Department of Radiology, Sun Yat-sen Memorial Hospital, Sun Yat-sen University, No. 107 Yanjiang Road West, Guangzhou 510120, China; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China.
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China.
Talanta. 2019 Apr 1;195:290-297. doi: 10.1016/j.talanta.2018.11.080. Epub 2018 Nov 23.
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.
本文通过快速简便的原位光聚合方法制备了一种稳健且均匀的多孔聚（3,4-乙二氧基噻吩）/石墨烯（PEDOT/石墨烯）薄膜表面辅助激光解吸/电离（SALDI）功能平台。嵌入石墨烯的 PEDOT 骨架很好地避免了传统碳基 SALDI 方法与飞行时间质谱（TOF MS）结合时的聚集相关问题。结果，SALDI 平台的重现性和定量能力得到了显著提高。此外，PEDOT/石墨烯薄膜具有高效的体外和体内固相微萃取（SPME）萃取性能。结果表明，具有丰富石墨烯掺杂的多孔形态有利于目标分析物的吸附和富集。由于 PEDOT/石墨烯薄膜具有优异的吸附能力和石墨烯固有的强激光吸收能力，预期的 SALDI 效应（比商业纳米材料辅助 LDI 板高 3-13 倍）和定量分析（线性范围 0.5-100μg/L）得以实现。对于实际应用，我们在微升体积水平上部署了 PEDOT/石墨烯薄膜 SALDI 平台来分析生物样品中的五种雌激素，无需繁琐的样品制备程序。获得了 60.6%至 99.0%的满意回收率。本研究表明，具有多孔形态的嵌入石墨烯的 PEDOT 骨架将作为有前途的涂层开发，用于吸附感兴趣的分析物。此外，PEDOT 与石墨烯的结合不仅扩展了 PEDOT 的应用领域，而且还提供了一种有效的制备均匀功能表面的策略，以实现 SALDI 方法中的定量分析。
