of TPE-bisUPy in the solution as well as that of the supramolecular polymers in organic solvent. The aggregation of TPE-bisUPy in the supramolecular polymeric nanoparticles leads to such fluorescence enhancement. The size of the nanoparticles was successfully controlled by adjusting the concentration of TPE-bisUPy. Supramolecular polymeric nanoparticles with three different sizes, 46, 66 and 91 nm as determined by DLS, were obtained. The photophysical properties of the supramolecular nanoparticles were tuned by their assembly with Eosin Y （EY）. The electrostatic assembly of negatively charged EY on the nanoparticles covered by positively charged surfactant of CTAB facilitated the excitation energy transfer from TPE-bisUPy to EY. The energy transfer efficiency of these three assemblies were 62%, 55% and 39%, respectively. Washed with water, the energy transfer efficiency of these assemblies decreased to 46%, 36% and 33%, respectively. These results indicated that the energy transfer process was dramatically influenced by the electrostatic interaction between the cationic CTAB and the negatively charged EY. The significance of the electrostatic interaction was also confirmed by replacing EY with positively charged Rhodamine 101 as the energy acceptor. Furthermore, the energy transfer was apparent by variation in the emission color of nanoparticles doped with EY upon UV lamp irradiation. The emission color of the assemblies could change from bright blue to bright green and to yellow color by adding different amounts of EY.

关 键 词：聚集诱导发光 超分子聚合物 能量传递 纳米球 

分 类 号：O631[理学—高分子化学]