The purpose of the present study is to develop new multifunctional environmentally friendly materials having applications both in medical and food packaging fields. New poly(lactic acid) (PLA)-based multifunctional materials containing additives derived from natural resources like chitosan (CS) and rosemary extract (R) were obtained by melt mixing. Each of the selected components has its own specific properties such as: PLA is a biodegradable thermoplastic aliphatic polyester derived from renewable biomass, heat-resistant, with mechanical properties close to those of polystyrene and polyethylene terephthalate, and CS offers good antimicrobial activity and biological functions, while R significantly improves antioxidative action necessary in all applications. A synergy of their combination, an optimum choice of their ratio, and processing parameters led to high performance antimicrobial/antioxidant/biocompatible/environmentally degradable materials. The polyethylene glycol (PEG)-plasticized PLA/chitosan/powdered rosemary extract biocomposites of various compositions were characterized in respect to their mechanical and rheological properties, structure by spectroscopy, antioxidant and antimicrobial activities, and in vitro and in vivo biocompatibility. Scanning electron microscopy images evidence the morphology features added by rosemary powder presence in polymeric materials. Incorporation of additives improved elongation at break, antibacterial and antioxidant activity and also biocompatibility. Migration of bioactive components into D1 simulant is slower for PEG-plasticized PLA containing 6 wt % chitosan and 0.5 wt % rosemary extract (PLA/PEG/6CS/0.5 R) biocomposite and it occurred by a diffusion-controlled mechanism. The biocomposites show high hydrophilicity and good in vitro and in vivo biocompatibility. No hematological, biochemical and immunological modifications are induced by subcutaneous implantation of biocomposites. All characteristics of the PEG-plasticized PLA-based biocomposites recommend them as valuable materials for biomedical implants, and as well as for the design of innovative drug delivery systems. Also, the developed biocomposites could be a potential nature-derived active packaging with controlled release of antimicrobial/antioxidant compounds.

New multifunctional materials containing additives derived from natural resources as powdered rosemary ethanolic extract were obtained by melt mixing and processed in good conditions without degradation and loss of additives. Incorporation of powdered rosemary ethanolic extract (R) into poly(lactic acid) (PLA) improved elongation at break, rheological properties, antibacterial and antioxidant activities, in addition to the biocompatibility. The good accordance between results of the chemiluminescence method and radical scavenging activity determination by chemical method evidenced the increased thermoxidative stability of the PLA biocomposites with respect to neat PLA, with R acting as an antioxidant. PLA/R biocomposites also showed low permeability to gases and migration rates of the bioactive compounds and could be considered as high-performance materials for food packaging. In vitro biocompatibility based on the determination of surface properties demonstrated a good hydrophilicity, better spreading and division of fibroblasts, and increased platelet cohesion. The implantation of PLA/R pellets, was proven to possess a good in vivo biocompatibility, and resulted in similar changes in blood parameters and biochemical responses with the control group, suggesting that these PLA-based materials demonstrate very desirable properties as potential biomaterials, useful in human medicine for tissue engineering, wound management, orthopedic devices, scaffolds, drug delivery systems, etc. Therefore, PLA/R-based materials show promising properties for applications both in food packaging and as bioactive biomaterials.

Several recipes based on PLA, bio-plasticizers, and active agents such as vitamin E and cold-pressed rosehip seed oil encapsulated into chitosan by the emulsion method named here as chitosan modified (CS-M) were elaborated by melt compounding for food packaging applications. Resulted biocomposites have been investigated from the point of view of physical-mechanical, thermal, barrier, antimicrobial, and antioxidant properties to select the formulations with the optimum features to produce food trays and films for packaging applications. The obtained results showed that the elaborated formulations exhibit tensile strength and flexibility dependent on their composition being either rigid or flexible, as well as antimicrobial and antioxidant activity, which will potentially lead to prolonged use for food packaging. The recipe with PLA matrix and 40:60 Lapol^®108 as masterbarch/polyethylene glycol (MB/PEG) bio-plasticizers ratio was distinguished by an improvement of over 100 times in terms of flexibility compared with neat PLA, while the highest antioxidant activity (36.27%) was recorded for the sample containing a CS-M and MB/PEG ratio of 60:40. An enhancement of ~50% for the water vapor barrier was recorded for PLA/CS-M_100:0 material. By modulating the MB and PEG bio-plasticizers ratio, the design of new eco-friendly food packaging materials with antimicrobial/antioxidant characteristics by using the existing technologies for processing synthetic polymers (melt mixing, compounding, pressing, thermoforming) has been successfully realized.

Antioxidant activity is an important feature for food contact materials such as packaging, aiming to preserve freshness and retard food spoilage. Common bioactive agents are highly susceptible to various forms of degradation; therefore, protection is required to maintain functionality and bioavailability. Poly(ε-caprolactone) (PCL), a biodegradable GRAS labeled polymer, was used in this study for encapsulation of α-tocopherol antioxidant, a major component of vitamin E, in the form of electrospun fibers. Rheological properties of the fiber forming solutions, which determine the electrospinning behavior, were correlated with the properties of electrospun fibers, e.g., morphology and surface properties. Interactions through hydrogen bonds were evidenced between the two components. These have strong effect on structuration of macromolecular chains, especially at low α-tocopherol amounts, decreasing viscosity and elastic modulus. Intra-molecular interactions in PCL strengthen at high α-tocopherol amounts due to decreased solvation, allowing good structural recovery after cease of mechanical stress. Morphologically homogeneous electrospun fibers were obtained, with ~6 μm average diameter. The obtained fibers were highly hydrophobic, with fast release in 95% ethanol as alternative simulant for fatty foods. This induced good in vitro antioxidant activity and significant in vivo reduction of microbial growth on cheese, as determined by respirometry. Therefore, the electrospun fibers from PCL entrapping α-tocopherol as bioactive agent showed potential use in food packaging materials.

Natural deep eutectic solvents (NADES)-hydroxypropyl cellulose (HPC) self-assembled gels with potential for pharmaceutical applications are prepared. FT-IR, ¹HNMR, DSC, TGA and rheology measurements revealed that hydrogen bond acceptor–hydrogen bond donor interactions, concentration of NADES and the water content influence significantly the physico-chemical characteristics of the studied gel systems. HPC-NADES gel compositions have thermal stabilities lower than HPC and higher than NADES components. Thermal transitions reveal multiple glass transitions characteristic of phase separated systems. Flow curves evidence shear thinning (pseudoplastic) behavior. The flow curve shear stress vs. shear rate were assessed by applying Bingham, Herschel–Bulkley, Vocadlo and Casson rheological models. The proposed correlations are in good agreement with experimental data. The studied gels evidence thermothickening behavior due to characteristic LCST (lower critical solution temperature) behavior of HPC in aqueous systems and a good biocompatibility with normal cells (human gingival fibroblasts). The order of antibacterial and antifungal activities (S.aureus, E.coli, P. aeruginosa and C. albicans) is as follows: citric acid >lactic acid > urea > glycerol, revealing the higher antibacterial and antifungal activities of acids.