Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.

Sviluppo di un metodo termoanalitico per la quantificazione di microplastiche in matrici complesse

Microplastics (MPs) are highly debated emerging contaminants that are widespread on Earth. Nowadays, assessment of the risk that MPs pose on human health and environment were not developed yet, and standardized analytical methods for their quantification in complex matrices do not exist. Therefore, the formulation of standards which regulating MPs emission in the environment is not possible. The purpose of this study was to develop and apply a method for the analysis of MPs in sewage sludges and water from a wastewater treatment plant (WWTP), due to the relevance of those matrices as important pathway for MPs to enter the environment. Seven polymers were selected, because of their relevance on market production and their frequency of occurrence in such plants: polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polycarbonate (PC), polyvinyl chloride (PVC), and nylon 6 (PA-6). In the study, a pre-treatment procedure was optimised using Fenton’s reagent and analyses carried out by combining thermochemolysis with Py-GC-MS after sample filtration on quartz (0.3 µm). Polymer quantification was performed with solid polymer mixture in silica and good correlations were obtained with internal calibration. As main results, Fenton's reagent negatively affected the recovery of some polymers (PP, PE, PS, PA-6) and a possible matrix interference was noticed, especially for PET and PVC. The WWTP allowed a good abatement of PS, PE, PP and PVC (on average 90 %) and comparable results were hypothesised for the other polymers. Polymer concentrations is sewage sludges ranged between < 2 μg/gdry and 3.5 mg/ gdry, for PC and PVC, respectively. Possible overestimations for PET and PVC, due to matrix interreferences, were taken into account and discussed.