An AIE-based fluorescent dye for selective staining of polyamide microplastics without pretreatment: Applications to environmental samples and zebrafish

Abstract

A novel staining dye, BEM ((1E,1'E)-1,1'-([2,2'-bithiophene]-5,5'-diyl)bis(N-(9-ethyl-9H-carbazol-3-yl)methanimine)) was synthesized for selective identification of polyamide (PA) micrplastics. BEM showed unique photophysical properties such as solvatochromism, intramolecular charge transfer (ICT), and aggregation induced emission (AIE) which were demonstrated through spectroscopic analysis and density functional theory (DFT) calculations. The optimal staining conditions for selective staining of PA by BEM were established by evaluating the staining efficiency according to the variation of the solvent compositions, concentrations of BEM, and staining durations. BEM demonstrated outstanding selective staining of PA among 11 types of microplastics (MPs) and 5 types of non-plastics through the emission of green fluorescence. BEM successfully identified PA without any noticeable influence on the size change of PA, aging of PA, and pH alteration of the solvent. In addition, BEM was practically applied to environmental samples like river water, seawater, and soil for selective identification of PA without pretreatment. In particular, the cost-effective technique of BEM-labeled PA allowed to monitor the location and accumulation of PA in living zebrafish. The interaction between PA and BEM was investigated through scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS), which suggested that BEM might be adsorbed onto the surface of PA. Moreover, non-covalent interaction (NCI) analysis demonstrated that the intermolecular hydrogen bonds and van der Waals interactions would play a significant role in the adsorption process between PA and BEM.

Keywords: Aggregation-Induced Emission; Environmental samples; Microplastic staining; Polyamide; Zebrafish.