A new enzymatic electrochemical biosensor has been developed with the PANI/Nafion composite system containing ferrite nanoparticles with four different transition metals. The ferrite nanoparticles containing copper, cobalt, nickel, and zinc metals were synthesized by the co-precipitation method and their surfaces were modified with tetraethoxysilane and (3-aminopropyl) triethoxysilane to obtain -NH2 function in order to develop the purposed sensing system. The modified and unmodified ferrite nanoparticles were characterized by physically, chemically, and morphologically. Ferrite nanoparticles with suitable for enzyme immobilization were integrated on the GCE surface and covered with PANI/Nafion. According toelectrochemical measurements, it was determined that copper ferrite nanoparticles, which have the lowest bandgap value, significantly increased the biosensor performance. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to monitor biosensor production and evaluate its performance. A detection limit of 0.17 µM and a wide linear range of 0.5-45.0 µM were obtained for the urea detection with the DPV method with the sensing system (Nf/PANI/CuF/Urs). The biosensor has been successfully applied to soil and milk samples with high accuracy. In addition, it has been determined that the proposed method has good reproducibility, selectivity, and stability.

There is an urgent need for sensing strategies to screen perfluoroalkyl substances (PFAS) in aqueous matrices. These strategies must be applicable in large-scale monitoring plans to face the ubiquitous use of PFAS, their wide global spread, and their fast evolution towards short-chain, branched molecules. To this aim, the changes in fluorinated self-assembled monolayers (SAM) with different architectures (pinholes/defects-free and with randomized pinholes/defects) were studied upon exposure to both long and short-chain PFAS. The applicability of fluorinated SAM in PFAS sensing was evaluated. Changes in the SAM structures were characterised combining electrochemical impedance spectroscopy and voltammetric techniques. The experimental data interpretation was supported by molecular dynamics simulations to gain a more in-depth understanding of the interaction mechanisms involved. Pinhole/defect-free fluorinated SAM were found to be applicable to long-chain PFAS screening within switch-on sensing strategy, while a switch-off sensing strategy was reported for screening of both short/long-chain PFAS. These strategies confirmed the possibility to play on fluorophilic interactions when designing PFAS screening methods.

Hollow peanut-shaped NiFe2O4/CoFe2O4 twinned nano-spherical shell composite materials have interconnected electron channels and excellent electrochemical performance, which prompted the use of this unique spatial structure to fabricate efficient electrochemical sensors. In this work, N-doped carbon dots (NCDs) incorporated into magnetic NiFe2O4/CoFe2O4 nanoparticle shell (NiFe2O4/CoFe2O4/NCDs) modified glassy carbon electrode (GCE) was applied to construct a dual-template molecularly imprinted polymer (MIP) based electrochemistry sensor (NiFe2O4/CoFe2O4/NCDs/MIP/GCE) for the simultaneous detection of catechin (CA) and theophylline (TPH). MIP was fabricated by an in-situ electrochemical polymerization strategy based on the theoretical exploration and density functional theory (DFT) computer directional simulation to screen out the optimal functional monomer (L-arginine) and the optimal ratio between the dual template molecules (CA and TPH) and functional monomer. The materials were characterized by SEM, TEM, XRD, XPS, and TGA. Besides, electron binding energy, binding constant, and imprinting factor were investigated. With the optimal conditions, the proposed electrochemical dual detection system showed outstanding analytical performance for the simultaneous sensing of CA and TPH, with an ultralow detection limit (LOD, S/N = 3) of 1.3 nM for CA in 0.01-1 μM (R2 = 0.9956) and 1-50 μM (R2 = 0.9928), as well as a LOD of 20.0 nM for TPH in the linear range of 0.1-100 μM (R2 = 0.9939), respectively. Also, the selectivity and anti-interference performances of the fabricated sensor were performed by differential pulse voltammetry and chronoamperometry, and successfully detected the analyte from tea drinks and human urine samples with the recovery rates ranging from 98.22% to 104.76% and relative standard deviations (RSD) were 1.19%-3.81%, demonstrated the sensor has excellent stability, repeatability, and reproducibility, which paves the way for other platforms to use this nanomaterial for the detection of antioxidant in the filed food safety.

This study addresses the rational design of a magnetic molecularly imprinted polymer (magnetic-MIP) for the selective recognition of the hormone levothyroxine. The theoretical study was carried out by the density functional theory (DFT) computations considering dispersion interaction energies, and using the D2 Grimme\'s correction. The B97-D/def2-SV(P)/PCM method is used not only for studying the structure of the template the and monomer-monomer interactions, but also to assess the stoichiometry, noncovalent binding energies, solvation effects and thermodynamics properties such as binding energy. Among the 13 monomers studied in silico, itaconic acid is the most suitable according to the thermodynamic values. In order to assess the efficiency of the computational study, three different magnetic-MIPs based on itaconic acid, acrylic acid and acrylamide were synthesized and experimentally compared. The theoretical results are in agreement with experimental binding studies based on laser confocal microscopy, magneto-actuated immunoassay and electrochemical sensing. Furthermore, and for the first time, the direct electrochemical sensing of L-thyroxine preconcentrated on magnetic-MIP was successfully performed on magneto-actuated electrodes within 30 min with a limit of detection of as low as 0.0356 ng mL-1 which cover the clinical range of total L-thyroxine. Finally, the main analytical features were compared with the gold standard method based on commercial competitive immunoassays. This work provides a thoughtful strategy for magnetic molecularly imprinted polymer design, synthesis and application, opening new perspectives in the integration of these materials in magneto-actuated approaches for replacing specific antibodies in biosensors and microfluidic devices.