The chemical modification of porphyran hydrocolloid is attempted, with the objective of enhancing its antioxidant and antimicrobial activities. Sulfated galactan porphyran is obtained from commercial samples of the red algae Porphyra dioica using Soxhlet extraction with water at 100 °C and precipitation with isopropyl alcohol. The extracted porphyran is then treated with modified L-tyrosines in aqueous medium in the presence of NaOH, at ca. 70 °C. The modified tyrosines L1 and L2 are prepared through a Mannich reaction with either thymol or 2,4-di-tert-butylphenol, respectively. While the reaction with 2,4-di-tert-butylphenol yields the expected tyrosine derivative, a mixture of products is obtained with thymol. The resulting polysaccharides are structurally characterized and the respective antioxidant and antimicrobial activities are determined. Porphyran treated with the N-(2-hydroxy-3,5-di-tert-butyl-benzyl)-L-tyrosine derivative, POR-L2, presents a noticeable superior radical scavenging and antioxidant activity compared to native porphyran, POR. Furthermore, it exhibited some antimicrobial activity against S. aureus. The surface morphology of films prepared by casting with native and modified porphyrans is studied by SEM/EDS. Both POR and POR-L2 present potential applicability in the production of films and washable coatings for food packaging with improved protecting characteristics.

This paper studies the effects of glycerol plasticizers and/or alginate, pectin, and carboxymethylcellulose polysaccharides on the mechanical and physical properties of porphyran-based films to evaluate the films’ ability to be used as food packaging. Films were characterized in terms of their composition, microstructural and morphological features, thermal properties, water interaction, and mechanical performance. All films are homogeneous, transparent, and slightly brownish in color. The structures are amorphous and crosslinked, showing the films’ thermoset nature. Moisture content and water solubility depend on the second polysaccharide added to the porphyran, but they both increase with the addition of glycerol to the formulations; water vapor permeability is strongly affected by the second polysaccharide in the formulation. The films display stiff and brittle mechanical behavior, but ductility increases significantly in formulations containing glycerol plasticizers. The barrier and mechanical performance values of the materials produced were found to be lower than those reported for commercial food packaging. The formulations containing glycerol displayed lower water vapor permeability values, ranging from 2.98 for porphyran/carboxymethylcellulose/glycerol to 6.65 mm·g·d−1·m−2·kPa−1 for porphyran/alginate/glycerol films. All films, except porphyran/glycerol and porphyran/alginate/glycerol, had ultimate tensile strengths above 10 MPa—the threshold value that ensures that a package is ductile enough to withstand handling and forming operations. Furthermore, the porphyran/pectin/glycerol and porphyran/carboxymethylcellulose/glycerol films displayed sufficiently high ductility values of 2.94 and 3.10%, respectively. These results indicate that the studied porphyran/pectin/glycerol and porphyran/carboxymethylcellulose/glycerol formulations have a combination of physical and mechanical properties that ensure adequate film integrity and function through the complete food packaging supply chain. The results here reported represent an opportunity to extend the scope of porphyran films to applications in the dry food packaging industry.

Non-biodegradable plastic is one of the biggest environmental problems of our lifetime and, considering the present societal needs, it will get worse. Consequently, there is an urgent need to develop sustainable and renewable alternatives to plastic, such as plastic-like materials obtained from biodegradable polymers, namely sulfated polysaccharides, considered one of the most viable alternatives. There is also a need to obtain these materials in an environmentally and economically sustainable way. The hereby developed process of obtaining film-forming solutions from semi-refined porphyran (PorphSR) uses a green solvent (hot water) with a high extraction yield of semi-refined porphyran (26.66 ± 0.27%) in a reproducible way and with low levels of contaminants. The obtained semi-refined porphyran showed good antioxidant potential in all tests performed: HPSA (Δ0.066 ± 0.002), DPPH (2.23 ± 0.78%), FRAP (0.420 ± 0.014 eq. ascorbic acid µg mg−1 of extract) and ABTS (20.46 ± 0.90%). After being cast into films, the most notable antioxidant properties were those of the semi-refined porphyran in the DPPH, FRAP and ABTS assays and of the pectin, (PorphSR_PcT and PorphSR_PcT_Gly) in the HPSA assay. Morphologically, the films showed relatively homogeneous and low roughness surfaces. It is concluded that the described method to obtain semi-refined porphyran is feasible and reproducible, and that the developed films, mainly PorfP2_PcT_Gly, proved to be a potential candidate for non-biodegradable plastic substitutes.

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