Aptamer-functionalized metal-organic framework-coated nanofibers with multi-affinity sites for highly sensitive, selective recognition of ultra-trace microcystin-LR

Abstract

A novel aptamer-functionalized metal-organic framework nanofibrous composite (viz. PAN/UiO@UiO2-N3-aptamer) with a high aptamer coverage density was proposed based on the electrospinning and seeded growth method, and used for specific affinity recognition of trace Microcystin-LR (MC-LR). Heterobifunctional ligand was used to modify the metal–organic framework nanoparticles (MOF NPs) surface, which could passivate the MOF surface with respect to unmodified DNA, followed by coupling massive aptamers on MOF of the solid-phase microextraction (SPME) fiber using click chemistry. Characterizations including morphology, spectra analysis, mechanical stability, binding capacity and specificity were fulfilled. Applied to the analysis of MC-LR, the good selective and sensitive recognition were obtained with the detection limit as low as 0.003 ng/mL, which was better than most non-specific SPME or solid-phase extraction (SPE) protocols. The stability and reproducibility were acceptable, and the intra-day, inter-day and column-to-column relative standard deviations (RSDs) for the recovery of MC-LR were gained in the range from 2.5% to 14.3%, respectively. Satisfactory recoveries of MC-LR in environmental water samples were measured as 96.3 ± 4.7% - 98.9 ± 2.7% (n = 3) in tap water, 94.4 ± 2.5% - 96.1 ± 3.5% (n = 3) in pond water, and 97.0 ± 2.1% - 97.9 ± 3.1% (n = 3) in river water, respectively. This work demonstrated that the electrospun nanofibrous composite with massive aptamers would be a better alternative for ultra-trace MC-LR detection with good selectivity, matrix-resistance ability and high resolution.