Iron-substituted crown-type polyoxometalate (POM) [P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)](20-) has been successfully immobilized onto glassy carbon electrode surfaces by means of the layer-by-layer (LBL) technique employing the cationic redox active dye, methylene blue (MB). The constructed multilayers exhibit pH-dependent redox activity for both the anionic POM and the cationic dye moieties, which is in good agreement with their solution behavior. The films have been characterized by alternating current impedance, atomic force microscopy, and X-ray photoelectron spectroscopy, whereby the nature of the outer layer within the assemblies was found to have an effect upon the film's behavior. Preliminary investigations show that the POM dye-based films show electrocatalytic ability toward the reduction of hydrogen peroxide, however, only when there is an outer anionic POM layer.

The rise of three-dimensional cell culture systems that provide in vivo-like environments for pharmaco-toxicological models has prompted the need for simple and robust viability assays suitable for complex cell architectural structures. This study addresses that challenge with the development of an in vitro enzyme based electrochemical sensor for viability/cytotoxicity assessment of two-dimensional (2D) monolayer and three-dimensional (3D) spheroid culture formats. The biosensor measures the cell viability/ toxicity via electrochemical monitoring of the enzymatic activity of nonspecific esterases of viable cells, through the hydrolysis of 1-naphthyl acetate to 1-naphthol. The proposed sensor demonstrated strong correlation (r = 0.979) with viable cell numbers. Furthermore, the model intestinal toxicants diclofenac (DFC, pharmaceutical), okadaic acid (OA, food-safety), and mancozeb (MZB, environmental) were used for the functional evaluation of the proposed sensor using 2D and 3D culture formats. Sensor performance showed high consistency with conventional cell viability/cytotoxicity assays (MTT/CFDA-AM) for all toxicants, with the sensor IC 50 values matching the relevant viability LC 50 values at the 95% confidence interval range for 2D (

Surface anchoring of an organic functionalized POM, TBA3K[SiW10O36(PhPO)2] was carried out by two methods, the layer-by-layer (LBL) assembly technique by employing a pentaerythritol-based ruthenium(II) metallodendrimer as a cationic moiety and also by entrapping the POM in a conducting polypyrrole film. The redox behavior of the constructed films was studied by using cyclic voltammetry and electrochemical impedance spectroscopy. The surface morphologies of the constructed multilayers were examined by scanning electron microscopy and atomic force microscopy. X-ray photoelectron spectroscopy was conducted to confirm the elements present within the fabricated films. The multilayer assembly was also investigated for its catalytic efficiency towards the reduction of nitrite.

Abstract

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