Antioxidant Edible Films Based on Pear Juice and Pregelatinized Cassava Starch: Effect of the Carbohydrate Profile at Different Degrees of Pear Ripeness.

Edible films based on fruit and vegetable purees combined with different food-grade biopolymeric binding agents (e.g., pectin, gelatin, starch, sodium alginate) are recognized as interesting packaging materials that benefit from the physical, mechanical, and barrier properties of biopolymers as well as the sensory and nutritional properties of purees. In the current contribution, edible antioxidant films based on pear juice and pregelatinized cassava starch were developed. In particular, the suitability of using pregelatinized cassava starch for the non-thermal production of these novel edible films was evaluated. In addition, the effects on the films' properties derived from the use of pear juice instead of the complete puree, from the content of juice used, and from the carbohydrate composition associated with the ripening of pears were all studied. The produced films were characterized in terms of their total polyphenol content, water sensitivity, and water barrier, optical, mechanical and antioxidant properties. Results showed that the use of pear juice leads to films with enhanced transparency compared with puree-based films, and that juice concentration and carbohydrate composition associated with the degree of fruit ripeness strongly govern the films' properties. Furthermore, the addition of pregelatinized cassava starch at room temperature discloses a significant and favorable impact on the cohesiveness, lightness, water resistance, and adhesiveness of the pear-juice-based films, which is mainly attributed to the effective interactions established between the starch macromolecules and the juice components.

Effect of Addition of Cross-Linked Starch on the Properties of Degraded PBAT Poly(butylene adipate-co-terephthalate) Films.

This work aimed to evaluate the properties of butylene adipate-co-terephthalate (PBAT) degraded after 1800 days of storage (DPBAT) by preparing blends (films) with crosslinked starch (Cm) through extrusion and thermocompression. Different ratios of DPBAT:Cm (70:30, 60:40, and 50:50 m/m) were prepared. The incorporation of Cm into DPBAT significantly changed the properties of the films by making them stiffer (increasing Young's modulus by up to 50%) and increasing the thermal resistance of DPBAT. The presence of crosslinked starch in the films made them less hydrophobic (with decreased contact angle and increased moisture content), but these parameters did not vary linearly with changes in the content of crosslinked starch in the blend (DPBAT:Cm). The microscopic images show an inhomogeneous distribution of Cm granules in the DPBAT matrix. Thus, the films prepared with PBAT show a significant decrease in their mechanical parameters and heat resistance after long-term storage. However, the preparation of blends of degraded DPBAT with crosslinked starch promoted changes in the properties of the films prepared by thermocompression, which could be useful for disposable packaging.

In situ syringe rotation system for heavy microparticle suspension stability in electrospinning technique.

Electrospinning allows the fabrication of polymeric nonwovens with a wide variety of inclusions in the micro-nanofibers. However, the electrospinning of microparticle-filled polymer solutions is still limited in particle size, density, and concentration, mainly due to suspension instability during the electrospinning process, so it is not commonly investigated despite the vast number of possible applications. In this study, a simple and effective novel rotation device was developed to prevent the settling of microparticles in the polymer solution during electrospinning. The stability of polyvinyl alcohol and polyvinylidene fluoride (PVDF) solutions with indium microparticles (IMPs) of (42 ± 7) µm diameter was evaluated using LASER transmittance inside a syringe, both static and rotating for 24 h. While the static suspensions completely settled at 7 min and 9 h, respectively, depending on solution viscosity, the rotating suspensions remained stable throughout the experiment. The number and distribution of IMPs in PVDF electrospun mats were determined by optic microscopy and a novel x-ray imaging mapping method, showing 165% more IMPs in the mat obtained with the rotating syringe device. A simple analysis of the theoretical background of settling and rotating suspensions was included to understand the working mechanism of the device. Also, the electrospinning of solutions with high loadings of IMPs (up to 400% w/w PVDF) was accomplished. The simplicity and outstanding efficiency of the device shown in this work may serve as a solution to technical difficulties and as an encouragement to future research in microparticle-filled solution electrospinning.

Black Tea Extracts/Polyvinyl Alcohol Active Nanofibers Electrospun Mats with Sustained Release of Polyphenols for Food Packaging Applications.

The efficiency in the capabilities to store and release antioxidants depends on the film morphology and its manufacturing process, as well as on the type and methodology used to obtain the polyphenol extracts. Here, hydroalcoholic extracts of black tea polyphenols (BT) were obtained and dropped onto different polyvinyl alcohol (PVA) aqueous solutions (water or BT aqueous extract with and without citric acid, CA) to obtain three unusual PVA electrospun mats containing polyphenol nanoparticles within their nanofibers. It was shown that the mat obtained through the nanoparticles precipitated in BT aqueous extract PVA solution presented the highest total polyphenol content and antioxidant activity, and that the addition of CA as an esterifier or PVA crosslinker interfered with the polyphenols. The release kinetics in different food simulants (hydrophilic, lipophilic and acidic) were fitted using Fick's diffusion law and Peppas' and Weibull's models, showing that polymer chain relaxation is the main mechanism in all food simulants except for the acidic, which presented an abrupt release by Fick's diffusion mechanism of about 60% before being controlled. This research provides a strategy for the development of promising controlled-release materials for active food packaging, mainly for hydrophilic and acidic food products.

A Review of Pectin-Based Material for Applications in Water Treatment.

Climate change and water are inseparably connected. Extreme weather events cause water to become more scarce, polluted, and erratic than ever. Therefore, we urgently need to develop solutions to reduce water contamination. This review intends to demonstrate that pectin-based materials are an excellent route to detect and mitigate pollutants from water, with several benefits. Pectin is a biodegradable polymer, extractable from vegetables, and contains several hydroxyl and carboxyl groups that can easily interact with the contaminant ions. In addition, pectin-based materials can be prepared in different forms (films, hydrogels, or beads) and cross-linked with several agents to change their molecular structure. Consequently, the pectin-based adsorbents can be tuned to remove diverse pollutants. Here, we will summarize the existing water remediation technologies highlighting adsorption as the ideal method. Then, the focus will be on the chemical structure of pectin and, from a historical perspective, on its structure after applying different cross-linking methods. Finally, we will review the application of pectin as an adsorbent of water pollutants considering the pectin of low degree methoxylation.

Evolution of the free volume during water desorption in thermoplastic starch/citric acid films: In situ positron annihilation studies.

The effect of citric acid (CA) concentration and water content on the free hole volume of thermoplastic cassava starch films (TPS) was studied. To this aim, continuous in situ positron annihilation lifetime spectroscopy measurements were performed at fixed moisture content and during water desorption. The results show that the increase in CA concentration leads to wider free hole volume distributions with lower mean values. During water desorption, the mean values and width of such distributions systematically decrease with the exposure time, and the evolution of the hole volumes was well-described using the Kohlrausch-Williams-Watts function. The water vapour permeability was significantly higher in films incorporating 5 % (w/w) of CA, in line with the more open network of this material that was revealed in the hole volumes distribution. The Young's modulus of all the developed films increased significantly after partial water desorption, which was attributed to the plasticizer loss reflected in a decrease in the mean hole volume value (between 4 % and 13 %). This work evidences that the control and report of the relative humidity are essential when testing TPS-based films, as their nanostructures are strongly dependent on external conditions.

Effect of TiO2 Nanoparticles and Extrusion Process on the Physicochemical Properties of Biodegradable and Active Cassava Starch Nanocomposites.

Biodegradable polymers have been strongly recognized as an alternative to replace traditional petrochemical plastics, which have become a global problem due to their long persistence in the environment. In this work, the effect of the addition of titanium dioxide nanoparticles (TiO2NP) on the morphology, physicochemical properties and biodegradation under industrial composting conditions of cassava starch-based nanocomposites obtained by extrusion at different screw speeds (80 and 120 rpm) were investigated. Films performed at 120 rpm (S120 and S120-TiO2NP) showed completely processed starch and homogeneously distributed nanoparticles, leading to much more flexible nanocomposites than those obtained at 80 rpm. The incorporation of TiO2NP led to an increase in storage modulus of all films and, in the case of S120-TiO2NP, to higher strain at break values. From the Kohlrausch-Williams-Watts theoretical model (KWW), an increase in the relaxation time of the nanocomposites was observed due to a decrease in the number of polymer chains involved in the relaxation process. Additionally, S120-TiO2NP showed effective protection against UV light, greater hydrophobicity and faster biodegradation in compost, resulting in a promising material for food packaging applications.

Pineapple Agro-Industrial Biomass to Produce Biomedical Applications in a Circular Economy Context in Costa Rica.

Pineapple is a highly demanded fruit in international markets due to its unique appearance and flavor, high fiber content, vitamins, folic acid, and minerals. It makes pineapple production and processing a significant source of income for producing countries, such as Costa Rica. This review collects bibliographic information dating back to the beginnings of pineapple production in Costa Rica to the state of the market today. It details the impacts of its production chain and proposes a biorefinery as a solution to environmental problems. Besides the potentiality of new sustainable markets to contribute to the post-COVID-19 economy in Costa Rica is highlighted. The general characteristics of pineapple by-products -cellulose, hemicellulose, lignin, and other high-value products like bromelain y saponin- are described, as well as the primary processes for their ex-traction via biorefinery and main applications in the medical field. Finally, a brief description of the main works in the literature involving modeling and simulation studies of pineapple by-products properties is included.

Adsorption of Methylene Blue and Tetracycline by Zeolites Immobilized on a PBAT Electrospun Membrane.

The detection of emerging contaminants in bodies of water has steadily increased in recent years, becoming a severe problem threatening human and ecosystem health. Developing new materials with adsorption properties to remove these pollutants represents an important step toward a potential solution. In this paper, a polybutylene adipate terephthalate (PBAT) nanofibrous membrane incorporating clinoptilolite zeolite was developed and its excellent performance in removing tetracycline (TC) and methylene blue (MB) from water was demonstrated. The composite membrane was prepared in two steps: firstly, a homogeneous dispersion of clinoptilolite (1 wt% respect to polymer) in a PBAT solution (12.6 wt%) was electrospun; secondly, the electrospun membrane was subjected to an acid treatment that improved its wettability through the protonation of the surface silanol groups of clinoptilolite. The resulting membrane was hydrophilic and showed higher adsorption for TC (800 mg/g) and MB (100 mg/g), using a low dose (90 mg/L) powdered zeolite. The maximum removal capacity was obtained at neutral pH, being the cation exchange reaction the main adsorption mechanism. Pseudo-second-order kinetics and Henry's law agree well with the proposed chemisorption and the high affinity of TC and MB for the adsorbent. The material can be reused after the removal process without generating additional contamination, although losing some effectivity.

Biohybrid membranes for effective bacterial vehiculation and simultaneous removal of hexavalent chromium (CrVI) and phenol.

The aim of the present study was to obtain an effective vehiculation system in which bacterial agents could maintain viability improving their removal capacity. Herein, we present a novel biohybrid membrane of polymeric nanofibers and free-living bacteria for the simultaneous removal of pollutants. In this system, bacteria are free within the pores between the nanofibers and adsorbed to the surface of the membranes. Association between bacteria and the membranes was performed through a self-formulated medium, and the presence of the bacteria in the polymeric matrix was evidenced through atomic force microscopy (AFM). Biohybrid membranes associated with the remediation agents Bacillus toyonensis SFC 500-1E and Acinetobacter guillouiae SFC 500-1A promoted a reduction of up to 2.5 mg/L of hexavalent chromium and up to 200 mg/L of phenol after 24 h of treatment in synthetic medium containing the contaminants. Similarly, more than 46% of the hexavalent chromium and all of the phenol content were removed after treatment of a tannery effluent with initial concentrations of 7 mg/L of Cr(VI) and 305 mg/L of phenol. Counts of the remediation agents from the membranes were always above 1.107 CFU/g, also in the reutilization assays performed without reinoculation. Biohybrid membranes were hydrolysis-resistant, reusable, and effective in the simultaneous removal of contaminants for more than 5 cycles. Viability of the microorganisms was maintained after long-term storage of the membranes at 4 °C, without the use of microbiological media or the addition of cryoprotectants. Graphical abstract KEY POINTS: • Polymeric membranes were effectively associated with the SFC 500-1 remediation consortium • Biohybrid membranes removed hexavalent chromium and phenol from different matrices • Removal of contaminants was achieved in many successive cycles without reinoculation.

Improvement of Andean Blueberries Postharvest Preservation Using Carvacrol/Alginate-Edible Coatings.

Edible coatings are attractive strategies for blueberries postharvest preservation. In this work, carvacrol/alginate coatings were developed for application on Andean blueberries. Coating formulations were prepared based on blends of sodium alginate (2% w/v), carvacrol (0%, 0.03%, 0.06% or 0.09%), glycerol, and water and applied to the fruits by dip-coating. Then, the fruits were immersed in a calcium batch to induce a crosslink reaction. Changes in the physicochemical and microbiological characteristics of the blueberries were monitored during 21 days of storage at 4 °C. Coated blueberries were better preserved throughout the 21 days of storage because of their lower respiration rate and water loss, in comparison with the uncoated ones. Besides, the coatings enhanced the appearance and the gloss of the fruits. Control fruits showed a significant decrease in the firmness, while, in the coated fruits, this critical postharvest quality was preserved during the entire storage. Coating formulations with 0.09% of carvacrol was the most effective in preventing mesophilic aerobic bacteria and molds/yeasts growth on the fruits during the storage. Edible carvacrol/alginate coatings can be considered as a useful alternative to complement the benefits of refrigerated storage by delaying post-harvest spoilage of Andean blueberries.

Effect of yerba mate extract on the performance of starch films obtained by extrusion and compression molding as active and smart packaging.

Native or hydrolyzed starch and yerba mate extract (10 wt.% or 20 wt.%) films prepared by extrusion and compression molding were investigated. Native starch material (TPNS) exhibited lower water vapor permeability and higher Young's Modulus (E) compared to hydrolyzed starch matrix (TPHS) but decreases in strain at break (εb) and toughness (T). The incorporation of 10 wt.% of extract in TPNS led to greater E and εb and it resulted the most hydrophobic material. Conversely, TPHS with 20 wt.% of additive resulted the film with the highest εb and T, indicating a plasticizing effect of the extract in this concentration and system. All materials disintegrated after 10 weeks of burial, contributing to waste reduction. Biofilms containing yerba mate extract showed antioxidant activity and color changes in different pH, indicating their promising role as active and smart packaging for food, in accordance with the new trends for biodegradable and functional packaging.

Characterization of Starches Isolated from Colombian Native Potatoes and Their Application as Novel Edible Coatings for Wild Andean Blueberries (Vaccinium meridionale Swartz).

Andean blueberry is a promissory fruit native to South America. The current work aimed to characterize starches isolated from Colombian native potatoes and to evaluate the effect of the application of starch edible coatings on the changes in the physicochemical quality parameters of the Andean blueberry during storage. Starches were isolated from three different potatoes varieties (pacha negra, mora, and alcarrosa) and characterized. Then, starch-based coatings were applied to Andean blueberries, and the changes in their quality parameters were monitored during 12 days of storage. Despite the phenotypical differences in the starch sources used, starches were similar in terms of their granule morphology, amylose content (~19%), crystallinity degree (~46%), and thermal properties. Coatings were able to reduce the gaseous exchange of the fruit, and, thus, the respiration rate of all coated blueberries was ~27% lower compared to the uncoated fruits (p < 0.05) at the end of the storage. While the application of starch coatings did not prevent water loss, all samples reached water loss of up 20%. Besides, the coated fruits showed soluble solids contents ~14% higher compared to the control one, as well as better bright and firmness. The new edible coatings can help add value to the Andean blueberry.

Potato starch-based biocomposites with enhanced thermal, mechanical and barrier properties comprising water-resistant electrospun poly (vinyl alcohol) fibers and yerba mate extract.

Water-resistant electrospun poly(vinyl alcohol) (PVA) mats and a yerba mate extract (YM) were incorporated together within potato starch (PS) matrices to prepare biocomposites (PS-YM/PVA/PS-YM). The thermal, mechanical and barrier properties of the PS-YM/PVA/PS-YM systems were compared with biocomposites without YM (PS/PVA/PS) and, with potato starch films without (PS) and with (PS-YM) the YM extract. Scanning electron microscopy analysis showed that the electrospun mats were fully incorporated into the biocomposites and that the PS/PVA interlayer adhesion was only slightly affected by the addition of the extract. Infrared spectra analysis confirmed that this behavior was due to the lower amount of hydroxyl groups available in the biocomposites. As compared with the other systems, the PS-YM/PVA/PS-YM biocomposites exhibited better light- and water vapor barrier properties. Moreover, the presence of the electrospun PVA core layer and the YM extract caused an increase of around 60% in the elastic modulus of these materials.

Influence of process (extrusion/thermo-compression, casting) and lentil protein content on physicochemical properties of starch films.

Starch films often present high water sensitivity, affecting their barrier and mechanical properties. The effects of processing technique, extrusion/thermo-compression and casting, and lentil protein concentration (0, 0.75 wt.% and 1.5 wt.%) on biodegradable starch films were investigated. Extrusion/thermo-compression process increased in 90% the mechanical resistance of starch films produced following the casting methodology and decreased their moisture content, water solubility and water vapor permeability in 35%, 23%, and 50%, respectively. In the presence of the protein, the mechanical properties (Young modulus and stress at break) and the water tolerance improved due to the crosslinking phenomenon prompted between the protein and the polymeric backbone, being these effects more pronounced on the extruded formulations. All samples resulted thermal stable until 240 °C and biodegraded in compost in 5 weeks. This work revealed that extrusion/thermo-compression process and proteins as crosslinking of starch are two alternatives to improve the drawbacks of starch-based materials.

High-Energy Dissipation Performance in Epoxy Coatings by the Synergistic Effect of Carbon Nanotube/Block Copolymer Conjugates.

Hierarchical assembly of hard/soft nanoparticles holds great potential as reinforcements for polymer nanocomposites with tailored properties. Here, we present a facile strategy to integrate polystyrene-grafted carbon nanotubes (PSgCNT) (0.05-0.3 wt %) and poly(styrene-b-[isoprene-ran-epoxyisoprene]-b-styrene) block copolymer (10 wt %) into epoxy coatings using an ultrasound-assisted noncovalent functionalization process. The method leads to cured nanocomposites with core-shell block copolymer (BCP) nanodomains which are associated with carbon nanotubes (CNT) giving rise to CNT-BCP hybrid structures. Nanocomposite energy dissipation and reduced Young's Modulus (E*) is determined from force-distance curves by atomic force microscopy operating in the PeakForce QNM imaging mode and compared to thermosets modified with BCP and purified carbon nanotubes (pCNT). Remarkably, nanocomposites bearing PSgCNT-BCP conjugates display an increase in energy dissipation of up to 7.1-fold with respect to neat epoxy and 53% more than materials prepared with pCNT and BCP at the same CNT load (0.3 wt %), while reduced Young's Modulus shows no significant change with CNT type and increases up to 25% compared to neat epoxy E* at a CNT load of 0.3 wt %. The energy dissipation performance of nanocomposites is also reflected by the lower wear coefficients of materials with PSgCNT and BCP compared to those with pCNT and BCP, as determined by abrasion tests. Furthermore, scanning electron microscopy (SEM) images taken on wear surfaces show that materials incorporating PSgCNT and BCP exhibit much more surface deformation under shear forces in agreement with their higher ability to dissipate more energy before particle release. We propose that the synergistic effect observed in energy dissipation arises from hierarchical assembly of PSgCNT and BCP within the epoxy matrix and provides clues that the CNT-BCP interface has a significant role in the mechanisms of energy dissipation of epoxy coating modified by CNT-BCP conjugates. These findings provide a means to design epoxy-based coatings with high-energy dissipation performance.

A simple green route to obtain poly(vinyl alcohol) electrospun mats with improved water stability for use as potential carriers of drugs.

Poly(vinyl alcohol) (PVA) is a hydrophilic, biocompatible and nontoxic polymer. However, because of its low water-resistance, some applications for PVA-based materials are limited (e.g., drug delivery systems and wound dressings). In the current work, PVA mats containing tetracycline hydrochloride (TC) were successfully developed by electrospinning. In order to improve the water stability of the systems, the cross-linking of the PVA matrix was induced by citric acid (CA) addition together with heating treatments (150°C or 190°C for 3min). TC presence led to a strong increase in the electrical conductivity of the blends and as a result, fibers with about 44% lower diameter (270nm) than that of the corresponding unloaded mats (485nm) were obtained. Laser scanning confocal microscopy images indicated that TC was well distributed along the PVA nanofibers. The mats were evaluated by FTIR, which revealed chemical interactions between PVA hydroxyl groups and CA carboxylic ones. The treatment at 150°C for 3min proved to be the more suitable for the preparation of TC-containing mats with improved water resistance, maintaining the TC antimicrobial activity against both Escherichia coli and Staphylococcus aureus almost unaltered. These mats showed a burst release of TC, giving around 95% of the drug within the first hour of immersion in water.

Biodegradability and plasticizing effect of yerba mate extract on cassava starch edible films.

Biodegradable and edible cassava starch-glycerol based films with different concentrations of yerba mate extract (0, 5 and 20wt.%) were prepared by casting. The plasticizing effect of yerba mate extract when it was incorporated into the matrix as an antioxidant was investigated. Thermal degradation and biodegradability of the obtained biofilms were also studied. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FTIR), X-ray diffraction analysis (XRD), water absorbance, stability in different solutions and biodegradability studies were performed. The clear correlation among the results obtained from the different analysis confirmed the plasticizing effect of yerba mate extract on the starch-glycerol matrix. Also, the extract led to a decrease in the degradation time of the films in soil ensuring their complete biodegradability before two weeks and to films stability in acidic and alkaline media. The plasticizing effect of yerba mate extract makes it an attractive additive for starch films which will be used as packaging or coating; and its contribution to an earlier biodegradability will contribute to waste reduction.

Data of thermal degradation and dynamic mechanical properties of starch-glycerol based films with citric acid as crosslinking agent.

Interest in biodegradable edible films as packaging or coating has increased because their beneficial effects on foods. In particular, food products are highly dependents on thermal stability, integrity and transition process temperatures of the packaging. The present work describes a complete data of the thermal degradation and dynamic mechanical properties of starch-glycerol based films with citric acid (CA) as crosslinking agent described in the article titled: "Biodegradable and non-retrogradable eco-films based on starch-glycerol with citric acid as crosslinking agent" González Seligra et al. (2016) [1]. Data describes thermogravimetric and dynamical mechanical experiences and provides the figures of weight loss and loss tangent of the films as a function of the temperature.

Biodegradable and non-retrogradable eco-films based on starch-glycerol with citric acid as crosslinking agent.

Biodegradable and non-retrogradable starch-glycerol based films were obtained using citric acid (CA) as crosslinking agent at 75°C. This material allowed decreasing water vapor permeability (WVP) more than 35%, remained amorphous for at least 45 days as a result of the network formed by the CA that avoided starch retrogradation and maintained the degradability in compost, occurring only six days after the films without citric acid. A simulation of the gelatinization process of starch-glycerol with and without CA, using a differential thermal analysis device, showed that the system with CA completed the gelatinization 5°C before than the other and, CA first reacted with glycerol and then starch-glycerol-CA reaction occurred. The temperature at which the gelatinization process was carried out was critical to obtain the best results. An increase of gelatinization process temperature at 85°C in system with CA, led to a worsening on WVP and its integrity after a swelling process with dimethylsulphoxide (DMSO), compared to the films processed at 75°C.