含磷酸酯侧链的超支化共轭聚合物纳米粒子的合成及其对己二胺的荧光检测

Hyperbranched conjugated polymer nanoparticles with phosphonate groups in the side chains for fluorescent detection of hexamethylendiamine

通过Suzuki细乳液聚合以及后功能化,制备了以四苯基乙烯和含磷酸酯侧链的芴为共轭单元、以胺活性二氰乙烯基为端基的超支化共轭聚合物纳米粒子HBCPN-P-DCV,并将其应用于醇中及含水体系中有机胺的荧光增强检测。与没有传感响应的仲胺和叔胺不同,烷基伯胺的加入导致HBCPN-P-DCV乙醇分散液的荧光极大增强(荧光增强可超过200倍),同时伴随着吸收及荧光颜色的明显改变。HBCPN-P-DCV对己二胺表现出最强的荧光增强响应,其检测限达5μmol·L^(-1)。利用核磁氢谱以及质谱证实了HBCPN-P-DCV的二氰乙烯基端基与烷基伯胺发生化学反应生成亚胺结构的检测机理。

Hyperbranched conjugated polymer nanoparticles with phosphonate groups as the side groups and amine-active dicyanovinyl as terminal groups( HBCPN-P-DCV) were prepared by a Suzuki polymerization in the form of a mini-emulsion. The initial construct was post-functionalization for architectural luminescence. The fluorescence "turn-on"sensing of organic amines in ethanol or water-contained system was evaluated. Comparing with secondary and tertiary amines,which had no effect on the absorption and fluorescence of HBCPN-P-DCV,primary alkylamine resulted in an over 200-fold fluorescence enhancement of the HBCPN-P-DCV construct with the change of absorption and fluorescence color. This HBCPNP-DCV system showed a stronger fluorescent response to hexamethylenediamine than other amines with the detection limit of 5 μmol·L-1. The formation of imine terminal group by the reaction between dicya-novinyl terminal groups and primary alkylamines was verified by 1 H NMR and MALDI-TOF MS analyses.