Key Lab of Colloid and Interface Chemistry (Shandong University) Ministry of Education, Shandong University, Jinan 250100, PR China.
Langmuir. 2010 Mar 2;26(5):3555-61. doi: 10.1021/la904052k.
A fluorescent material with methylene viologen units bonded into the pore walls of the mesoporous MCM-48 silica is synthesized using the method of periodic mesoporous organosilicas with bridging groups (PMOs), in which the methylene viologen units are located within the channel walls through the cohydrolysis and cocondensation of dichloride of N,N'-bis(triethoxysilylmethyl)-4,4'-bipyridinium (VP) and tetraethoxysilane (TEOS). It is found that the suspension of the hybrid emits fluorescence at ca. 380 and 420 nm, which is attributed to the S(1) state (pi* --> pi) of the viologen and the charge-transfer complex between the bipyridinium units as electron acceptor and accompanying halide (Br(-), Cl(-)) as donor components, respectively. The fluorescent emission intensity increases with increasing the amount of the VP covalently bonded to MCM-48 framework. The fluorescent intensity of VP adsorbed on the surface of the pore channel of MCM-48 was greatly weaker than that of the hybrid MCM-48-VP at the same molar ratio of TEOS to VP. No fluorescence was observed for pure VP. The different fluorescent intensity is ascribed to the fact that restricted degree of the rotation between two pyridine rings is different. It could be prospected that this material is potentially applied in drug delivery and fluorescence probing for medical diagnosis and synchronous therapy.
一种将亚甲二氧基乙烯单元键合到介孔 MCM-48 硅孔壁中的荧光材料,是通过带有桥接基团的周期性介孔有机硅(PMOs)的方法合成的,其中亚甲二氧基乙烯单元通过 N,N'-双(三乙氧基甲硅烷基甲基)-4,4'-联吡啶二氯化物(VP)和四乙氧基硅烷(TEOS)的共水解和共缩合而位于通道壁内。发现该杂化物的悬浮液在约 380nm 和 420nm 处发射荧光,这归因于二聚体的 S(1)态(pi* --> pi)和联吡啶单元作为电子受体与伴随的卤化物(Br(-)、Cl(-))作为供体部分之间的电荷转移络合物。与共价键合到 MCM-48 骨架上的 VP 的量成正比,荧光发射强度增加。在 TEOS 与 VP 的相同摩尔比下,VP 吸附在 MCM-48 孔道表面上的荧光强度远弱于杂化 MCM-48-VP。纯 VP 没有观察到荧光。不同的荧光强度归因于两个吡啶环之间的旋转受限程度不同。可以预期,这种材料在药物输送和荧光探测方面具有潜在的应用,可用于医学诊断和同步治疗。