Roxana Petronela Damaschin

Porous hydrogels have brought more advantages than conventional hydrogels when used as chromatographic materials, controlled release vehicles for drugs and proteins, matrices for immobilization or separation of molecules and cells, or as scaffolds in tissue engineering. Polysaccharide-based porous hydrogels, in particular, can address challenges related to bioavailability, solubility, stability, and targeted delivery of natural antioxidant compounds. Their porous structure enables the facile encapsulation and controlled release of these compounds, enhancing their therapeutic effectiveness. In this context, in the present study, the cryogelation technique has been adopted to prepare novel dextran (Dx)-based porous hydrogels embedding polyphenol-rich natural extract from Picea abies spruce bark (SBE). The entrapment of the SBE within the Dx network was proved by FTIR, SEM, and energy-dispersive X-ray spectroscopy (EDX). SEM analysis showed that entrapment of SBE resulted in denser cryogels with smaller and more uniform pores. Swelling kinetics confirmed that higher concentrations of Dx, EGDGE, and SBE reduced water uptake. The release studies demonstrated the effective stabilization of SBE in the Dx-based cryogels, with minimal release irrespective of the approach selected for SBE incorporation, i.e., during synthesis (~3–4%) or post-synthesis (~15–16%). In addition, the encapsulation of SBE within the Dx network endowed the hydrogels with remarkable antioxidant and antimicrobial properties. These porous biomaterials could have broad applications in areas such as biomedical engineering, food preservation, and environmental protection, where stability, efficacy, and safety are paramount.

Polysaccharides have recently attracted growing attention as adsorbents for various pollutants, since they can be extracted from a variety of renewable sources at low cost. An interesting hydrophilic and biodegradable polysaccharide is dextran (Dx), which is well-known for its applications in the food industry and in medicine. To extend the application range of this biopolymer, in this study, we investigated the removal of crystal violet (CV) and methylene blue (MB) dyes from an aqueous solution by Dx-based cryogels using the batch technique. The cryogel adsorbents, consisting of cross-linked Dx embedding a polyphenolic (PF) extract of spruce bark, were prepared by the freeze-thawing approach. It was shown that the incorporation of PF into the Dx-based matrix induced a decrease in porosity, pore sizes and swelling ratio values. Moreover, the average pore sizes of the DxPF cryogels loaded with dyes further decreased from 42.30 ± 7.96 μm to 23.68 ± 2.69 μm, indicating a strong interaction between the functional groups of the cryogel matrix and those of the dye molecules. The sorption performances of the DxPF adsorbents were evaluated in comparison to those of the Dx cryogels and of the PF extract. The experimental sorption capacities of the DxPF cryogel adsorbents were higher in comparison to those of the Dx cryogels and the PF extract. The DxPF cryogels, particularly those with the highest PF contents (sample DxPF2), demonstrated sorption capacities of 1.2779 ± 0.0703 mmol·g⁻¹, for CV, and 0.3238 ± 0.0121 mmol·g⁻¹, for MB. The sorption mechanisms were analyzed using mathematical models, including Langmuir, Freundlich, Sips and Dubinin–Radushkevich isotherms, and kinetic models, like pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich and intra-particle diffusion (IPD). The sorption process was best described by the Sips isotherm and PSO kinetic models, indicating chemisorption as the dominant mechanism. This study outlines the importance of developing advanced renewable materials for environmental applications.