A robust and homogeneous porous poly(3,4-ethylenedioxythiophene)/graphene thin film for high-efficiency laser desorption/ionization analysis of estrogens in biological samples.

Herein, a robust and homogeneous porous poly(3,4-ethylenedioxythiophene)/graphene (PEDOT/graphene) thin film surface-assisted laser desorption/ionization (SALDI) functional platform was prepared through a rapid and facile in-situ photopolymerization method. The graphene-embedded PEDOT skeleton well circumvented the aggregation-related problems in the traditional carbon-based SALDI method which combined with time-of-flight mass spectrometer (TOF MS). As a result, the reproducibility and quantitative capacity of the SALDI platform were significantly improved. Furthermore, the highly efficient adsorption performance of the PEDOT/graphene thin film was demonstrated in terms of in vitro and in vivo solid-phase microextraction (SPME) extraction. It showed that porous morphology with abundant graphene doping favored the adsorption and enrichment of target analytes. Owing to the excellent adsorption capability of the PEDOT/graphene thin film and the inherent strong laser absorption ability of graphene, expected SALDI effect (3-13 times higher than the commercial nanomaterial-assisted LDI plate) and quantitative analysis (linear range 0.5-100 μg L) of the PEDOT/graphene functional surfaces were achieved. As for the real-world applications, we deployed the PEDOT/graphene thin film SALDI platform for the analysis of five estrogens in biological samples at microliter-volume level, without tedious sample preparation procedures. Satisfactory recoveries ranging from 60.6% to 99.0% were obtained. The present study suggested that the graphene-embedded PEDOT skeleton with porous morphology would be developed as promising coating for the adsorption of analytes of interest. Additionally, the combination of PEDOT with graphene not only expanded the application fields of PEDOT, but also offered an efficient strategy for preparing homogeneous functional surfaces to realize the quantitative analysis in SALDI method.