RESUMEN
In recent years, castration-resistant prostate cancer (CRPC) has profoundly impacted the lives of many men, and early diagnosis of medication and illness is crucial. Therefore, a highly efficient detection method for CRPC biomarkers and curing drugs is required. However, the complex and diverse structures of CRPC drugs pose significant challenges for their detection and differentiation. Lanthanide metal-organic frameworks (Ln-MOFs) show great potential for sensing applications due to their intense and characteristic luminescence. In this work, a series of new bimetallic Ln-MOFs (EuxTb1-x-MOF) based luminescent sensor arrays have been developed to identify CRPC drugs, including in mixtures, via principal component analysis (PCA) and hierarchical cluster analysis (HCA) methods. These Ln-MOFs are built with a highly conjugated H2L linker (H2L = 5-(4-(triazole-1-yl)phenyl)isophthalic acid) and exhibit robust strong luminescence emissions (mainly located at 543 and 614 nm) and high energy transfer efficiencies. More specifically, Eu0.096Tb0.904-MOF (MOF 3) has demonstrated good sensing performances for CRPC curing drugs in real human serum samples. Furthermore, the curing drug hydroxyflutamide has been combined with MOF 3, to construct a robust composite sensing platform MOF 3@hydroxyflutamide for highly efficient detection of CRPC biomarkers such as the androgen receptor (AR) and prostate-specific antigen (PSA). Finally, luminescence lifetime measurements, zeta potential measurements, and density functional theory (DFT) calculations were performed to gain insights into the sensing mechanism.
RESUMEN
Metal-organic frameworks (MOFs) with exceptional features such as high structural diversity and surface area as well as controlled pore size has been considered a promising candidate for developing room temperature highly-sensitive gas sensors. In comparison, the hetero-metallic MOFs with redox-active open-metal sites and mixed metal nodes may create peculiar surface properties and synergetic effects for enhanced gas sensing performances. In this work, the Fe atoms in the Fe3 (Porous coordination network) PCN-250 MOFs are partially replaced by transition metal Co, Mn, and Zn through a facile hydrothermal approach, leading to the formation of hetero-metallic MOFs (Fe2IIIMII, M = Co, Mn, and Zn). While the PCN-250 framework is maintained, the morphological and electronic band structural properties are manipulated upon the partial metal replacement of Fe. More importantly, the room temperature NO2 sensing performances are significantly varied, in which Fe2Mn PCN-250 demonstrates the largest response magnitude for ppb-level NO2 gas compared to those of pure Fe3 PCN-250 and other hetero-metallic MOF structures mainly attributed to the highest binding energy of NO2 gas. This work demonstrates the strong potential of hetero-metallic MOFs with carefully engineered substituted metal clusters for power-saving and high-performance gas sensing applications.