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  • Molecular Imprinting on Nanozymes for Sensing Applications
    Publication . Cardoso, Ana Rita; Frasco, Manuela F.; Serrano, Verónica; Fortunato, Elvira; Sales, Maria Goreti Ferreira
    As part of the biomimetic enzyme field, nanomaterial-based artificial enzymes, or nanozymes, have been recognized as highly stable and low-cost alternatives to their natural counterparts. The discovery of enzyme-like activities in nanomaterials triggered a broad range of designs with various composition, size, and shape. An overview of the properties of nanozymes is given, including some examples of enzyme mimics for multiple biosensing approaches. The limitations of nanozymes regarding lack of selectivity and low catalytic efficiency may be surpassed by their easy surface modification, and it is possible to tune specific properties. From this perspective, molecularly imprinted polymers have been successfully combined with nanozymes as biomimetic receptors conferring selectivity and improving catalytic performance. Compelling works on constructing imprinted polymer layers on nanozymes to achieve enhanced catalytic efficiency and selective recognition, requisites for broad implementation in biosensing devices, are reviewed. Multimodal biomimetic enzyme-like biosensing platforms can offer additional advantages concerning responsiveness to different microenvironments and external stimuli. Ultimately, progress in biomimetic imprinted nanozymes may open new horizons in a wide range of biosensing applications.
  • In-situ production of Histamine-imprinted polymeric materials for electrochemical monitoring of fish
    Publication . Serrano, Verónica; Cardoso, Ana Rita; Diniz, Mário; Sales, Maria Goreti Ferreira
    Histamine (HIS) is a major public health problem due to its toxic properties. High levels can cause a chronic toxicity as poisoning and can be used as a signal of food hygiene. Thus, a new electrochemical sensor for HIS detection in fish is presented herein, prepared by tailoring a molecularly imprinted polymer (MIP) sensing material on a gold screen-printed electrode (Au-SPEs), in which the polymeric film was generated in-situ. This film was obtained by electropolymerizing aniline under conditions that preserved the chemical structure of HIS. Raman spectroscopy followed the chemical changes occurring at each stage of the electrode modification. The device performance was assessed by evaluating the changes in electron transfer properties of a standard redox probe [Fe(CN)6]4−/[Fe(CN)6]3−, by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). EIS was also used to calibrate the sensor, being the standard solutions prepared under different background media (electrolyte or a blank sample of fish extract). The device displayed a linear response from 500 nM to 1 mM, with a limit of detection of 210 nM, and a selective behaviour against tyramine, another amine related to fish degradation. The sensing system was further employed to monitor the HIS content in samples in different time points of storage at ambient temperature. The obtained results were in agreement with the ELISA method, while offering more reproducible data. In general, the optimized sensor allowed reproducible and accurate analysis of fish samples subject to degradation and was completely assembled in-situ, in a very simple and straightforward approach. The device is low cost and suitable for further adaptation to on-site analysis, as required in food control.