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This work presents an efficient method for the preparation of magnetic nanoparticles modified with molecularly imprinted polymers (Mag-MIP) through core-shell method for the determination of biotin in milk food samples. The functional monomer acrylic acid was selected from molecular modeling, EGDMA was used as cross-linking monomer and AIBN as radical initiator. The Mag-MIP and Mag-NIP were characterized by FTIR, magnetic hysteresis, XRD, SEM and N2-sorption measurements. The capacity of Mag-MIP for biotin adsorption, its kinetics and selectivity were studied in detail. The adsorption data was well described by Freundlich isotherm model with adsorption equilibrium constant (KF) of 1.46 mL g(-1). The selectivity experiments revealed that prepared Mag-MIP had higher selectivity toward biotin compared to other molecules with different chemical structure. The material was successfully applied for the determination of biotin in diverse milk samples using HPLC for quantification of the analyte, obtaining the mean value of 87.4% recovery.

Advances in analysis are required for rapid and reliable clinical diagnosis. Graphene is a 2D material that has been extensively used in the development of devices for the medical proposes due to properties such as an elevated surface area and excellent electrical conductivity. On the other hand, architectures have been designed with the incorporation of different biological recognition elements such as antibodies/antigens and DNA probes for the proposition of immunosensors and genosensors. This field presents a great progress in the last few years, which have opened up a wide range of applications. Here, we highlight a rather comprehensive overview of the interesting properties of graphene for in vitro, in vivo, and point-of-care electrochemical biosensing. In the course of the paper, we first introduce graphene, electroanalytical methods (potentiometry, voltammetry, amperometry and electrochemical impedance spectroscopy) followed by an overview of the prospects and possible applications of this material in electrochemical biosensors. In this context, we discuss some relevant trends including the monitoring of multiple biomarkers for cancer diagnostic, implantable devices for in vivo sensing and, development of point-of-care devices to real-time diagnostics.

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A B S T R A C TAn electrochemical sensor modified with a molecularly imprinted polymer (MIP) and carboxylfunctionalized multi-walled carbon nanotubes (MWCNT-COOH) was developed for the sensitive and selective detection of diuron in river water samples. An MIP was obtained by bulk polymerization using the best monomer (methacrylic acid) selected by computational simulation. The surface characteristics of the MIP and NIP (control polymer) samples were evaluated by means of surface area and pore volume determinations, using the BET method. The adsorption efficiency of the MIP was determined in adsorption tests that revealed high adsorption, relative to the control polymer. In addition, MWCNTs functionalized with carboxyl groups were used to enhance the performance of the sensor. Electrochemical studies of diuron using the MIP and MWCNT-COOH immobilized on a carbon paste electrode were performed with wave square voltammetry (SWV). The analytical parameters pH, buffer composition, and amounts of MWCNT-COOH and MIP were investigated and optimized. Excellent results were obtained with a linear range of between 5.2 Â 10 À8 and 1.25 Â 10 À6 mol L À1 , detection limit of 9.0 Â 10 À9 mol L À1 , and sensitivity of 5.1 Â10 5 mA L mol À1 . The MWCNT-COOH-MIP/CPE showed an enhanced electrochemical response, with sensitivity 7.9-fold greater than for a plain carbon paste electrode (CPE). Application of the sensor using river water samples resulted in recoveries between 96.1 and 99.5% and RSD <5% (n=3), demonstrating the reliability of this device.

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