水热法制备非共轭聚集诱导发光聚合物及其在Fe^3+检测中的应用

Non-conjugated AIE Polymers Prepared by Hydrothermal Reaction and Its Application in Fe^3+Detection

以“自稳定沉淀聚合”制备的聚马来酸酐-醋酸乙烯酯线性交替共聚物(PMV)为原料,利用水热法制得3种新型非共轭聚集诱导发光(AIE)聚合物.通过荧光光谱、紫外-可见光光谱、傅里叶变换红外光谱(FTIR)、X射线光电子能谱分析(XPS)等表征方法,研究了3种聚合物的荧光和结构特性,并考察了其在Fe3+检测的应用.实验结果表明:3种PMV衍生物均具有AIE性质,随着水热时间的延长,聚合物的发光颜色从蓝色红移至黄色,且水热1 h所得产物固体的绝对量子产率最高,可达17.05%;所得非共轭AIE聚合物可用于Fe3+检测,当Fe3+浓度为5~200μmol/L时,猝灭效率与Fe3+浓度符合线性关系,调整确定系数为0.9922,最低检测限可低至1.22μmol/L.

In recent years,non-conjugated aggregation-induced emission(AIE)polymers without traditionalπ-aromatic chromophores have attracted much attention.Although there have been many relevant studies focused on oxygen-,nitrogen-,and heteroatom-containing systems,there is still a lack of researches on those polymers with only oxygen groups.In this study,three novel non-conjugated AIE polymers were prepared with hydrothermal method,in which the poly(maleic anhydride-alt-vinyl acetate)(PMV)prepared by“self-stable precipitation polymerization”is regarded as the raw material.The fluorescence and structural properties of these three polymers and their applications in Fe3+detection were investigated by using fluorescence spectroscopy,UV-Vis spectroscopy,FTIR,XPS and other characterization methods.It is found that all PMV derivatives have typical AIE characteristcs,and their luminious color is shifted from blue to yellow with the increase of hydrothermal time,in which the maximum emission peaks of these three polymers were 488,527 and 608 nm,respectively.The highest absolute quantum yield of 17.05%is obtained under the condition that the hydrothermal time is 1 h.Structural characterizations exhibit that none of the three polymers had conjugated groups,and the fluorescent mechanism may be ascribed to the intra-and inter-molecular interaction of oxygen-containing groups caused by hydrothermal reaction.Furthermore,the obtained non-conjugated AIE polymers can be effectively used for Fe3+detection.Particularly,when the Fe3+concentration is 5−200μmol/L,there is a linear relationship between the quenching efficiency and the Fe3+concentration,which could be conformed to Stern-Volmer equation.In this case,the adjustment coefficient of determination is 0.9922,and the limit of detect can be as low as 1.22μmol/L.This study provided a new strategy to prepare non-conjugated AIE polymers,and further enriched the AIE family.