Significant research has been directed toward the incorporation of bioactive plant extracts or essential oils (EOs) into polymers to endow the latter with antimicrobial functionality. EOs offer a unique combination of having broad antimicrobial activity from a natural source, generally recognized as safe (GRAS) recognition in the US, and a volatile nature. However, their volatility also presents a major challenge in their incorporation into polymers by conventional high-temperature-processing techniques. Herein, antimicrobial polypropylene (PP) cast films were produced by incorporating carvacrol (a model EO) or carvacrol, loaded into halloysite nanotubes (HNTs), via melt compounding. We studied the composition-structure-property relationships in these systems, focusing on the effect of carvacrol on the composition of the films, the PP crystalline phase and its morphology and the films' mechanical and antimicrobial properties. For the first time, molecular dynamics simulations were applied to reveal the complex interactions between the components of these carvacrol-containing systems. We show that strong molecular interactions between PP and carvacrol minimize the loss of this highly-volatile EO during high-temperature polymer processing, enabling semi-industrial scale production. The resulting films exhibit outstanding antimicrobial properties against model microorganisms (Escherichia coli and Alternaria alternata). The PP/(HNTs-carvacrol) nanocomposite films, containing the carvacrol-loaded HNTs, display a higher level of crystalline order, superior mechanical properties and prolonged release of carvacrol, in comparison to PP/carvacrol blends. These properties are ascribed to the role of HNTs in these nanocomposites and their effect on the PP matrix and retained carvacrol content.

This work describes the fabrication of antimicrobial multilayered polymeric films containing carvacrol (used as a model essential oil) by co-extrusion and multiplication technique. The microlayering process was utilized to produce films, with up to 65 alternating layers, of carvacrol-containing low-density polyethylene (LDPE) and ethylene vinyl alcohol copolymer (EVOH). Carvacrol was melt compounded with LDPE or loaded into halloysite nanotubes (HNTs) in a pre-compounding step prior film production. The detailed nanostructure and composition (in terms of carvacrol content) of the films were characterized and correlated to their barrier properties, carvacrol release rate, and antibacterial and antifungal activity. The resulting films exhibit high carvacrol content despite the harsh processing conditions (temperature of 200 °C and long processing time), regardless of the number of layers or the presence of HNTs. The multilayered films exhibit superior oxygen transmission rates and carvacrol diffusivity values that are more than two orders of magnitude lower in comparison to single-layered carvacrol-containing films (i.e., LDPE/carvacrol and LDPE/(HNTs/carvacrol)) produced by conventional cast extrusion. The (LDPE/carvacrol)/EVOH and (LDPE/[HNTs/carvacrol])/EVOH films demonstrated excellent antimicrobial efficacy against E. coli and Alternaria alternata in in vitro micro-atmosphere assays and against A. alternata and Rhizopus in cherry tomatoes, used as the food model. The results presented here suggest that sensitive essential oils, such as carvacrol, can be incorporated into plastic polymers constructed of tailored multiple layers, without losing their antimicrobial efficacy.