Fast Equilibrium Micro-Extraction from Biological Fluids with Biocompatible Core–Sheath Electrospun Nanofibers

Sample preparation methods with high temporal resolution and matrix resistance will benefit fast direct analysis of analytes in a complex matrix, such as drug monitoring in biofluids. In this work, the core-sheath biocompatible electrospun nanofiber was fabricated as a micro-solid phase extraction material. With the poly(N-isopropylacrylamide) (PNIPAAm) as sheath polymer and polystyrene (PS) as core polymer, the fiber membrane was highly hydrophilic and exhibited good antifouling ability to proteins and cells. Its complete expansion in aqueous solution and its nanoscale fiber (100-200 nm) structure offered high mass transfer rate of analytes between liquid and solid phases. The equilibration time of microextraction with this membrane was all shorter than 2 min for eight drugs tested, and the linear ranges covered more than 3 orders of magnitude for most of them. This membrane could be applied to monitor free drugs in plasma and their protein binding kinetics by equilibrium-microextraction with a 2 min temporal resolution. The results showed that the core-sheath electrospun nanofiber membrane would be a better alternative of solid phase material for microextraction with good matrix-resistance ability and high temporal resolution.