Metal oxide nanoparticles for safe active and intelligent food packaging
Introduction
The food industry is under constant and crucial pressure to provide appetizing and safe food products. To satisfy these consumer demands, the food industry regularly improves both the food quality and packaging technology. Food packaging is essential in maintaining the safety and quality of products from processing and manufacturing, through handling and storage until it reaches the consumers. Petroleum-based plastic materials (like polyethylene terephthalate, polypropylene, polystyrene) are usually used to envelop food in order to protect its content from contamination and spoilage and to facilitate its transport and storage. However, plastic materials cannot fully protect food from the environment and, thus, cannot completely ensure product quality and safety. In addition, plastic undergoes continuous fragmentation, and may create micro- and nano-plastics that have potential toxic impacts on human health. Plastic pollution has increased due to the COVID-19 pandemic (Silva et al., 2020). To improve plastic inability to stop light, oxygen and other gases from penetrating and reaching the consumables and causing their degradation, as well as to prolong shelf-life of food and protect human health, novel materials are employed to envelop food products.
Starting from the beginning of the twentieth century, three main approaches have been applied to improve food packaging. The first approach consists in improving plastic polymers by mixing them with other materials. Doping or formation of nanoparticle-polymer composites improves mechanical properties of the packaging material, which can enforce the temperature and humidity resistance properties or improve oxygen barriers (Khajavi et al., 2020). Biopolymers, as ecologically sound “green” materials often suffer from degradation and mechanical issues so application of these materials in food packaging can be accomplished in the form of nanocomposites. The second approach aims to develop “active packaging” in which particles added to the packaging material interact directly with food and protect it from UV, oxygen, ethylene or microbiological contamination (Rai et al., 2019; Vilela et al., 2018). Active packaging systems can be classified as active scavenging systems (absorbers) that remove undesired elements from the product, such as moisture, carbon dioxide oxygen, ethylene and odour and active releasing systems (emitters) that release into the packaging in the form of antioxidants, carbon dioxide or antimicrobial compounds (Yildirim et al., 2018). Finally, the third approach develops “intelligent packaging”, which allows real-time monitoring of food safety (Müller & Schmid, 2019; Rai et al., 2019). For this, sensing elements are combined with the packaging material to transform the food envelope into a miniaturized device for tracking. Intelligent packaging may provide monitoring of food freshness and quality, its storage condition, and, in that way, improve safety and convenience, and help to extend food shelf-life. Thus, enhanced functionality of food packaging is obtained by smart packaging that includes both active and intelligent components, as shown in Fig. 1.
Nanomaterials and nanoparticles are used in the development of all three advanced packaging approaches. Adding nanomaterials including nano-metal oxides to different polymers to form nanocomposites can make packaging lighter, stronger and less permeable (Y. Huang, Mei, Chen, & Wang, 2018). Nanomaterials with an intrinsic antimicrobial activity incorporated in active and intelligent packaging contribute to extending the shelf-life of products by keeping food safe from harmful and spoilage bacteria, fungi and viruses, and by providing freshness during longer storage time. Metal oxide nanoparticles (NPs) have unique properties and morphology and a great potential for application in food industry NPs in nanocomposite packaging can perform oxygen and ethylene scavenging and UV- blocking as part of active packaging functions contributing to extending the product shelf life (Gaikwad, Singh, & Lee, 2018; Gaikwad, Singh, & Negi, 2020).
The objective of this review is to provide an overview of the methodologies and procedures carried out in earlier literature on the development of active and intelligent packaging utilizing metal oxide nanoparticles. As the physicochemical properties of nanoparticles and their stability in nanobiocomposites are essential for the development of packaging films we describe the state-of-the art techniques for nanoparticle synthesis, characterization and incorporation in polymers. Antibacterial properties of active packaging containing metal oxides and current available data on the antiviral aspect is presented. Antifungal and antiviral activities, also significant for food protection, are briefly mentioned. To point out that the cytotoxicity of nanoparticles is the main barrier for their applications in food packaging, we provide a condensed assessment of toxicity of metal oxide nanoparticles at the level of cells, mucus and microbiota. It is noteworthy that new regulations, consumer attitudes and acceptability, the societal involvement and impact, have been comprehensively described in some recent reviews (Garcia, Shin, & Kim, 2018; Omerović et al., 2021). Finally, an overview of the current research covering the potential for utilizing metal oxide nanoparticles in smart packaging for oxygen and ethylene scavenging, moisture control and in food safety sensors is also given.
Section snippets
Legislation
The active packaging technology is defined in the European regulations as “new types of materials and articles designed to actively maintain or improve the condition of the food” (1935/2004/EC) and as “deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food” (450/2009/EC). The intelligent packaging technology is “designed to monitor the condition of the food” (1935/2004/EC). Both technologies are closely
Synthesis and antimicrobial properties of metal oxide NPs
Incorporation of metal oxide NPs in food packaging leads to improved mechanical, thermal and barrier properties combined with excellent antimicrobial activity. The synthesis method greatly influences properties of NPs including their antimicrobial and cytotoxic effects (Y. Huang et al., 2018; Stankic, Suman, Haque, & Vidic, 2016). NPs due to their small size have a larger surface area per mass, thus a larger number of active surface states available for reaction with foodborne pathogens. These
Nanoparticle-biopolymer composites for active packaging
Classical food protecting films are made from polymers such as polyamide (PA), polystyrene (PS), polypropylene (PP), polyethylene (PE), polyvinylchloride (PVC), and polyethylene terephthalate (PET) as raw materials. These plastics have been widely used because of their high accessibility, low cost and good mechanical properties (Omerović et al., 2021). However, they cannot be recycled and are not completely biodegradable. Efforts have been made to replace petroleum plastics with bio-based
Nanoparticle migration from nanocomposites and food stimulants
The antibacterial efficiency of NPs imbedded into a packaging film is usually inferior of that used for film production. Cierech et al. have shown that the concentration of released ZnO NPs from a nanocomposite was several times lower than the concentration of the nanoparticle in the film (Cierech et al., 2019). This parameter has to be evaluated for packaging films. Migration of nanoparticles into enveloped food is a diffusion process when low molecular mass particles initially incorporated in
Oxygen and ethylene scavenging and moisture absorption in active packaging
In many cases food deterioration is caused by oxygen, ethylene or excess of moisture. Active packaging systems incorporating metal oxide nanoparticles offer an advantage of actively contributing to reducing food waste, by scavenging oxygen and ethylene and/or by moisture absorption.
The presence of oxygen in packaging has a detrimental influence on shelf-life and quality of packaged food, as it leads to oxidation of the product and proliferation of bacteria, molds and insects (Yildirim et al.,
Antimicrobial mechanisms of metal oxide nanoparticles
Prior to their integration into a packaging film, nanoscaled engineering materials and particles are tested for their ability to inhibit proliferation of microorganisms in pure cultures. The methods used to estimate antimicrobial efficiency include disk diffusion, broth dilution, agar dilution, and the microtiter plate-based method (Auger et al., 2019; Auger et al., 2018; Stankic et al., 2016; Vasiljevic et al., 2020; Vidic et al., 2013). The broth dilution method is most commonly used as it
Antiviral activity of metal oxide nanoparticles
Transmission of viruses via contaminated surfaces is one of the important routes for their spreading. The antiviral activity of some metal oxide NPs has motivated research into the development of consumer protective packaging. For instance, CuO, ZnO, TiO2 and LaxMnO3 have shown a virucidal activity towards enveloped viruses, such as Influenza A virus, yellow fever virus, respiratory virus, and non-enveloped viruses, such as rhinovirus-2 (Imani et al., 2020). Since surfaces coated with NPs
Toxicity of metal oxide nanoparticles
Humans may be exposed to nanoparticle dissolute from food packaging films either directly through food or indirectly by ingestion of inhaled particles. It is, thus, very important to test potential cytotoxicity of nano-enforcers used in active packaging. Cytotoxicity of NPs has most commonly been evaluated by measuring cell viability after cell exposure to nanoparticles in a buffer or in a cell culture medium. Metal oxide NPs have been shown to reduce cell viability, induce membrane lipid
Intelligent packaging – application of metal oxide NPs in food safety sensors
The food industry regularly performs microbiological and chemical tests of the products during production and before distribution. However, in most cases, there is no such control when food items arrive to the market. Intelligent packaging does not interact with food, but monitors the condition of the packaged product and informs on food quality degradation using indicators (labels) and sensors, and enables traceability with unique codes and tags such as bar codes, RFID tags, smart tags or NFC
Conclusions
Effective utilization of metal oxide nanoparticles in smart packaging using biopolymers has been demonstrated through a review of recent research. Besides improving film properties, such as tensile strength and water barrier, packaging with metal oxides has shown improved antimicrobial (antibacterial, antifungal and antiviral), barrier, UV blocking, oxygen and ethylene scavenging and moisture absorption potential. An added benefit of using metal oxides in smart packaging is incorporation in
Acknowledgments
JV acknowledges the European Union's support through the Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement N° 872662 (IPANEMA). MVN and ZZV acknowledge financial support of the Ministry for Education, Science and Technological Development of the Republic of Serbia, contract with the Institute for Multidisciplinary Research, University of Belgrade 451-03-9/2021–14/200053.
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