Yang Po-Chih, Li Si-Qiao, Chien Yueh-Han, Tao Ta-Lun, Huang Ruo-Yun, Chen Hsueh-Yu
Department of Chemical Engineering and Materials Science, Yuan Ze University, Chung-Li, Taoyuan City 32003, Taiwan.
Polymers (Basel). 2017 Sep 7;9(9):427. doi: 10.3390/polym9090427.
We report the responsive fluorescence chemosensory phenomena of a carbazole-functionalized crosslinked polymer (PCaT) with pendent terpyridine (tpy) groups as receptors of metal ions. The polymer was synthesized using Heck polymerization between 3,6-dibromide groups in a carbazole-based polymer (PC2Br) and divinyl tpy monomer. The effects of the polymeric structure on the optical and chemosensory properties of the PCaT were compared with those of a carbazole-tpy alternating conjugated polymer (PCT). Photoluminescence titrations demonstrated that the PCaT and PCT had the high sensing ability toward Fe ions, with Stern⁻Volmer constants of 8.10 × 10⁴ and 6.68 × 10⁴ M, respectively. The limit of detection (LOD) toward Fe of the PCaT and PCT was estimated to be 1.31 × 10 and 1.81 × 10 M, respectively, and the superior LOD of the PCaT was ascribed to its lowly crosslinked structure. The fluorescence of the solutions of these polymers that were quenched by Fe ions recovered when trace CN anions were added because of the high stability constant of the CN⁻Fe complex. Micellar aggregates with a mean diameter of approximately 239.5 nm were formed by dissolving the PCaT in tetrahydrofuran (THF) solution. Our results suggest that the PCaT is a promising material for chemosensory applications.
我们报道了一种咔唑官能化的交联聚合物（PCaT）的响应性荧光化学传感现象，该聚合物带有侧基三联吡啶（tpy）基团作为金属离子受体。该聚合物通过咔唑基聚合物（PC2Br）中的3,6 - 二溴基团与二乙烯基tpy单体之间的Heck聚合反应合成。将PCaT的聚合物结构对其光学和化学传感性能的影响与咔唑 - tpy交替共轭聚合物（PCT）进行了比较。光致发光滴定表明，PCaT和PCT对Fe离子具有高传感能力，其Stern - Volmer常数分别为8.10×10⁴和6.68×10⁴ M。PCaT和PCT对Fe的检测限（LOD）分别估计为1.31×10 和1.81×10 M，PCaT的优异LOD归因于其低度交联结构。由于CN⁻Fe络合物的高稳定性常数，当加入痕量CN阴离子时，这些被Fe离子猝灭的聚合物溶液的荧光得以恢复。通过将PCaT溶解在四氢呋喃（THF）溶液中形成了平均直径约为239.5 nm的胶束聚集体。我们的结果表明，PCaT是一种有前途的化学传感应用材料。
