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-

Zinc Polyaleuritate Ionomer Coatings as a Sustainable, Alternative Technology for Bisphenol A-Free Metal Packaging

Sustainable coatings for metal food packaging were prepared from ZnO nanoparticles (obtained by the thermal decomposition of zinc acetate) and a naturally occurring polyhydroxylated fatty acid named aleuritic (or 9,10,16-trihydroxyhexadecanoic) acid. Both components reacted, originating under specific conditions zinc polyaleuritate ionomers. The polymerization of aleuritic acid into polyaleuritate by a solvent-free, melt polycondensation reaction was investigated at different times (15, 30, 45, and 60 min), temperatures (140, 160, 180, and 200 °C), and proportions of zinc oxide and aleuritic acid (0:100, 5:95, 10:90, and 50:50, w/w). Kinetic rate constants calculated by infrared spectroscopy decreased with the amount of Zn due to the consumption of reactive carboxyl groups, while the activation energy of the polymerization decreased as a consequence of the catalyst effect of the metal. The adhesion and hardness of coatings were determined from scratch tests, obtaining values similar to robust polymers with high adherence. Water contact angles were typical of hydrophobic materials with values ≥94°. Both mechanical properties and wettability were better than those of bisphenol A (BPA)-based resins and most likely are related to the low migration values determined using a hydrophilic food simulant. The presence of zinc provided a certain degree of antibacterial properties. The performance of the coatings against corrosion was studied by electrochemical impedance spectroscopy at different immersion times in an aqueous solution of NaCl. Considering the features of these biobased lacquers, they can be potential materials for bisphenol A-free metal packagingPeer reviewe

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

Long-chain polyhydroxyesters from natural occurring aleuritic acid as potential material for food packaging

Fatty polyhydroxyesters (C≥16) are present in nature as barrier polymers like cutin in some protective tissues of higher plants. The mimicry of these biopolymers is regarded as a strategy to design nontoxic and fully biodegradable food packaging films and coatings. To obtain cutin inspired materials we have used a natural occurring polyhydroxylated monomer like aleuritic (9,10,16-trihydroxypalmitic) acid and a direct and scalable synthesis route consisting in the noncatalyzed melt-condensation polymerization in air. To reduce the number of hydroxyl groups and to increase hydrophobicity, palmitic acid has been used as a capping agent. Aleuritic-palmitic polyhydroxyesteres films have been obtained and characterized.Peer reviewe

Polyhydroxyester Films Obtained by Non-Catalyzed Melt-Polycondensation of Natural Occurring Fatty Polyhydroxyacids

Free-standing polyesters films from mono and polyhydroxylated fatty acids (C16 and C18) have been obtained by non-catalyzed melt-condensation polymerization in air at 150°C. Chemical characterization by Fourier transform infrared spectroscopy and 13C Magic Angle Spinning Nuclear Magnetic Resonance (13C MAS–NMR) has confirmed the formation of the corresponding esters and the occurrence of hydroxyl partial oxidation, which extent depends on the type of hydroxylation of the monomer (primary or secondary). Generally, polyester films obtained are hydrophobic, insoluble in common solvents, amorphous and infusible as revealed by X-ray diffraction and differential scanning calorimetry. In ω-polyhydroxy acids, esterification reaction with primary hydroxyls is preferential and, therefore, the structure can be defined as linear with variable branching depending on the amount of esterified secondary hydroxyls. The occurrence side oxidative reactions like the diol cleavage are responsible for chain cross-linking. Films are thermally stable up to 200–250°C though this limit can be extended up to 300°C in the absence of ester bonds involving secondary hydroxyls. By analogy with natural occurring fatty polyesters (i.e., cutin in higher plants), these polymers are proposed as biodegradable and non-toxic barrier films or coatings to be used, for instance, in food packing.Funding is provided by the Spanish Ministerio de Economía y Competitividad under project CTQ2011-24299 and by the Consejería de Economía, Innovación, Ciencia y Empleo of the Andalussian Government (Junta de Andalucía-FEDER) grant TEP-7418. JH-G acknowledges the support of the Marie Curie Intra-European Fellowship (BIOPROTO project).Peer reviewedPeer Reviewe

Applications and potentialities of Atomic Force Microscopy in fossil and extant plant cuticle characterization

Atomic Force Microscopy (AFM) is a versatile technique of surface characterization, providing accurate information about the topography and other wide variety of magnitudes at submicron scale. It is extensively utilized in materials science, but its use in other disciplines such as paleobotany is infrequent. In this review, we introduce the main concepts of AFM to paleobotanists, comparing the characteristics of this technique to common electronic and optical microscopies. Then, main works with extant plants, in particular plant cuticles, are described. Finally, realistic applications with fossils are reviewed and their potential use in the characterization of plant fossils discussed. AFM is proposed as a complementary technique to common microscopies to characterize plant cuticle fine details at nanoscale

The Response of Tomato Fruit Cuticle Membranes Against Heat and Light

Two important biophysical properties, the thermal and UV-Vis screening capacity, of isolated tomato fruit cuticle membranes (CM) have been studied by differential scanning calorimetry (DSC) and UV-Vis spectrometry, respectively. A first order melting, corresponding to waxes, and a second order glass transition (Tg) thermal events have been observed. The glass transition was less defined and displaced toward higher temperatures along the fruit ripening. In immature and mature green fruits, the CM was always in the viscous and more fluid state but, in ripe fruits, daily and seasonal temperature fluctuations may cause the transition between the glassy and viscous states altering the mass transfer between the epidermal plant cells and the environment. CM dewaxing reduced the Tg value, as derived from the role of waxes as fillers. Tg reduction was more intense after polysaccharide removal due to their highly interwoven distribution within the cutin matrix that restricts the chain mobility. Such effect was amplified by the presence of phenolic compounds in ripe cuticle membranes. The structural rigidity induced by phenolics in tomato CMs was directly reflected in their mechanical elastic modulus. The heat capacity (Cprev) of cuticle membranes was found to depend on the developmental stage of the fruits and was higher in immature and green stages. The average Cprev value was above the one of air, which confers heat regulation capacity to CM. Cuticle membranes screened the UV-B light by 99% irrespectively the developmental stage of the fruit. As intra and epicuticular waxes contributed very little to the UV screening, this protection capacity is attributed to the absorption by cinnamic acid derivatives. However, the blocking capacity toward UV-A is mainly due to the CM thickness increment during growth and to the absorption by flavone chalconaringenin accumulated during ripening. The build-up of phenolic compounds was found to be an efficient mechanism to regulate both the thermal and UV screening properties of cuticle membranes.Agencia Estatal de Investigación, Ministerio de Ciencia e Innovación RTI2018-094277- B/AEI/10.13039/501100011033 (co-financed by the European Regional Development Fund, ERDF)Ministerio de Ciencia, Innovación y Universidades” RYC2018-025079-I/AEI/10.13039/501100011033 (co-financed by the European Social Fund, ESF).Spanish Research Council (CSIC) PIE project 202040E003MINECO FPU grant (FPU17/01771).Peer reviewe

Polyhydroxyester Films Obtained by Non-Catalyzed Melt-Polycondensation of Natural Occurring Fatty Polyhydroxyacids

Free-standing polyesters films from mono and polyhydroxylated fatty acids (C16 and C18) have been obtained by non-catalyzed melt-condensation polymerization in air at 150°C. Chemical characterization by Fourier transform infrared spectroscopy and 13C Magic Angle Spinning Nuclear Magnetic Resonance (13C MAS–NMR) has confirmed the formation of the corresponding esters and the occurrence of hydroxyl partial oxidation, which extent depends on the type of hydroxylation of the monomer (primary or secondary). Generally, polyester films obtained are hydrophobic, insoluble in common solvents, amorphous and infusible as revealed by X-ray diffraction and differential scanning calorimetry. In ω-polyhydroxy acids, esterification reaction with primary hydroxyls is preferential and, therefore, the structure can be defined as linear with variable branching depending on the amount of esterified secondary hydroxyls. The occurrence side oxidative reactions like the diol cleavage are responsible for chain cross-linking. Films are thermally stable up to 200–250°C though this limit can be extended up to 300°C in the absence of ester bonds involving secondary hydroxyls. By analogy with natural occurring fatty polyesters (i.e., cutin in higher plants), these polymers are proposed as biodegradable and non-toxic barrier films or coatings to be used, for instance, in food packing.España Mineco CTQ2011-24299Junta de Andalucía-FEDER TEP-7418. JH-

Plant cuticle under global change: Biophysical implications

Peer Reviewe