Biodegradation behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) containing phenolic compounds in seawater in laboratory testing conditions.

Biodegradation in marine medium of PHBV films with or without 5 % wt. of phenolic compounds (catechin, ferulic acid, and vanillin) was assessed at laboratory scale. Respirometric analyses and film disintegration kinetics were used to monitor the process over a period of 162 days. Structural changes in the films were analyzed throughout the exposure period using FESEM, DSC, Thermogravimetric analyses, XRD, and FTIR spectra. Respirometric tests showed complete biodegradation of all materials during the exposure period (the biodegradation half-time ranged between 63 and 79 days) but at different rates, depending on the phenolic compound incorporated. Ferulic acid and vanillin accelerate the PHBV biodegradation, whereas catechin delayed the process. Disintegration kinetics confirmed these results and showed that degradation occurred from the surface to the interior of the films. This was controlled by the degradation rate of the polymer amorphous phase and the formation of a biomass coating on the film surface. This is the result of the compounds generated by polymer degradation in combination with excretions from microorganisms. This coating has the potential to affect the enzyme diffusion to the polymer substrate. Moreover, the cohesion forces of the amorphous phase (reflected in its glass transition temperature) affected its degradation rate, while the slower degrading crystalline fragments were released, thus contributing to the disintegration process on the film's surface. Ferulic acid, with its hydrolytic effect, enhanced degradation, as did vanillin for its plasticizing and weakening effect in the amorphous phase of polymer matrix. In contrast, catechin with cross-linking effect hindered the progress of the material degradation, considerably slowing down the process rate.

Stability and Composting Behaviour of PLA-Starch Laminates Containing Active Extracts and Cellulose Fibres from Rice Straw.

The stability and composting behaviour of monolayers and laminates of poly (lactic acid) (PLA) and starch with and without active extracts and cellulose fibres from rice straw (RS) were evaluated. The retrogradation of the starch throughout storage (1, 5, and 10 weeks) gave rise to stiffer and less extensible monolayers with lower water vapour barrier capacity. In contrast, the PLA monolayers, with or without extract, did not show marked changes with storage. However, these changes were more attenuated in the bilayers that gained water vapour and oxygen barrier capacity during storage, maintaining the values of the different properties close to the initial range. The bioactivity of the active films exhibited a slight decrease during storage, so the antioxidant capacity is better preserved in the bilayers. All monolayer and bilayer films were fully composted within 90 days but with different behaviour. The bilayer assembly enhanced the biodegradation of PLA, whose monolayer exhibited a lag period of about 35 days. The active extract reduced the biodegradation rate of both mono- and bilayers but did not limit the material biodegradation within the time established in the Standard. Therefore, PLA-starch laminates, with or without the valorised fractions from RS, can be considered as biodegradable and stable materials for food packaging applications.

Active Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) Films Containing Phenolic Compounds with Different Molecular Structures.

To obtain more sustainable and active food packaging materials, PHBV films containing 5% wt. of phenolic compounds with different molecular structures (ferulic acid, vanillin, and catechin) and proved antioxidant and antimicrobial properties were obtained by melt blending and compression molding. These were characterized by their structural, mechanical, barrier, and optical properties, as well as the polymer crystallization, thermal stability, and component migration in different food simulants. Phenolic compounds were homogenously integrated within the polymer matrix, affecting the film properties differently. Ferulic acid, and mainly catechin, had an anti-plasticizing effect (increasing the polymer glass transition temperature), decreasing the film extensibility and the resistance to breaking, with slight changes in the elastic modulus. In contrast, vanillin provoked a plasticizing effect, decreasing the elastic modulus without notable changes in the film extensibility while increasing the water vapor permeability. All phenolic compounds, mainly catechin, improved the oxygen barrier capacity of PHBV films and interfered with the polymer crystallization, reducing the melting point and crystallinity degree. The thermal stability of the material was little affected by the incorporation of phenols. The migration of passive components of the different PHBV films was lower than the overall migration limit in every simulant. Phenolic compounds were released to a different extent depending on their thermo-sensitivity, which affected their final content in the film, their bonding forces in the polymer matrix, and the simulant polarity. Their effective release in real foods will determine their active action for food preservation. Catechin was the best preserved, while ferulic acid was the most released.

Production of Polyhydroxyalkanoates for Biodegradable Food Packaging Applications Using Haloferax mediterranei and Agrifood Wastes.

Polyhydroxyalkanoates (PHAs) are high-value biodegradable polyesters with thermoplastic properties used in the manufacturing of different products such as packaging films. PHAs have gained much attention from researchers and industry because of their biobased nature and appropriate features, similar to conventional synthetic plastics. This review aims to discuss some of the recent solutions to challenges associated with PHA production. The implementation of a cost-effective process is presented by following different strategies, such as the use of inexpensive carbon sources, the selection of high-producing microorganisms, and the functionalization of the final materials to make them suitable for food packaging applications, among others. Research efforts are needed to improve the economic viability of PHA production at a large scale. Haloferax mediterranei is a promising producer of PHAs due to its ability to grow in non-sterile conditions and the possibility of using seawater to prepare the growth medium. Additionally, downstream processing for PHA extraction can be simplified by treating the H. mediterranei cells with pure water. Further research should focus on the optimization of the recycling conditions for the effluents and on the economic viability of the side streams reutilization and desalinization as an integrated part of PHA biotechnological production.

Subcritical Water Extraction for Valorisation of Almond Skin from Almond Industrial Processing.

Almond skin (AS) is an agro-industrial residue from almond processing that has a high potential for valorisation. In this study, subcritical water extraction (SWE) was applied at two temperatures (160 and 180 °C) to obtain phenolic-rich extracts (water-soluble fraction) and cellulose fibres (insoluble fraction) from AS. The extraction conditions affected the composition and properties of both valorised fractions. The dry extracts obtained at 180 °C were richer in phenolics (161 vs. 101 mg GAE. g-1 defatted almond skin (DAS)), with greater antioxidant potential (1.063 vs. 1.490 mg DAS.mg-1 DPPH) and showed greater antibacterial effect (lower MIC values) against L. innocua (34 vs. 90 mg·mL-1) and E. coli (48 vs. 90 mg·mL-1) than those obtained at 160 °C, despite the lower total solid yield (21 vs. 29%) obtained in the SWE process. The purification of cellulose from the SWE residues, using hydrogen peroxide (H2O2), revealed that AS is not a good source of cellulose material since the bleached fractions showed low yields (20-21%) and low cellulose purity (40-50%), even after four bleaching cycles (1 h) at pH 12 and 8% H2O2. Nevertheless, the application of a green, scalable, and toxic solvent-free SWE process was highly useful for obtaining AS bioactive extracts for different food, cosmetic, or pharmaceutical applications.

Circular Bioeconomy: Novel Processes and Materials for Food Preservation.

Food preservation is a set of procedures and resources aimed at blocking the action of external and internal agents that may alter the original characteristics of food [...].

Biodegradation of PLA-PHBV Blend Films as Affected by the Incorporation of Different Phenolic Acids.

Films based on a 75:25 polylactic acid (PLA) and Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) blend, containing 2% (w/w) of different phenolic acids (ferulic, p-coumaric or protocatechuic acid), and plasticised with 15 wt. % polyethylene glycol (PEG 1000), were obtained by melt blending and compression moulding. The disintegration and biodegradation of the film under thermophilic composting conditions was studied throughout 35 and 45 days, respectively, in order to analyse the effect of the incorporation of the antimicrobial phenolic acids into the films. Sample mass loss, thermo-degradation behaviour and visual appearance were analysed at different times of the composting period. No effect of phenolic acids was observed on the film disintegration pattern, and the films were completely disintegrated at the end of the composting period. The biodegradation analysis through the CO2 measurements revealed that PLA-PHBV blend films without phenolic acids, and with ferulic acid, completely biodegraded after 20 composting days, while p-coumaric and protocatechuic slightly retarded full biodegradation (21 and 26 days, respectively). Phenolic acids mainly extended the induction period, especially protocatechuic acid. PLA-PHBV blend films with potential antimicrobial activity could be used to preserve fresh foodstuff susceptible to microbial spoilage, with their biodegradation under composting conditions being ensured.

Antimicrobial PLA-PVA multilayer films containing phenolic compounds.

Multilayer materials with good interlayer-adhesion were obtained by thermocompression for laminating an internal poly (vinyl alcohol) (PVA) layer with two external poly (lactic acid) (PLA) layers. Carvacrol or ferulic acid were incorporated into the PVA sheet to obtain active materials. The multilayer films were characterised as to their microstructure, thermal behaviour, tensile and barrier properties. Furthermore, the antimicrobial capacity of the materials was analysed in packaged beef meat samples for 17 days at 5 °C. The laminates exhibited tensile properties close to those of the PLA films, but with enhanced stretchability. Compared to the monolayers, the barrier capacity of multilayers was much improved by combining polyester and PVA layers, which provide the laminate with water vapour and oxygen barrier capacity, respectively. Active multilayers were effective at controlling microbial growth in beef meat during cold storage. Therefore, the materials developed were functionally adequate for food packaging purposes and successfully promoted the meat preservation.

Biodegradable Antimicrobial Films for Food Packaging: Effect of Antimicrobials on Degradation.

The environmental problem generated by the massive consumption of plastics makes necessary the developing of biodegradable antimicrobial materials that can extend food shelf-life without having a negative impact on the environment. The current situation regarding the availability of biodegradable food packaging materials has been analysed, as well as different studies where antimicrobial compounds have been incorporated into the polymer matrix to control the growth of pathogenic or spoilage bacteria. Thus, the antimicrobial activity of active films based on different biodegradable polymers and antimicrobial compounds has been discussed. Likewise, relevant information on biodegradation studies carried out with different biopolymers in different environments (compost, soil, aquatic), and the effect of some antimicrobials on this behavior, are reviewed. In most of the studies, no relevant effect of the incorporated antimicrobials on the degradation of the polymer were observed, but some antimicrobials can delay the process. The changes in biodegradation pattern due to the presence of the antimicrobial are attributed to its influence on the microorganism population responsible for the process. More studies are required to know the specific influence of the antimicrobial compounds on the biodegradation behavior of polymers in different environments. No studies have been carried out or marine media to this end.

Liposomal Encapsulation of Carvacrol to Obtain Active Poly (Vinyl Alcohol) Films.

Lecithins of different origins and compositions were used for the liposomal encapsulation of carvacrol within the framework of the development of active films for food packaging. Liposomes were incorporated into aqueous polymeric solutions from fully (F) and partially (P) hydrolysed Poly (vinyl alcohol) (PVA) to obtain the films by casting. The particle size distribution and ζ-potential of the liposomal suspensions, as well as their stability over time, were evaluated. Liposomal stability during film formation was analysed through the carvacrol retention in the dried film and the film microstructure. Subtle variations in the size distributions of liposomes from different lecithins were observed. However, the absolute values of the ζ-potential were higher (-52, -57 mV) for soy lecithin (SL) liposomes, followed by those of soy lecithin enriched with phosphatidylcholine (SL-PC) (-43, -50 mV) and sunflower lecithin (SFL) (-33, -38 mV). No significant changes in the liposomal properties were observed during the study period. Lyotropic mesomorphism of lipid associations and carvacrol leakage occurred to differing extents during the film drying step, depending on the membrane lipid composition and surface charge. Liposomes obtained with SL-PC were the most effective at maintaining the stability of carvacrol emulsion during film formation, which led to the greatest carvacrol retention in the films, whereas SFL gave rise to the least stable system and the highest carvacrol losses. P-PVA was less sensitive to the emulsion destabilisation due to its greater bonding capacity with carvacrol. Therefore, P-PVA with carvacrol-loaded SL-PC liposomes has great potential to produce active films for food packaging applications.

Application of Ultrasound Pre-Treatment for Enhancing Extraction of Bioactive Compounds from Rice Straw.

The extraction of water-soluble bioactive compounds using different green methods is an eco-friendly alternative for valorizing agricultural wastes such as rice straw (RS). In this study, aqueous extracts of RS (particles < 500 µm) were obtained using ultrasound (US), reflux heating (HT), stirring (ST) and a combination of US and ST (USST) or HT (USHT). The extraction kinetics was well fitted to a pseudo-second order model. As regards phenolic compound yield, the US method (342 mg gallic acid (GAE). 100 g-1 RS) was more effective than the ST treatment (256 mg GAE.100 g-1 RS), reaching an asymptotic value after 30 min of process. When combined with HT (USHT), the US pre-treatment led to the highest extraction of phenolic compounds from RS (486 mg GAE.100 g-1 RS) while the extract exhibited the greatest antioxidant activity. Furthermore, the USHT extract reduced the initial counts of Listeria innocua by 1.7 logarithmic cycles. Therefore, the thermal aqueous extraction of RS applying the 30 min US pre-treatment, represents a green and efficient approach to obtain bioactive extracts for food applications.

Polylactic acid-based materials encapsulating carvacrol obtained by solvent casting and electrospinning.

Polylactic acid (PLA) dissolved (15 wt.%) in ethyl acetate (EtAc): dimethyl sulfoxide (DMSO) binary systems (0:1; 1:3, and 2:3 v/v) was used as carrier to obtain carvacrol (CA)-loaded (20 wt.% with respect to PLA) matrices by electrospinning, in comparison with solvent casting. Field emission scanning electron microscopy (FESEM) observations showed that CA-loaded electrospun fibers were thinner than the CA-free ones, and their encapsulating efficiency (EE) increased when EtAc was present in the solvent. The cast films had higher EE (up to 89%) than the electrospun mats (maximum 68%). Thermogravimetric analysis and differential scanning calorimetry revealed that CA-free matrices retain more solvent than the samples with CA; this effect is being more noticeable in fibers rather than in cast films. The thermal analysis revealed stronger retention forces of CA in the fibers than in the cast material and the CA plasticizing effect in the PLA matrices, in accordance with its retained amount. PRACTICAL APPLICATION: The carvacrol-loaded polylactic acid materials obtained in this study are intended to serve as possible active layer in obtaining active (antimicrobial and/or antioxidant) multilayer materials for the packaging of foodstuffs, when applied onto a supporting polymer layer. Active properties of the material, as well as the potential carvacrol sensory impact, in packaged products should be assessed in further studies.

The Incorporation of Carvacrol into Poly (vinyl alcohol) Films Encapsulated in Lecithin Liposomes.

Lecithin-encapsulated carvacrol has been incorporated into poly (vinyl alcohol) (PVA) for the purpose of obtaining active films for food packaging application. The influence of molecular weight (Mw) and degree of hydrolysis (DH) of the polymer on its ability to retain carvacrol has been analysed, as well as the changes in the film microstructure, thermal behaviour, and functional properties as packaging material provoked by liposome incorporation into PVA matrices. The films were obtained by casting the PVA aqueous solutions where liposomes were incorporated until reaching 0 (non-loaded liposomes), 5 or 10 g carvacrol per 100 g polymer. The non-acetylated, high Mw polymer provided films with a better mechanical performance, but less CA retention and a more heterogeneous structure. In contrast, partially acetylated, low Mw PVA gave rise to more homogenous films with a higher carvacrol content. Lecithin enhanced the thermal stability of both kinds of PVA, but reduced the crystallinity degree of non-acetylated PVA films, although it did not affect this parameter in acetylated PVA when liposomes contained carvacrol. The mechanical and barrier properties of the films were modified by liposome incorporation in line with the induced changes in crystallinity and microstructure of the films.

Incorporation of natural antioxidants from rice straw into renewable starch films.

This study showed that rice straw waste is a valuable source for the extraction of water-soluble phenolic compounds that can be successfully incorporated into bioactive starch-based films. The major phenolic compounds in the extract were identified as ferulic, p-coumaric and protocatechuic acid using UHPLC-MS. Homogeneous films with antioxidant properties were produced by melt blending and compression molding and the changes in the physico-chemical properties were evaluated. The produced antioxidant starch films were slightly reddish-colored and exhibited good in-vitro antiradical scavenging activity against DPPH*. The addition of the antioxidant extract improved the oxygen barrier properties without negatively affecting the thermal and the water vapor barrier properties. However, antioxidant starch films turned more brittle with increasing amount of the antioxidant extract, which was probably due to interactions of phenolic compounds with the starch chains. The film forming process induced chain scission of starch molecules in all films, shown in a decrease in molecular weight of native starch from 9.1 × 106 Da to values as low as 1.0-3.5 × 106 Da. This study aids a circular economy by recycling rice straw for the production of bioactive food packaging.

Encapsulation of eugenol by spray-drying using whey protein isolate or lecithin: Release kinetics, antioxidant and antimicrobial properties.

The encapsulation of eugenol (E) by spray-drying using whey protein (WP) or soy lecithin (LE) and maltodextrin in combination with oleic acid (OA) and chitosan (CH) was analysed in order to obtain antioxidant and antimicrobial powders for food applications. Formulations with only WP or LE showed higher encapsulation efficiencies (EE) (95-98%) and antibacterial effect against E. coli and L. innocua due to their greater E load. Incorporation of OA or CH promoted lower EE, which negatively affected the antimicrobial and antioxidant activities of the powders. Furthermore, the addition of CH implied less thermal protection against the E losses. The eugenol release was not notably affected by pH or polarity of the food simulant, but the release rate significantly decreased when incorporating OA and CH. The E-LE formulations better retained the eugenol than E-WP powders when heated above 200 °C, this being relevant for the powder inclusion in thermally treated products.

Antioxidant starch films containing sunflower hull extracts.

This study explores the preparation of antioxidant starch food packaging materials by the incorporation of valuable phenolic compounds extracted from sunflower hulls, which are an abundant by-product from food industry. The phenolic compounds were extracted with aqueous methanol and embedded into starch films. Their effect on starch films was investigated in terms of antioxidant activity, optical, thermal, mechanical, barrier properties and changes in starch molecular structure. The starch molecular structure was affected during thermal processing resulting in a decrease in molar mass, smaller amylopectin molecules and shorter amylose branches. Already 1-2% of extracts were sufficient to produce starch films with high antioxidant capacity. Higher amounts (4-6%) of extract showed the highest antioxidant activity, the lowest oxygen permeability and high stiffness and poor extensibility. The phenolic extracts affected predominantly the mechanical properties, whereas other changes could mainly be correlated to the lower glycerol content which was partially substituted by the extract.

Release of polyphenols from starch-chitosan based films containing thyme extract.

The release kinetics of thyme extract polyphenols (TE) from chitosan (CH), pea starch (S) and CH:S blend films in different solvents was evaluated, as well as their antioxidant activity in each release media. Pure starch films showed the fastest delivery rate and the highest delivery ratio of polyphenols, although the corresponding release media exhibited the lowest antioxidant capacity. TE provided CH based films with remarkable antioxidant activity, despite the lower polyphenol release obtained in all solvents, due to the strong polyphenols-chitosan interactions. The maximum amount of polyphenols delivered was found in the acetic acid solution, due to the high solubility of CH. The incorporation of tannic acid (TA) into CH films promoted cross-linking effect, which delays the TE release rate in water and ethanol aqueous solutions, except for CH:S:TA films. Thus, the polarity of the solvents and the polyphenols-matrix interactions markedly affected the polyphenol release and the antioxidant activity of the films.

Combination of Poly(lactic) Acid and Starch for Biodegradable Food Packaging.

The massive use of synthetic plastics, in particular in the food packaging area, has a great environmental impact, and alternative more ecologic materials are being required. Poly(lactic) acid (PLA) and starch have been extensively studied as potential replacements for non-degradable petrochemical polymers on the basis of their availability, adequate food contact properties and competitive cost. Nevertheless, both polymers exhibit some drawbacks for packaging uses and need to be adapted to the food packaging requirements. Starch, in particular, is very water sensitive and its film properties are heavily dependent on the moisture content, exhibiting relatively low mechanical resistance. PLA films are very brittle and offer low resistance to oxygen permeation. Their combination as blend or multilayer films could provide properties that are more adequate for packaging purposes on the basis of their complementary characteristics. The main characteristics of PLA and starch in terms of not only the barrier and mechanical properties of their films but also of their combinations, by using blending or multilayer strategies, have been analyzed, identifying components or processes that favor the polymer compatibility and the good performance of the combined materials. The properties of some blends/combinations have been discussed in comparison with those of pure polymer films.

Antioxidant edible films based on chitosan and starch containing polyphenols from thyme extracts.

The aim of this study was to analyse the antioxidant activity of different polymeric matrices based on chitosan and starch, incorporating a thyme extract (TE) rich in polyphenols. TE provided the films with remarkable antioxidant activity. When mixed with chitosan, the polyphenols interacted with the polymer chains, acting as crosslinkers and enhancing the tensile behaviour of films. The opposite effect was observed when incorporated into the starch matrix. All the films became darker, more reddish and less transparent when TE was incorporated. These colour changes were more marked in starch matrices, which suggests that TE compounds were poorly encapsulated. The use of chitosan-based matrices carrying TE polyphenols is recommended as a means of obtaining antioxidant films, on the basis of their tensile response and greater antioxidant activity, which could be associated with the development of polyphenol-chitosan interactions, contributing to a better protection of the functionality of polyphenols during film formation and conditioning.

Physical and Antimicrobial Properties of Starch-PVA Blend Films as Affected by the Incorporation of Natural Antimicrobial Agents.

In this work, active films based on starch and PVA (S:PVA ratio of 2:1) were developed by incorporating neem (NO) and oregano essential oils (OEO). First, a screening of the antifungal effectiveness of different natural extracts (echinacea, horsetail extract, liquid smoke and neem seed oil) against two fungus (P. expansum and A. niger) was carried out. The effect of NO and OEO incorporation on the films' physical and antimicrobial properties was analyzed. Only composite films containing OEO exhibited antibacterial and antifungal activity. Antibacterial activity occurred at low OEO concentration (6.7%), while antifungal effect required higher doses of OEO in the films. Incorporation of oils did not notably affect the water sorption capacity and water vapor barrier properties of S-PVA films, but reduced their transparency and gloss, especially at the highest concentrations. The mechanical response of the S-PVA films was also negatively affected by oil incorporation but this was only relevant at the highest oil ratio (22%). S-PVA films with 6.7% of OEO exhibited the best physical properties, without significant differences with respect to the S-PVA matrix, while exhibiting antibacterial activity. Thus, the use of OEO as a natural antimicrobial incorporated into starch-PVA films represents a good and novel alternative in food packaging applications.