水杨醛席夫碱修饰的交联化聚乙烯亚胺荧光纳米微粒的合成与发光性质
Synthesis and Luminescence Properties Investigation of Fluorescent Nanoparticles Based on Cross-linked Polyethylemine with Salicylidene Schiff base-functionalized
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摘要: 将5-氯甲基水杨醛与商品化聚乙烯亚胺(25KDa)按摩尔比1:1进行投料, 在甲醇中65℃下同时进行N-季铵化反应和醛-胺缩合反应, 获得交联度和水杨醛席夫碱生色团含量适中的交联化聚乙烯亚胺。通过紫外-可见分光光谱(UV-Vis)、荧光发射光谱(FLL)和动态光散射(DLS)分别对合成的纳米微粒的发光性质和粒径大小分布进行了表征。结果表明, 合成的交联化聚乙烯亚胺兼具聚乙烯亚胺和水杨醛席夫碱的特性, 在除去溶剂甲醇干燥后, 可在纯水中进行超声分散, 形成一种粒径约为~170nm、最大荧光发射波长在~500nm处的荧光纳米微粒。由于通过pH值变化可调控水杨醛席夫碱键的形成和断裂, 因而纳米微粒的交联结构和荧光发射对pH值具有荧光响应性。此外, 纳米微粒还可以进一步Zn2+离子进行配位反应, 引起荧光发射波长从~500nm处蓝移至~460nm处并伴随着荧光的增强。Abstract: Across-linked polyethylemine with Salicylidene Schiff base-functionalized was achieved via combination quaternarization and aldehyde-amine condensation with 5-Cholromethylsalicylaldehyde as the cross-linking agent and commercial polyethylemine(25 KDa) in methanol at 65℃. 5-Cholromethylsalicylaldehyde with reactive cholromethyl and salicylaldehyde groups could react directly with polyethylemine to afford with optimized the degree of cross-linking density and the amount of Salicylidene Schiff base with the mole ratio of 1:1. Thus, the luminescence properties and form of the obtained cross-linked polyethylemine nanoparticles was investigated by UV-vis spectra(UV-vis), fluorescence spectra(FLL) and dynamic light scattering(DLS).The results showed that after drying to remove methanol the resultant cross-linked polyethylemine could be re-dispersed readily in pure water under ultrasound to obtain luminescent nanoparticles with sizes of ~170 nm by DLS determination and a maximum emission peak around ~500 nm as a result of the aggregation-induced fluorescence enhance. The existence of salicylidene Schiff base linkages(i.e., salicylaldimine ligands) can not only endow the resulting fluorescent nanoparticles pH-controllable in terms of its fluorescence emission and cross-linking structure due to the reversibility of Schiff base linkage in response to pH stimuli, but also endow the resulting fluorescent nanoparticles with a further Zn2+-coordinating function to result in a blue shift of a maximum emission peak from ~500 nm to 460 nm, concomitantly a remarkable fluorescence enhancement.
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