Bio-Based Coatings for Food Metal Packaging Inspired in Biopolyester Plant Cutin.

Metals used for food canning such as aluminum (Al), chromium-coated tin-free steel (TFS) and electrochemically tin-plated steel (ETP) were coated with a 2-3-µm-thick layer of polyaleuritate, the polyester resulting from the self-esterification of naturally-occurring 9,10,16-trihydroxyhexadecanoic (aleuritic) acid. The kinetic of the esterification was studied by FTIR spectroscopy; additionally, the catalytic activity of the surface layer of chromium oxide on TFS and, in particular, of tin oxide on ETP, was established. The texture, gloss and wettability of coatings were characterized by AFM, UV-Vis total reflectance and static water contact angle (WCA) measurements. The resistance of the coatings to solvents was also determined and related to the fraction of unreacted polyhydroxyacid. The occurrence of an oxidative diol cleavage reaction upon preparation in air induced a structural modification of the polyaleuritate layer and conferred upon it thermal stability and resistance to solvents. The promoting effect of the tin oxide layer in such an oxidative cleavage process fosters the potential of this methodology for the design of effective long-chain polyhydroxyester coatings on ETP

Polyester films obtained by noncatalyzed melt-condensation polymerization of aleuritic (9,10,16-Trihydroxyhexadecanoic) acid in air

To mimic nontoxic and fully biodegradable biopolymers like the plant cutin, polyester films from a natural occurring fatty polyhydroxyacid like aleuritic (9,10,16-trihydroxyhexadecanoic) acid have been prepared by noncatalyzed melt-polycondensation at moderate temperature (150°C) directly in air. The course of the reaction has been followed by infrared spectroscopy, 13C magic angle spinning nuclear magnetic resonance spectroscopy, differential scanning calorimetry and X-ray diffraction and well differentiated stages are observed. First, a high conversion esterification reaction leads to an amorphous rubbery, infusible, and insoluble material whose structure is made out of ester linkages mostly involving primary hydroxyls and partially branched by minor esterification with secondary ones. Following the esterification stage, the cleavage of vicinal secondary hydroxyls and further oxidation to carboxylic acid is observed at the near surface region of films. New carboxylic groups created also undergo esterification and generate cross-linking points within the polymer structure. Additionally, and despite the harsh preparation conditions used, very little additional side reaction like peroxidation and dehydration are observed. Results demonstrate the feasibility of polyester films fabrication from a reference fatty polyhydroxyacid like aleuritic acid by noncatalyzed melt-polycondensation directly in air. The methodology can potentially be extended to similar natural occurring hydroxyacids to obtain films and coatings to be used, for instance, as nontoxic and biodegradable food packaging materialPeer reviewe

Valorization of Tomato Processing by-Products: Fatty Acid Extraction and Production of Bio-Based Materials

A method consisting of the alkaline hydrolysis of tomato pomace by-products has been optimized to obtain a mixture of unsaturated and polyhydroxylated fatty acids as well as a non-hydrolysable secondary residue. Reaction rates and the activation energy of the hydrolysis were calculated to reduce costs associated with chemicals and energy consumption. Lipid and non-hydrolysable fractions were chemically (infrared (IR) spectroscopy, gas chromatography/mass spectrometry (GC-MS)) and thermally (differential scanning calorimetry (DSC), thermogravimetric analysis (TGA)) characterized. In addition, the fatty acid mixture was used to produce cutin-based polyesters. Freestanding films were prepared by non-catalyzed melt-polycondensation and characterized by Attenuated Total Reflected-Fourier Transform Infrared (ATR-FTIR) spectroscopy, solid-state nuclear magnetic resonance (NMR), DSC, TGA, Water Contact Angles (WCA), and tensile tests. These bio-based polymers were hydrophobic, insoluble, infusible, and thermally stable, their physical properties being tunable by controlling the presence of unsaturated fatty acids and oxygen in the reaction. The participation of an oxidative crosslinking side reaction is proposed to be responsible for such modifications.Andalusian Regional Government P11-TEP-7418Spanish Ministerio de Economía y Competitividad AGL2015-65246-R and AGL2017-83036-RFondo Europeo de Desarrollo Regional (FEDER) AGL2015-65246-R and AGL2017-83036-

Chemical-physical characterization of isolated plant cuticles subjected to low-dose γ-irradiation

Isolated tomato fruit cuticles were subjected to low dose (80 Gy) γ-irradiation, as a potential methodology to prevent harvested fruit and vegetables spoilage. Both irradiated and non-irradiated samples have been morphologically and chemically characterized by scanning electron (SEM), atomic force (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopies. Additionally, electrochemical measurements comprising membrane potential and diffusive permeability were carried out to detect modifications in transport properties of the cuticle as the fruit primary protective membrane. It has been found that low dose γ-irradiation causes some textural changes on the surface but no significant chemical modification. Texture modification is found to be due to a partial removal of outermost (epicuticular) waxes which is accompanied by mild changes of electrochemical parameters such as the membrane fixed charge, cation transport number and salt permeability. The modification of such parameters indicates a slight reduction of the barrier properties of the cuticle upon low dose γ-irradiation.

Biodegradable Polyester Films from Renewable Aleuritic Acid: Surface Modifications Induced by Melt-polycondensation in Air.

Good water barrier properties and biocompatibility of long-chain biopolyesters like cutin and suberin have inspired the design of synthetic mimetic materials. Most of these biopolymers are made from esterified mid-chain functionalized ω-long chain hydroxyacids. Aleuritic (9,10,16-trihydroxypalmitic) acid is such a polyhydroxylated fatty acid and is also the major constituent of natural lac resin, a relatively abundant and renewable resource. Insoluble and thermostable films have been prepared from aleuritic acid by meltcondensation polymerization in air without catalysts, an easy and attractive procedure for large scale production. Intended to be used as a protective coating, the barrier's performance is expected to be conditioned by physical and chemical modifications induced by oxygen on the air-exposed side. Hence, the chemical composition, texture, mechanical behavior, hydrophobicity, chemical resistance and biodegradation of the film surface have been studied by attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR), atomic force microscopy (AFM), nanoindentation and water contact angle (WCA). It has been demonstrated that the occurrence of side oxidation reactions conditions the surface physical and chemical properties of these polyhydroxyester films. Additionally, the addition of palmitic acid to reduce the presence of hydrophilic free hydroxyl groups was found to have a strong influence on these parametersPeer reviewe

Biodegradable Polyester Films from Renewable Aleuritic Acid: Surface Modifications Induced by Melt-polycondensation in Air.

Good water barrier properties and biocompatibility of long-chain biopolyesters like cutin and suberin have inspired the design of synthetic mimetic materials. Most of these biopolymers are made from esterified mid-chain functionalized ω-long chain hydroxyacids. Aleuritic (9,10,16-trihydroxypalmitic) acid is such a polyhydroxylated fatty acid and is also the major constituent of natural lac resin, a relatively abundant and renewable resource. Insoluble and thermostable films have been prepared from aleuritic acid by meltcondensation polymerization in air without catalysts, an easy and attractive procedure for large scale production. Intended to be used as a protective coating, the barrier's performance is expected to be conditioned by physical and chemical modifications induced by oxygen on the air-exposed side. Hence, the chemical composition, texture, mechanical behavior, hydrophobicity, chemical resistance and biodegradation of the film surface have been studied by attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR), atomic force microscopy (AFM), nanoindentation and water contact angle (WCA). It has been demonstrated that the occurrence of side oxidation reactions conditions the surface physical and chemical properties of these polyhydroxyester films. Additionally, the addition of palmitic acid to reduce the presence of hydrophilic free hydroxyl groups was found to have a strong influence on these parametersEspaña Mineco CTQ2011-24299Junta de Andalucia TEP-7418. JAH-GBIOPROTO FP

Graphene and polytetrafluoroethylene synergistically improve the tribological properties and adhesion of nylon 66 coatings

Abstract In this work, we exploit the bidimensional structure and high stiffness of graphene to improve the tribological response of nylon-based composites. Graphene nanoplatelets, coupled with polytetrafluoroethylene microparticles, synergistically improve the friction coefficient and wear rate, as well as the adhesion to the substrate. The enhancement, as high as threefold for both friction and wear rate at the optimal graphene concentration (0.5% in weight), depends upon the formation of a continuous, robust transfer film with the steel rubbing counterpart, as shown by Raman measurements. The graphene-nylon coating also shows three-fold improved adhesion to the underlying substrate, attributed to the high surface energy of graphene

Direct Transformation of Edible Vegetable Waste into Bioplastics

Bioplastics with a wide range of mechanical properties were directly obtained from industrially processed edible vegetable and cereal wastes. As model systems, we present bioplastics synthesized from wastes of parsley and spinach stems, rice hulls, and cocoa pod husks by digesting in trifluoroacetic acid (TFA), casting, and evaporation. In this way, amorphous cellulose-based plastics are formed. Moreover, many other natural elements present in these plants are carried over into the bioplastics rendering them with many exceptional thermo-physical properties. Here, we show that, due to their broad compatibility with cellulose, amorphous cellulose can be naturally plasticized with these bioplastics by simply mixing during processing. Comparison of their mechanical properties with that of various petroleum based synthetic polymers indicates that these bioplastics have equivalent mechanical properties to the nondegrading ones. This opens up possibilities for replacing some of the nondegrading polymers with the..

Levulinic acid-based bioplasticizers: a facile approach to enhance the thermal and mechanical properties of polyhydroxyalkanoates

PHB has been engineered by incorporating different levulinic acid-based bioplasticizers, which enhance flexibility and thermal processability of the neat biopolymer, while retaining excellent biocompatibility and biodegradability

Biomimetic approach for liquid encapsulation with nanofibrillar cloaks.

Technologies that are able to handle microvolumes of liquids, such as microfluidics and liquid marbles, are attractive for applications that include miniaturized biological and chemical reactors, sensors, microactuators, and drug delivery systems. Inspired from natural fibrous envelopes, here, we present an innovative approach for liquid encapsulation and manipulation using electrospun nanofibers. We demonstrated the realization of non-wetting soft solids consisting of a liquid core wrapped in a hydrophobic fibrillar cloak of a fluoroacrylic copolymer and cellulose acetate. By properly controlling the wetting and mechanical properties of the fibers, we created final architectures with tunable mechanical robustness that were stable on a wide range of substrates (from paper to glass) and floated on liquid surfaces. Remarkably, the realized fiber-coated drops endured vortex mixing in a continuous oil phase at high stirring speed without bursting or water losses, favoring mixing processes inside the entrapped liquid volume. Moreover, the produced cloak can be easily functionalized by incorporating functional particles, active molecules, or drugs inside the nanofibers