Antimicrobial activity of metal cation-exchanged zeolites and their evaluation on injection-molded pieces of bio-based high-density polyethylene

[EN] In this study, three different natural types of unmodified zeolite (chabazite, mordenite, and faujasite) were initially characterized for their morphology, elemental composition, and antimicrobial activity against foodborne bacteria and fungi. The chabazite-type zeolite was selected due to its optimal morphology and lowest silicon to aluminum ratio (Si/Al). This was then solution exchanged with different combinations of silver (Ag+), copper (Cu2+), and zinc (Zn2+) ions to prepare single, binary, and ternary metal cation-modified zeolites. Antimicrobial results clearly indicated that Ag-based zeolites exhibited more antimicrobial activity than Cu- and Zn-based zeolites. Interestingly, the multi-ionic zeolite, that is, the ternary Ag-Cu-Zn-zeolite, was the most efficient antimicrobial sample in terms of the amount of added silver. In the last step, the obtained multi-ionic zeolite was, for the first time, incorporated at different weight amounts (1, 5, 10, and 15 wt%) into a bio-based high-density polyethylene (bio-HDPE) matrix by extrusion and shaped into pieces by injection molding. Novel sustainable polymer composite pieces with improved stiffness and hardness and high antimicrobial activity were obtained. These treated materials offer industrial relevance to control the growth of harmful microorganisms in hygiene applications related to the food industry.Spanish Ministry of Economy and Competitiveness, Grant/Award Number: Project MAT2014-59242-C2-1-R; Conselleria d'Educacio, Cultura i Esport - Generalitat Valenciana, Grant/Award Number: GV/2014/008Torres-Giner, S.; Torres, A.; Ferrándiz, M.; Fombuena, V.; Balart, R. (2017). Antimicrobial activity of metal cation-exchanged zeolites and their evaluation on injection-molded pieces of bio-based high-density polyethylene. Journal of Food Safety. 37(4). https://doi.org/10.1111/jfs.12348Se1234837

Quality and Shelf-Life Stability of Pork Meat Fillets Packaged in Multilayer Polylactide Films

[EN] In the present study, the effectiveness of a multilayer film of polylactide (PLA), fully bio-based and compostable, was ascertained to develop a novel sustainable packaging solution for the preservation of fresh pork meat. To this end, the multilayer PLA films were first characterized in terms of their thermal characteristics, structure, mechanical performance, permeance to water and aroma vapors and oxygen, and optical properties and, for the first time, compared with two commercial high-barrier multilayer packaging films. Thereafter, the multilayers were thermosealed to package fillets of fresh pork meat and the physicochemical changes, lipid oxidation levels, and microbiological counts were monitored in the food samples during storage under refrigeration conditions. Results showed that the meat fillets packaged in PLA developed a redder color and showed certain indications of dehydration and oxidation, being more noticeably after 11 days of storage, due to the higher water vapor and oxygen permeance values of the biopolymer multilayer. However, the pH changes and bacterial growth in the cold-stored fresh pork meat samples were minimal and very similar in the three tested multilayer films, successfully accomplishing the requirements of the food quality and safety standards at the end of storage.This research was funded by the Spanish Ministry of Science and Innovation (MICI), grant number PID2019-105207RB-I00. E.H.-G. and S.T.-G. acknowledge MICI for her predoctoral research grant (BES2017-082040) and his Ramón y Cajal contract (RYC2019-027784-I). The authors are also grateful to the Packaging Technologies Department of AINIA for the technical support provided during the determination of the multilayer structures. Derprosa is also acknowledged for gently providing the multilayer PLA film.Hernandez-Garcia, E.; Vargas, M.; Torres-Giner, S. (2022). Quality and Shelf-Life Stability of Pork Meat Fillets Packaged in Multilayer Polylactide Films. Foods. 11(3):1-20. https://doi.org/10.3390/foods1103042612011

Electrospraying assisted by pressurized gas as an innovative high-throughput process for the microencapsulation and stabilization of docosahexaenoic acid-enriched fish oil in zein prolamine

[EN] Zein, a prolamine obtained from maize, was employed to encapsulate a fish oil highly enriched with docosahexaenoic acid (DHA) by an innovative process termed electrospraying assisted by pressurized gas (EAPG). This technology combines high electric voltage with pneumatic spray to yield a high-throughput encapsulation process. Semi-spherical zein flowable capsules with mean sizes of 1.4 mu m containing the DHA-enriched fish oil were produced by EAPG from inert ethanol solutions at room conditions, presenting a high encapsulation efficiency. The oxidative stability tests carried out in the zein microcapsules obtained by EAPG showed that the DHA-enriched fish oil was efficiently protected over storage time. Sensory tests were also performed on fortified reconstituted milk with the freshly prepared zein/DHA-enriched fish oil microcapsules, suggesting negligible oxidation effects after 45 days. The results described herein indicate that EAPG is a promising innovative high-throughput electrospraying-based methodology for the encapsulation of bioactives and, therefore, the resultant DHA-enriched fish oil containing microcapsules can be industrially applied for the formulation of fortified foods. Industrial relevance: An innovative process, termed electrospraying assisted by pressurized gas (EAPG), is herein originally presented as a novel encapsulation methodology. This technology is based on the combination of high voltage and pneumatic spray, allowing the formation of microcapsules at room temperature conditions. Thus, EAPG shows a great deal of potential to encapsulate nutraceuticals and other bioactives that are sensitive to thermal degradation and/or oxidation. The resultant bioactive-containing capsules can be, thereafter, applied to develop novel fortified food products.The authors would like to thank the Spanish Ministry of Economy and Competitiveness (MINECO) project AGL2015-63855-C2-1-R and to the H2020 EU project YPACK (reference number 773872) for funding.Busolo, M.; Torres-Giner, S.; Prieto, C.; Lagaron, JM. (2019). Electrospraying assisted by pressurized gas as an innovative high-throughput process for the microencapsulation and stabilization of docosahexaenoic acid-enriched fish oil in zein prolamine. Innovative Food Science & Emerging Technologies. 51:12-19. https://doi.org/10.1016/j.ifset.2018.04.007S121951Aghbashlo, M., Mobli, H., Madadlou, A., & Rafiee, S. (2012). The correlation of wall material composition with flow characteristics and encapsulation behavior of fish oil emulsion. Food Research International, 49(1), 379-388. doi:10.1016/j.foodres.2012.07.031Anwar, S. H., & Kunz, B. (2011). The influence of drying methods on the stabilization of fish oil microcapsules: Comparison of spray granulation, spray drying, and freeze drying. Journal of Food Engineering, 105(2), 367-378. doi:10.1016/j.jfoodeng.2011.02.047Anwar, S. H., Weissbrodt, J., & Kunz, B. (2010). Microencapsulation of Fish Oil by Spray Granulation and Fluid Bed Film Coating. Journal of Food Science, 75(6), E359-E371. doi:10.1111/j.1750-3841.2010.01665.xBakry, A. M., Abbas, S., Ali, B., Majeed, H., Abouelwafa, M. Y., Mousa, A., & Liang, L. (2015). Microencapsulation of Oils: A Comprehensive Review of Benefits, Techniques, and Applications. Comprehensive Reviews in Food Science and Food Safety, 15(1), 143-182. doi:10.1111/1541-4337.12179Busolo, M. A., & Lagaron, J. M. (2012). Oxygen scavenging polyolefin nanocomposite films containing an iron modified kaolinite of interest in active food packaging applications. 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Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil

[EN] Thiswork reports the effect of acrylated epoxidized soybean oil (AESO) addition on the mechanical, thermal, and thermomechanical properties of polylactide (PLA) parts obtained by injection molding. To this end, AESO, a chemically multi-functionalized vegetable oil, was incorporated into PLA during melt processing. The PLA parts with AESO contents in the 2.5¿7.5 wt% range showed a remarkable enhancement in both elongation at break and impact-absorbed energy while their tensile and flexural strength as well as thermomechanical properties were maintained or slightly improved. Additionally, the AESO-containing PLA parts presented higher thermal stability and lower crystallinity. The improvement achievedwas ascribed to a dual effect of plasticization in combination with a chain-extension and/or cross-linking process of the PLA chains by the highly reactive acrylate and epoxy groups present in AESO. The use of AESO thus represents an environmentally friendly solution to obtain toughened PLA materials of high interest in, for instance, rigid packaging, automotive or building and construction applications.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) [grant numbers MAT2014-59242-C2-1-R & AGL2015-63855-C2-1-R]. L. Quiles-Carrillo thanks the Spanish Ministry of Education, Culture, and Sports (MECD) for financial support through the FPU program [grant number FPU15/03812].Quiles-Carrillo, L.; Duart, S.; Montanes, N.; Torres-Giner, S.; Balart, R. (2018). Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil. Materials & Design. 140:54-63. https://doi.org/10.1016/j.matdes.2017.11.031S546314

Optimization of microwave-assisted extraction of phenolic compounds with antioxidant activity from carob pods

[EN] A microwave-assisted extraction (MAE) procedure to obtain phenolic compounds from carob bark was optimized by using response surface methodology. A four-factor, three-level Box-Behnken design with five central points was used to evaluate the influence of temperature, solid-liquid ratio, ethanol concentration and time in carob bark extraction in terms of antioxidant activity (DPPH) and total extraction yield. Optimal extraction conditions were found using 80 ºC, 35% (v/v) ethanol, a ratio of 35 mL/g and 29.5 min. Total phenolics content (TPC), antioxidant activity (DPPH, FRAP, ABTS), carbohydrates content and main polyphenols composition (HPLC) were determined at optimal conditions. An experimental total yield of 66.5% was obtained with a TPC value of 33.6 mg GAE/g DW and polysaccharides content of 345.4 mg glucose/g DW. A high antioxidant activity was also shown by the three methods tested. The results showed the potential of carob pods skin as a natural source of phenolic compounds, in particular gallic acid, and the effectiveness of MAE as extraction technique for the revalorization of this agro-food waste.This research was supported by the Spanish Ministry of Science, Innovation and Universities (MICIU) programs MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R and by the EU H2020 project YPACK (reference number 773872). Quiles-Carrillo wants to thank GV for his FPI grant (ACIF/2016/182) and MECD for his FPU grant (FPU15/03812). Torres-Giner also thank MINECO for his Juan de la Cierva contract (IJCI-2016-29675).Quiles-Carrillo, L.; Mellinas, C.; Garrigos, M.; Balart, R.; Torres-Giner, S. (2019). Optimization of microwave-assisted extraction of phenolic compounds with antioxidant activity from carob pods. 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Ductility and Toughness Improvement of Injection-Molded Compostable Pieces of Polylactide by Melt Blending with Poly(e-caprolactone) and Thermoplastic Starch

[EN] The present study describes the preparation and characterization of binary and ternary blends based on polylactide (PLA) with poly("-caprolactone) (PCL) and thermoplastic starch (TPS) to develop fully compostable plastics with improved ductility and toughness. To this end, PLA was first melt-mixed in a co rotating twin-screw extruder with up to 40 wt % of different PCL and TPS combinations and then shaped into pieces by injection molding. The mechanical, thermal, and thermomechanical properties of the resultant binary and ternary blend pieces were analyzed and related to their composition. Although the biopolymer blends were immiscible, the addition of both PCL and TPS remarkably increased the flexibility and impact strength of PLA while it slightly reduced its mechanical strength. The most balanced mechanical performance was achieved for the ternary blend pieces that combined high PCL contents with low amounts of TPS, suggesting a main phase change from PLA/TPS (comparatively rigid) to PLA/PCL (comparatively flexible). The PLA-based blends presented an ¿island-and-sea¿ morphology in which the TPS phase contributed to the fine dispersion of PCL as micro-sized spherical domains that acted as a rubber-like phase with the capacity to improve toughness. In addition, the here-prepared ternary blend pieces presented slightly higher thermal stability and lower thermomechanical stiffness than the neat PLA pieces. Finally, all biopolymer pieces fully disintegrated in a controlled compost soil after 28 days. Therefore, the inherently low ductility and toughness of PLA can be successfully improved by melt blending with PCL and TPS, resulting in compostable plastic materials with a great potential in, for instance, rigid packaging applications.This research was supported by the Ministry of Science, Innovation, and Universities (MICIU) program numbers MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R, and by the EU H2020 project YPACK (reference number 773872).Quiles-Carrillo, L.; Montanes, N.; Pineiro, F.; Jorda-Vilaplana, A.; Torres-Giner, S. (2018). Ductility and Toughness Improvement of Injection-Molded Compostable Pieces of Polylactide by Melt Blending with Poly(e-caprolactone) and Thermoplastic Starch. Materials. 11(11):1-20. https://doi.org/10.3390/ma11112138S1201111Hopewell, J., Dvorak, R., & Kosior, E. (2009). Plastics recycling: challenges and opportunities. 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Innovative solutions and challenges to increase the use of poly(3-hydroxybutyrate) in food packaging and disposables

[EN] Poly(3-hydroxybutyrate) (PHB) has gain in recent years a huge interest in the food packaging field due to its renewable origin from waste as well as non-food crops, high mechanical strength, medium-to-high barrier performance, and inherent biodegradability in natural environments. Despite these advantages, PHB also shows a narrow processing window and high brittleness since this homopolyester shows low thermal stability and high crystallinity, limiting its industrial application. The present review provides an updated state of the art of the most relevant aspects in terms of processing and properties of PHB materials with a particular emphasis for their use in sustainable food packaging. It also describes the most potential strategies that can be applied to improve both the processability and mechanical properties of PHB, including the melt blending with green plasticizers and flexible biodegradable polymers as well as the development of more ductile co-polyesters. Finally, the waste management of the newly developed PHB-based articles is discussed, from their potential compostability to develop more biopolymers to more economically favored alternatives such as mechanical and chemical recycling technologies.This work was funded by the Spanish Ministry of Science and Innovation (MICINN, Spain), grant PID2021-123753NA-C32 funded by MCIN/AEI/10.13039/501100011033 and by "ERDF A way of making Europe", by the "European Union"; Comunidad de Madrid (Spain) by CIRCULAGROPLAST, a research Project that has been funded by the Comunidad de Madrid through the call Research Grants for Young Investigators from Universidad Politécnica de Madrid; as well as by the Generalitat Valenciana (Spain) through the BEST Program (CIBEST/2021/94). S. Torres-Giner acknowledges the Spanish Ministry of Science and Innovation (MICINN, Spain) for his Ramón y Cajal contract (RYC2019-027784-I).Garcia-Garcia, D.; Quiles-Carrillo, L.; Balart, R.; Torres-Giner, S.; Arrieta, MP. (2022). Innovative solutions and challenges to increase the use of poly(3-hydroxybutyrate) in food packaging and disposables. European Polymer Journal. 178:1-20. https://doi.org/10.1016/j.eurpolymj.2022.11150512017

The impact of electrospun films of poly(epsilon-caprolactone) filled with nanostructured zeolite and silica microparticles on in vitro histamine formation by Staphylococcus aureus and Salmonella Paratyphi A

[EN] This research study originally reports the preparation and characterization of electrospun films based on poly(epsilon-caprolactone) (PCL) with high histamine-binding capacity. To this end, submicron PCL fibers filled with nanostructured zeolite or silica (SiO2) microparticles in the 5-20 wt% range were first prepared by solution electrospinning. The resultant electrospun composite fiber mats were thereafter thermally post-treated at 55 degrees C to successfully develop contact-transparent films with reduced porosity and improved mechanical strength. The capacity of the developed composite films to entrap histamine was evaluated in vitro by the culture media method using Staphylococcus aureus (S. aureus) and Salmonella Paratyphi A (S. Paratyphi A) foodborne bacteria. Both electrospun zeolite- and SiO2-containing PCL films exhibited high histamine-binding capacity, being more effective for S. aureus. The histamine entrapment performance was significantly higher for the PCL films filled with zeolite due to the enhanced porous structure and more optimal adsorption selectivity of this inorganic filler. The here-developed electrospun composite films can be applied as novel active-scavenging packaging materials to entrap heat-stable histamine and other biogenic amines released from fish and fishery products.This research was funded by the Spanish Ministry of Science, Innovation, and Universities (MICIU) program number AGL2015-63855-C2-1-R and by the EU H2020 YPACK project (reference number 773872). The authors also thank the Republic of Turkey Ministry of Agriculture and Forestry General Directorate of Agricultural Research and Policies (TAGEM) and Central Fisheries Research Institute SUMAE) for funding support through the projects TAGEM/HSGYAD/14/A05/P05/70 and TAGEM/HSGYAD/17/A03/P05/133. Figueroa Lopez is a recipient of a Santiago Grisolia (GRISOLIAP/2017/101) grant of the Generalitat Valenciana (GVA) and Torres-Giner is on a Juan de la Cierva-Incorporacion contract (IJCI-2016-29675) from MICIU.Alp-Erbay, E.; Figueroa-López, KJ.; Lagaron, JM.; Çaglak, E.; Torres-Giner, S. (2019). The impact of electrospun films of poly(epsilon-caprolactone) filled with nanostructured zeolite and silica microparticles on in vitro histamine formation by Staphylococcus aureus and Salmonella Paratyphi A. Food Packaging and Shelf Life. 22:1-13. https://doi.org/10.1016/j.fpsl.2019.100414S11322Alp Erbay, E., Dağtekin, B. B. (Gözü), Türe, M., Yeşilsu, A. F., & Torres-Giner, S. (2017). Quality improvement of rainbow trout fillets by whey protein isolate coatings containing electrospun poly(ε-caprolactone) nanofibers with Urtica dioica L. extract during storage. LWT, 78, 340-351. doi:10.1016/j.lwt.2017.01.002Alp-Erbay, E., Yeşi̇lsu, A. F., & Türe, M. (2019). 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Reactive toughening of injection-molded polylactide pieces using maleinized hemp seed oil

[EN] The present study describes the effect of maleinized hemp seed oil (MHO) on the physical performance of polylactide (PLA) pieces. To this end, PLA pieces with varying MHO contents in the 0¿10 wt% range were manufactured by twin-screw extrusion (TSE) followed by injection molding. The resultant pieces were characterized in terms of their mechanical, thermal, and thermomechanical properties. The obtained properties suggested that, unlike typical plasticizers, MHO does not only induce an increment in elongation at break and impact resistance but it also enhances both elastic modulus and tensile strength. In addition, a moderate decrease in the glass transition temperature (Tg) was observed. This was ascribed to simultaneous linear chain-extension, branching, and/or cross-linking phenomena due to the reaction of the multiple maleic anhydride (MAH) groups present in MHO with the terminal hydroxyl groups of the PLA chains. Furthermore, morphology characterization revealed that, though certain phase separation occurred at its highest content, MHO was finely dispersed as submicron droplets within the PLA matrix contributing to improving toughness. The use of multi-functionalized reactive vegetable oils thus represents a highly sustainable solution to reduce the intrinsic brittleness of PLA materials without compromising their mechanical resistance and the toughened biopolymer pieces described herein can find interesting applications in, for instance, rigid packaging.This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) (projects MAT2014-59242-C2-1-R and AGL2015-63855-C2-1-R.). L. Quiles-Carrillo acknowledges Generalitat Valenciana (GV) for financial support through a FPI grant (ACIF/2016/182) and the Spanish Ministry of Education, Culture, and Sports (MECD) for his FPU grant (FPU15/03812).Quiles-Carrillo, L.; Blanes-Martínez, M.; Montanes, N.; Fenollar, O.; Torres-Giner, S.; Balart, R. (2018). Reactive toughening of injection-molded polylactide pieces using maleinized hemp seed oil. European Polymer Journal. 98:402-410. https://doi.org/10.1016/j.eurpolymj.2017.11.039S4024109

A comparative study on the reactive compatibilization of melt-processed polyamide 1010/polylactide blends by multi-functionalized additives derived from linseed oil and petroleum

[EN] This research work describes the manufacturing and characterization of novel engineering materials consisted of fully bio-based blends of polyamide 1010 (PA1010) with 20 wt% of polylactide (PLA). Four different compatibilizers were used to enhance the miscibility and the performance of the biopolymer blends. Two multi-functionalized vegetable oils (maleinized linseed oil (MLO) and epoxidized linseed oil (ELO)) and two petroleum-derived glycidyl-based additives (epoxy styrene-acrylic oligomer (ESAO) and styrene-glycidyl methacrylate copolymer (PS-GMA)) were tested during melt compounding. The resultant biopolymer blends were processed by either cast film extrusion or injection molding to obtain films and pieces, respectively. Thin films with an average thickness of 50¿60 µm and thick pieces of 4 mm were obtained, and their mechanical, morphological, thermal, thermomechanical, barrier and, optical properties were characterized. Although all four compatibilizers successfully provided compatibilization to the blends, the chemically modified vegetable oils, that is, MLO and ELO yielded the injection-molded pieces with the most balanced mechanical properties in terms of strength and toughness. Besides, the resultant films showed very low oxygen transmission rate values, thus broadening the potential of these biopolymer blends for the food packaging industryThis research work was funded by the Spanish Ministry of Science, Innovation, and Universities (MICIU) project numbers MAT2017-84909-C2-2-R and AGL2015-63855-C2-1-R. Quiles-Carrillo and Torres-Giner are recipients of a FPU grant (FPU15/03812) from the Spanish Ministry of Education, Culture, and Sports (MECD) and a Juan de la Cierva contract (IJCI-2016-29675) from MICIU, respectively. Microscopy services at UPV are acknowledged for their help in collecting and analyzing FESEM images. Authors thank Polyscope for kindly supplying XibondTM 920 for this study.Quiles-Carrillo, L.; Fenollar, O.; Balart, R.; Torres-Giner, S.; Rallini, M.; Dominici, F.; Torre, L. (2020). A comparative study on the reactive compatibilization of melt-processed polyamide 1010/polylactide blends by multi-functionalized additives derived from linseed oil and petroleum. eXPRESS Polymer Letters. 14(6):583-604. https://doi.org/10.3144/expresspolymlett.2020.48S58360414