A mesoporous graphene @ zirconium-based metal–organic frameworks as a matrix and an adsorbent for steroid detection using surface-assisted laser desorption/ionization time-of-flight mass spectrometry

Endocrine-disrupting chemicals (EDCs) in environmental water samples, a rapid, sensitive, and high-throughput method should be developed. In this study, an in situ-synthesized composite material of three-dimensional mesoporous graphene (3D-MG) and zirconium-based metal-organic frameworks (MOFs), denoted as MG@UiO-66, was used as both the adsorbent and matrix in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) for steroid detection. Both graphene-based materials and MOFs have proven to be ineffective in detecting steroids as a matrix; however, their composites can detect steroids with higher sensitivity and lower interference. After screening different types of MOFs, a composite of UiO-66 and 3D-MG was selected as the new matrix for steroid detection. The combination of 3D-MG and UiO-66 further enhanced the ability of the material to enrich steroids, and reduced the limit of detection (LOD) of steroids. The method was evaluated for linearity, LODs, limit of quantitation (LOQs), reproducibility, and precision under optimized conditions. The results showed that the linear relationships of three steroids are kept in the range of 0-300 nM/L with a correlation coefficient r ≥ 0.97. The LODs and LOQs of the steroids were in the range of 3-15 and 10-20 nM/L, respectively. Recoveries (n = 5) of 79.3-97.2% were obtained at three spiked levels in the blank water samples. This fast and efficient method of using SALDI-TOF MS can be extended to detect the steroids in EDCs in environmental water samples.