In this work, we explored by means of electron paramagnetic resonance (EPR) spectroscopy the accessibility of a series of spin probes, covering a scale of molecular weights in the range of 200–60,000 Da, in a variety of hydrogels: covalent network, ionotropic, interpenetrating polymer network (IPN) and semi-IPN. The covalent gel network consists of polyethylene or polypropylene chains linked via isocyanate groups with cyclodextrin, and the ionotropic gel is generated by alginate in the presence of Ca2+ ions, whereas semi-IPN and IPN gel networks are generated in a solution of alginate and chitosan by adding crosslinking agents, Ca2+ for alginate and glutaraldehyde for chitosan. It was observed that the size of the diffusing species determines the ability of the gel to uptake them. Low molecular weight compounds can diffuse into the gel, but when the size of the probes increases, the gel cannot uptake them. Spin-labelled Pluronic F127 cannot be encapsulated by any covalent gel, whereas spin-labelled albumin can diffuse in alginate gels and in most of the IPN networks. The EPR spectra also evidenced the specific interactions of spin probes inside hydrogels. The results suggest that EPR spectroscopy can be an alternate method to evaluate the mesh size of gel systems and to provide information on local interactions inside gels.

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Means of eliminating water pollutants or transforming them into less hazardous compounds by green catalysis are desired. The current work was developed with the goal of discovering supports suited for laccase (Lc) immobilization. The effect of the chitosan (CS) molecular weight (Mw) or the polyacrylic acid (PAA) addition was evaluated in microsphere formulation and enzyme immobilization by ESEM, rheology, operational stability, and kinetics. As a practical application, the synthesized products were tested in the methyl red (MR) decomposition and the product identification was performed by high-resolution mass spectrometry. Depending on the required properties, the laccase activity profile (pH, temperature, storage, and Michaelis–Menten parameters) and rheological strength can be modulated by varying the molecular mass of CS or by adding PAA in the support formulation. The immobilized products having the best features regarding MR degradation and recycling abilities were the medium Mw CS microspheres and the system with low Mw CS complexed by PAA, respectively. The degradation mechanism of the dye was proposed accordingly with the identified products by mass spectroscopy. The findings emphasize the potential of the proposed immobilization products to be exploited as viable biocatalysts for dye-contaminated water.

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