Producing and optimizing the properties of chitosan-organic nanofiber biodegradable nanocomposite based containing O. vulgare subsp. gracile and C. copticum essential oils and its application on the oxidative stability of Canola oil

Due to increasing attention to the environment, as well as consumer demand for healthy, nutritive food products and extended shelf life, in the recent years, the food and packaging industries have paid increasing attention to biodegradable edible packaging prepared from biopolymers such as proteins, polysaccharides, and lipids or their combinations. These biodegradable films may act as carrier of wide variety of additives, such as antimicrobial, antioxidant agents, flavors, colorants and spices which improve the functionality of the packaging materials by addition of novel or extra functions. In the present study, an antioxidant/antimicrobial active packaging based on chitosan biopolymer was designed. For this purpose, lignocellulose nanofibers (LCNF) and cellulose nanofibers (CNF) at concentration of 4% were used as reinforcement of biopolymer properties, as well as to control the release of Origanum vulgare subsp. gracile and Carum copticum essential oils (as antioxidant/antimicrobial agent) from the packaging material into the foodstuff. The O. vulgare ssp. gracile leaves and C. copticum seeds were obtained from wild plants in mountains of Urmia (Iran). LCNF (average diameter about 55 nm, average length about 2–5 μm, 99% purity) produced from unbleached hardwood pulp through mechanical and acid treatments and CNF (average diameter about 28 nm, average length about 2–3 μm, 99% purity) prepared from softwoods through mechanical disintegration were kindly provided by Nano Novin Polymer Co. (Saari, Iran). Chitosan (medium molecular weight, from shrimp shell with a deacetylation degree of 75–85%), purchased from Sigma-Aldrich (St. Louis, MO, USA). Chitosan based bionanocomposite films incorporated with organic nanofillers and essential oils were developed by solvent casting method. The synthesized films were characterized by XRD and DSC analyses. To determine the prepared films would have potential to be used as an active packaging, water vapor permeability, water solubility, color, transparency, mechanical properties, antimicrobial and antioxidant activity of the films were also evaluated. In order to determine the efficiency of activated nanocomposites, the effect of these films was evaluated on the oxidative stability of rapeseed oil without antioxidants and compared with the effect of TBHQ synthetic antioxidant. The results showed that the addition of essential oils did not have a significant effect on the crystallinity and thermal properties of the films, while organic reinforcement increased the crystalline properties and thermal resistance of nanocomposite films. By applying the essential oils and CNF and LCNF in the structure of the films, the apparent transparency and consequently the amount of light passage from them decreased compared to the control sample. With addition of essential oils separately and in combination, as well as CNF and LCNF in the structure of films, solubility and film permeability decreased compared to pure chitosan film. By adding of two essential oils with a ratio of 50:50, tensile strength (UTS) and strain to break (STB) of films were increased, while organic nanofibers led to an increase in UTS and a significant reduction in STB of nanocomposites. It was also found that active films containing different ratios of essential oil had remarkable antioxidant activity and high antimicrobial activity against E.coli and B.cereus bacteria, which by adding CNF and LCNF these features were reduced due to the role of controlling the release of essential oil compounds by nanofibers. With the numerical optimization of the software, the optimal amount for the essential oils of C. copticum and O. vulgare oils were 2.29 and 2.71% (5% mix) respectively, in combination with the LCNF nanofibers. The results of oxidative stability of Canola oil showed that nanocomposites containing 5% essential oil were considerably able to keep the oil freshness during storage at ambient temperature and delay the oxidation of the oil.