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. 2025 May 29;17(11):1518.
doi: 10.3390/polym17111518.

Eugenol@Montmorillonite vs. Citral@Montmorillonite Nanohybrids for Gelatin-Based Extruded, Edible, High Oxygen Barrier, Active Packaging Films

Affiliations

Eugenol@Montmorillonite vs. Citral@Montmorillonite Nanohybrids for Gelatin-Based Extruded, Edible, High Oxygen Barrier, Active Packaging Films

Achilleas Kechagias et al. Polymers (Basel). .

Abstract

In the context of the circular economy, the valorization of bio-derived waste has become a priority across various production sectors, including food processing and packaging. Gelatin (Gel), a protein which can be recovered from meat industry byproducts, offers a sustainable solution in this regard. In this study, pork-derived gelatin was used to develop novel edible active packaging films, designed for meat products. Glycerol (Gl) was used as a plasticizer. Two types of montmorillonite-based nanohybrids were employed as both reinforcing agents and carriers of antioxidant/antibacterial compounds: eugenol-functionalized montmorillonite (EG@Mt) and citral-functionalized montmorillonite (CT@Mt). The active films were formulated as Gel/Gl/xEG@Mt and Gel/Gl/xCT@Mt, where x = 5, 10, or 15 wt.%. Controlled-release kinetics showed that EG@Mt released up to 95% of its adsorbed eugenol, whereas CT@Mt released up to 55% of its adsorbed citral. The films were evaluated using the DPPH (2,2-diphenyl-1-picrylhydrazyl) assay and tested for antibacterial activity against Escherichia coli and Listeria monocytogenes. Results demonstrated that the Gel/Gl/xEG@Mt films exhibited superior antioxidant and antibacterial performance compared to the Gel/Gl/xCT@Mt films. All formulations were impermeable to oxygen. Although the incorporation of EG and CT slightly reduced cell viability, values remained above 80%, indicating non-toxicity. In conclusion, the film containing 15 wt.% EG@Mt achieved an oxygen transmission rate of zero, an effective concentration (EC60) of 9.9 mg/L to reach 60% antioxidant activity, and reduced E. coli and L. monocytogenes populations by at least 5.8 log CFU/mL (p < 0.05), bringing them below the detection limit. Moreover, it successfully extended the shelf life of fresh minced pork by two days.

Keywords: active packaging; citral; edible packaging; eugenol; gelatin; high oxygen barrier; minced pork; montmorillonite; shelf life.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
EG and CT desorption isotherm kinetic plots (in triplicates) for EG@Mt (left part (ac) plots) and CT@Mt (right part (df) plots) nanohybrids at 70 °C ((a,d) plots), 90 °C ((b,e) plots), and 110 °C ((c,f) plots). Line plots show the simulation plots according to the pseudo-second-order kinetic model.
Figure 2
Figure 2
ln(1/k2) values as a function of (1/T) plots for (a) EG@Mt and (b) CT@Mt nanohybrids.
Figure 3
Figure 3
XRD plots of (1) Mt as received, (2) dried Mt, (3) EG@Mt nanohybrid, and (4) CT@Mt nanohybrid.
Figure 4
Figure 4
(a) FTIR plots of (1) pure EG, (2) pure Mt, and (3) EG@Mt nanohybrid, (b) FTIR plots of (1) pure CT, (2) pure Mt, and (3) CT@Mt nanohybrid.
Figure 5
Figure 5
HR-SEM images of (ac) pure Mt, (df) EG@Mt nanohybrid, and (gi) CT@Mt nanohybrid.
Figure 6
Figure 6
XRD patterns in the 2θ range of 2° to 30° for: (a) (1) Gel/Gl film, (2) Gel/Gl/5Mt film, and (3) Gel/Gl/10Mt film; (b) (1) Gel/Gl film, (2) Gel/Gl/5EG@Mt film, (3) Gel/Gl/10EG@Mt film, and (4) Gel/Gl/15EG@Mt film; (c) (1) Gel/Gl film, (2) Gel/Gl/5CT@Mt film, and (3) Gel/Gl/10CT@Mt film.
Figure 7
Figure 7
FTIR plots of (1) Gel/Gl, (2) Gel/Gl/5Mt, (3) Gel/Gl/5EG@Mt, and (4) Gel/l/5CT@Mt films.
Figure 8
Figure 8
HR-SEM images of (a) pure Gel/Gl film, (b) Gel/Gl/5Mt film, (c) Gel/Gl/10Mt film, (d) Gel/Gl/5EG@Mt active film, (e) Gel/Gl/10EG@Mt active film, (f) Gel/Gl/15EG@Mt active film, (g) Gel/Gl/5CT@Mt active film, and (h) Gel/Gl/10CT@Mt active film.
Figure 9
Figure 9
Stress–strain curves for (1) Gel/Gl, (2) Gel/Gl/5Mt, (3) Gel/Gl/10Mt, (4) Gel/Gl/5EG@Mt, (5) Gel/Gl/10EG@Mt, (6) Gel/Gl/15EG@Mt, (7) Gel/Gl/5CT@Mt, and (8) Gel/Gl/10CT@Mt film.
Figure 10
Figure 10
HaCaT skin cell viability in direct contact with films for 24 h. Different letters (A, B, C, D and E) indicate statistically significant differences between the different groups (p < 0.05). Error bars represent the standard deviation. See also Table S3 in the Supplementary Materials.
Figure 11
Figure 11
Mean populations of Listeria monocytogenes (a) and Escherichia coli (b) in Gel/Gl/xMt, Gel/Gl/xEG@Mt, and Gel/Gl/xCT@Mt films. Data are presented as log10 transformations. Different letters (A, B, C, and D) indicate statistically significant differences between the groups (p < 0.05). Error bars represent the standard deviation. The detection limit for each bacterial population was 1.0 log CFU/mL. See also Table S4 in the Supplementary Materials.
Figure 12
Figure 12
Minced pork wrapped in (a) Gel/Gl/15EG@Mt and (b) Gel/Gl/10CT@Mt active films after six days of storage at 4 ± 1 °C.

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