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Bio-based lacquers prepared from an underutilized tomato processing residue such as pomace have been investigated as sustainable alternatives to bisphenol A (BPA)-based coatings for metal food packaging. The fabrication methodology consisted of a two-step process: spray-coating of a paste of the lipid fraction of tomato pomace with a mixture ethanol:H2O (3:1, v:v) on common metal substrates, used for food canning, such as aluminum (Al), chromium-coated tin-free steel (TFS), and electrochemically tin-plated steel (ETP), followed by the self melt-polycondensation of such lipid fraction. The polymerization reaction was conducted at 200 ◦C for different times (10, 20, 30, 40, 50, and 60 min) and was monitored by specular infrared spectroscopy, resulting in maximum degrees of esterification of ~92% for Al and ~85% for TFS and ETP substrates. The anticorrosion performance of the coatings was studied by electrochemical impedance spectroscopy at different immersion times (time intervals of 2–5 h during an overall stability test up to 170 h) in an aqueous solution of 1 wt% NaCl. The degree of polymerization and the physical properties of the coatings showed a strong dependence on the metal substrate used. In general, the best results were found for tomato pomace-based lacquers applied on aluminum, achieving higher mechanical strength (critical load of 1739 ± 198 mN for Al, 1078 ± 31 mN for ETP, and 852 ± 206 mN for TFS), hydrophobicity (water contact angle ~95◦ for Al, ~91◦ for ETP, and ~88◦ for TFS), and improved anticorrosion performance (coating resistance of 0.7 MΩcm2 after 170 h of immersion for Al, 0.7 MΩcm2 after 70 h of immersion for TFS, and negligible coating resistance for ETP). In view of the technical innovation proposed in the present paper, the estimation of the environmental sustainability of the process has been considered relevant to fit the circular economy target. For this purpose, a life cycle analysis (LCA) was applied to the overall process, revealing multiple advantages for both the environment and human health.

Producción Científica, The excellent catalytic properties of copper nanoparticles (CuNPs) for the degradation of the highly toxic and recalcitrant chlorpyrifos pesticide are widely known. However, CuNPs generally present low stability caused by their high sensitivity to oxidation, which leads to a change of the catalytic response over time. In the current work, the immobilization of CuNPs into a polycaprolactone (PCL) matrix via electrospinning was demonstrated to be a very effective method to retard air and solvent oxidation and to ensure constant catalytic activity in the long term. CuNPs were successfully anchored into PCL electrospun fibers in the form of Cu2O at different concentrations (from 1.25 wt % to 5 wt % with respect to the PCL), with no signs of loss by leaching out. The PCL mats loaded with 2.5 wt % Cu (PCL-2.5Cu) almost halved the initial concentration of pesticide (40 mg/L) after 96 h. This process was performed in two unprompted and continuous steps that consisted of adsorption, followed by degradation. Interestingly, the degradation process was independent of the light conditions (i.e., not photocatalytic), expanding the application environments (e.g., groundwaters). Moreover, the PCL-2.5Cu composite presents high reusability, retaining the high elimination capability for at least five cycles and eliminating a total of 100 mg/L of chlorpyrifos, without exhibiting any sign of morphological damages., Ministerio de Ciencia e Innovación (PID2021-127108OB-I00), Ministerio de Ciencia e Innovación (MCIN/AEI/ 10.13039/501100011033), EU NextGenerationEU/PRTR program (PLEC2021-007705), Ministerio de Ciencia, Innovación and Ministerio de Universidades - FEDER (RTI2018−098749−B-I00 and RTI2018−097367-A-I00), Junta de Castilla y León and EU-FEDER program (CLU-2019-04 and VA202P20)

Plasticizers are the most used polymer additives world-wide. Nowadays, conventional plasticizers (e.g. phthalates) do not meet the requirements in terms of renewability, biodegradability and cytotoxicity that have become necessary, especially if they are compounded with biopolymers. In this study, novel bioplasticizers are synthesized from levulinic acid via a protecting-group-free three-step process. After FT-IR and NMR characterization of the synthesized molecules, their plasticization effect has been tested with poly(3-hydroxybutyrate) (PHB) as a model semicrystalline biopolyester characterized by a narrow processing window, slow re-crystallization and high brittleness, which limit its processability and diffusion. The proposed bioplasticizers show remarkable miscibility with PHB and low leaching. The bioplasticizers also show a remarkable plasticization effect in terms of reducing the glass transition and melting temperatures (17 °C and 8 °C, respectively), which are comparable with the performance of the best commercially available green plasticizers. Furthermore, flexibility and crystallinity are positively affected, leading to an overall reduction in the typical brittleness of PHB. The observed effects result in an expansion of the temperature range in which PHB can be processed without thermal degradation. Moreover, the incorporation of the levulinic acid-based additives does not significantly affect the typical biodegradability and biocompatibility of PHB, showing their promising features as bioplasticizers for both environmental and biomedical applications.

Free-standing, robust, and transparent bioplastics were obtained by blending cellulose and naringin at different proportions. Optical, thermal, mechanical, antioxidant, and antimicrobial properties were systematically investigated. In general, the incorporation of naringin produced important UV blocking and plasticizer effects and good antioxidant and antibacterial properties. Moreover, the barrier properties were characterized by determination of their water and oxygen transmission rates, finding that both parameters decreased by increasing the naringin content and reaching values similar to other petroleum-based plastics and cellulose derivatives used for food packaging applications. Finally, the biodegradability of these films was determined by measurement of the biological oxygen demand (BOD) in seawater, demonstrating an excellent decomposition in such conditions.

Multifunctional bioplastics have been prepared by amorphous reassembly of cellulose, hemicelluloses (xylan), and hydrolyzed lignin. For this, the biopolymers were dissolved in a trifluoroacetic acid-trifluoroacetic anhydride mixture and blended in different percentages, simulating those found in natural woods. Free-standing and flexible films were obtained after the complete evaporation of the solvents. By varying xylan and hydrolyzed lignin contents, the physical properties were easily tuned. In particular, higher proportions of hydrolyzed lignin improved hydrodynamics, oxygen barrier, grease resistance, antioxidant, and antibacterial properties, whereas a higher xylan content was related to more ductile mechanical behavior, comparable to synthetic and bio-based polymers commonly used for packaging applications. In addition, these bioplastics showed high biodegradation rates in seawater. Such new polymeric materials are presented as alternatives to common man-made petroleum-based plastics used for food packaging.

Plastic pollution is becoming one of the most critical global problems nowadays. On the other hand, polymers are very versatile materials, and their products cannot be eliminated totally, but alternatives must be found. A very promising candidate is fungal mycelium. It is a self-growing, natural material, made of well-organized natural polymers, whose morphology, hydrodynamic, and mechanical properties can be tuned by changing the substrate of growth. In this work, we show that even small modifications in the composition of a standard fungal growth medium, potato dextrose broth (PDB), can induce significant differences in the morphology, chemical, and hydrodynamic properties of

The valorization of biomass from different renewable resources (i [...]

In this study, active biocomposite films of low-density polyethylene (LDPE) containing 5% wt. of curcumin, a natural chemical produced by some plants, are developed by melt extrusion and hot pressing. The detailed study of the physicochemical properties of the formed films demonstrates that the curcumin molecules, homogeneously dispersed in the whole volume of the LDPE matrix, cause a notable increase in the thermal stability of the LDPE polymer, without altering its thermal processability. At the same time the LDPE's water vapor barrier properties are significantly improved, while an effective antioxidant scavenging activity is observed against the 2,2-diphenyl-1-picrylhydrazyl free radicals (DPPH•). These results indicate that the developed active films based on the combination of LDPE and curcumin, following industrially applied preparation methods, are ideal candidates for active food packaging applications.

Tridecafluorononanoic acid (TFNA), a C6-fluorinated carboxylic acid, was esterified with cellulose at different molar ratios (0:1, 1:1, 2:1, and 3:1) in a trifluoroacetic acid (TFA):trifluoroacetic anhydride (TFAA):CHCl3 (2:1:1, v:v:v) solvent mixture. Free-standing films were obtained for all formulations and are presented as alternatives to composites and blends of paper with fluorinated molecules. Mechanical properties were investigated by tensile tests, and a plasticizer effect of fluorinated chains was observed. Interestingly, the wettability of these new cellulose derivatives was similar or even better than other common cellulose derivatives and fluorinated polymers employed in food packaging. Hydrodynamic properties were also improved by addition of TFNA, resulting in materials with water vapor permeability values comparable to other cellulose-based food packaging materials. In addition, films with the higher amounts of TFNA showed the required oil resistance for papers used in food packaging applications, as determined by the Kit Test. Finally, the biodegradation of these C6-fluorinated cellulose esters, assessed by biological oxygen demand (BOD) in seawater, was higher than typical bio-based polymers used in food packaging. The bioplastic synthesized at a molar ratio 1:1 (TFNA:cellulose) showed excellent performances in terms of greaseproof, hydrophobicity, ductility, and biodegradability, representing a sustainable alternative to typical plastics used in food packaging., This work has been partially supported by the Spanish “Ministerio de Ciencia, Innovación y Universidades” project RYC2018-025079-I/AEI/ 10.13039/501100011033 (cofinanced by the European Social Fund, ESF) and by the Spanish Research Council (CSIC) project 202040E003.

The fabrication of pectin-cellulose nanocrystal (CNC) biocomposites has been systematically investigated by blending both polysaccharides at different relative concentrations. Circular free-standing films with a diameter of 9 cm were prepared by simple solution of these carbohydrates in water followed by drop-casting and solvent evaporation. The addition of pectin allows to finely tune the properties of the biocomposites. Textural characterization by AFM showed fibrous morphology and an increase in fiber diameter with pectin content. XRD analysis demonstrated that pectin incorporation also reduced the degree of crystallinity though no specific interaction between both polysaccharides was detected, by ATR-FTIR spectroscopy. The optical properties of these biocomposites were characterized for the first time and it was found that pectin in the blend reduced the reflectance of visible light and increased UV absorbance. Thermal stability, analyzed by TGA, was improved with the incorporation of pectin. Finally, pectin-cellulose nanocrystal biocomposites showed a good biodegradability in seawater, comparable to other common bioplastics such as cellulose and low-molecular weight polylactide, among others.

Polyvinylpyrrolidone (commonly known as povidone or PVP) rapidly dissolves in water. This significantly hinders its use in sustained release formulations developed for the biomedical field. Electrospun fibers of PVP dissolve even faster due to larger surface to volume ratio. In this work, we propose a way to circumvent this problem by developing and using functional fibrous materials in hydrogel form. In particular, we demonstrate that ethanolic solutions of PVP containing two hydroxycinnamic acid derivatives, namely p-coumaric and ferulic acids could be electrospun into functional hydrogel fiber mats. After electrospinning, the formed composite mats were first thermally treated at 130 °C for 20 h and subsequently were immersed in aqueous media, where they turned into hydrogels. Thermal annealing did not degrade hydroxycinnamic acid derivatives, preserving their functionality. We propose these hydrogel fiber mats as potential wound dressings and to that end, in vitro tests showed up to 8 days of antioxidants’ release, and consequent protection of A549 epithelial cells against oxidative stresses. Biocompatibility tests using human red blood cells, A549 and HaCaT cell lines indicated no adverse effects. Model studies of mice skin burns induced by UV-B radiation showed that the hydrogel fiber dressings significantly reduced the levels of matrix metallopeptidase, (MMP-9), and glutathione peroxidase 1 (GPX-1), which are usually upregulated by reactive oxidative species on burnt skin. Finally, ex-vivo human skin investigations demonstrated skin regeneration and control of the inflammatory phase as indicated by low levels of pro-inflammatory cytokines (IL-6 and IL-8). Therefore, our outcomes indicate that the developed PVP-based fiber hydrogels, produced using a simple protocol, are promising candidates for active wound dressings.

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 packaging., Sustainable zinc polyaleuritate ionomer-based coatings are fabricated by green manufacturing and presented as an alternative technology for BPA-free metal packaging.

Cellulose ester films were prepared by esterification of cellulose with a multibranched fluorinated carboxylic acid, "BRFA" (BRanched Fluorinated Acid), at different anhydroglucose unit:BRFA molar ratios (i.e., 1:0, 10:1, 5:1, and 1:1). Morphological and optical analyses showed that cellulose-BRFA materials at molar ratios 10:1 and 5:1 formed flat and transparent films, while the one at 1:1 M ratio formed rough and translucent films. Degrees of substitution (DS) of 0.06, 0.09, and 0.23 were calculated by NMR for the samples at molar ratios 10:1, 5:1, and 1:1, respectively. ATR-FTIR spectroscopy confirmed the esterification. DSC thermograms showed a single glass transition, typical of amorphous polymers, at -11 °C. The presence of BRFA groups shifted the mechanical behavior from rigid to ductile and soft with increasing DS. Wettability was similar to standard fluoropolymers such as PTFE and PVDF. Finally, breathability and water uptake were characterized and found comparable to materials typically used in textiles.

The replacement of plastic with eco-friendly and biodegradable materials is one of the most stringent environmental challenges. In this respect, cellulose stands out as a biodegradable polymer. However, a significant challenge is to obtain biodegradable materials for high-end photonics that are robust in humid environments. Here, we demonstrate the fabrication of high-quality micro- and nanoscale photonic and plasmonic structures via replica molding using pure cellulose and a blended version with nonedible agro-wastes. Both materials are biodegradable in soil and seawater according to the ISO 17556 standard. The pure cellulose films are transparent in the vis–NIR spectrum, having a refractive index similar to glass. The microstructured photonic crystals show high-quality diffractive properties that are maintained under extended exposure to water. Nanostructuring the cellulose transforms it to a biodegradable metasurface manifesting bright structural colors. A subsequent deposition of Ag endowed the metasurface with plasmonic properties used to produce plasmonic colors and for surface-enhanced Raman scattering.

The aerial parts of plants, including the leaves, fruits and non-lignified stems, are covered with a protective cuticle, largely composed of the polyester cutin. Two mechanisms of cutin deposition have been identified in tomato (Solanum lycopersicum) fruit. The contribution of each mechanism to cutin synthesis and deposition has shown a temporal and coordinated sequence that correlates with the two periods of organ growth, cell division and cell expansion. Cutinsomes, self-assembled particles composed of esterified cutin monomers, are involved in the synthesis of the procuticle during cell division and provide a template for further cutin deposition. CUTIN SYNTHASE1 (CUS1), an acyl transferase enzyme that links cutin monomers, contributes to massive cuticle deposition during the early stages of the cell expansion period by incorporating additional cutin to the procuticle template. However, cutin deposition and polymerization appear to be part of a more complex biological scenario, which is yet not fully understood. CUS1 is also associated with the coordinated growth of the cutinized and non-cutinized domains of the outer epidermal wall, and affects cell size. A dynamic and complex interplay linking cutin synthesis with cell wall development and epidermal cell size has been identified.

Coral reefs are vital for the marine ecosystem and their potential disappearance can have unequivocal consequences on our environment. Aside from pollution-related threats (changes in water temperature, plastics, and acidity), corals can be injured by diseases, predators, humans and other invasive species. Diseases play an important role in this decline, but so far very few mitigation strategies have been proposed and developed to control this threat. In this work, we demonstrate that recently developed bi-layer human skin wound treatment patches containing antiseptics and natural antioxidants with controlled-release capacity can be adapted to treat scleractinian coral wounds effectively. A hydrophilic bilayer film based on polyvinylpyrrolidone (PVP) and hyaluronic acid was used to cover the open wounds while delivering the antiseptics for rapid action. Afterwards, the hydrophilic bi-layer covered wound was sealed with an antioxidant and hydrophobic ε-caprolactone-p-coumaric acid copolymer by melt injection at low temperatures. Treated coral injuries were monitored both in aquaria system and in natural environment in Maldives for over 4 months to reduce the number of entry points for organisms that could lead to diseases. The corals well-tolerated both biomaterials as well as the antiseptics incorporated in these materials. The treatments displayed self-adhering properties, tuneable dissolution time, and biocompatibility and stimulated regeneration properties within the coral wound. As such, this work demonstrates that certain human skin wound treatment materials can be successfully adapted to the curing of coral wounds and delivery of specific drugs to slow down, reduce or even stop the spread of diseases in scleractinian corals as well as in all other benthic organisms affected by uncontrolled pathologies.

Plant cuticles have been used as models to produce hydrophobic films composed of sodium alginate, the fatty acid fraction of tomato pomace agrowaste, and beeswax. The fabrication process consisted of the blending of components in green solvents (water and ethanol) and a subsequent thermal treatment (150 °C, 8 h) to polymerize unsaturated and polyhydroxylated fatty acids from tomato pomace. When sodium alginate and tomato pomace fatty acids were blended, free-standing films were obtained. These films were characterized to evaluate their morphological (SEM), chemical (solid-state NMR, ATR-FTIR), mechanical (tensile tests), thermal (TGA), and hydrodynamic (water contact angle, uptake, and permeability) properties. A comparison between nonpolymerized and polymerized samples was carried out, revealing that the thermal treatment represents a sustainable route to create structured, composite networks of both components. Finally, beeswax was added to the blend with the same amounts of sodium alginate and tomato pomace fatty acids. The presence of the wax improved the hydrophobicity and the mechanical and water barrier properties as well as decreased the water uptake. These results indicate that polymerized plant cuticle-like films have valuable potential for packaging applications.

Cellulose acetate oleate ester has been synthesized from oleic acid and cellulose acetate by using a mixed anhydride system based on a mixture of trifluoroacetic acid and trifluoroacetic acid anhydride with chloroform as a co-solvent. In absence of oleic acid, cellulose acetate was deacetylated in this mixed anhydride system. However, when oleic acid was added, hydrolysis was prevented and oleate groups bound to the cellulose acetate chain were detected as confirmed by Nuclear Magnetic Resonance spectroscopy. Compared to cellulose acetate, cellulose acetate oleate ester showed a mechanical behavior closer to ductile materials and a lower glass transition temperature, indicating that oleate groups can act as an internal plasticizer of the polymer chains. The contact angle values increased from 61° for cellulose acetate to 106° for cellulose acetate oleate, which presented a low surface energy value (16 mJ/m2) with no contribution of the polar component. Furthermore, the esterified cellulose acetate oleate material showed a decrease in the water vapor transmission rates by ∼76% compared to those of pure cellulose acetate films. The oxygen permeability was also decreased by ∼90% after grafting the oleate group onto the cellulose acetate repetitive units because of the creation of a densely packed matrix, confirmed by SEM analysis. This behaviour was attributed to the oleate chain length, which creates a chemical interaction between water and oxygen molecules with free hydroxyl and oleate groups of cellulose acetate oleate.

A new and straightforward single-step route to decorate melamine foams with silver nanoparticles (ME/Ag) is proposed. Uniform coatings of silver nanoparticles with diameters less than 10 nm are formed in situ directly on the struts surface of the foams, after their dipping in an AgNO3 solution. We prove that the nanoparticles are stably adhered on the foams, and that their amount can be directly controlled by the concentration of the AgNO3 solution and the dipping time. Following this production route, ME/Ag foams can be obtained with silver content ranging between 0.2 and 18.6 wt % and excellent antibacterial performance, making them appropriate for various applications. Herein we explore the possibility to use them as antibacterial filters for water treatment, proving that they are able to remove completely Escherichia coli bacteria from water when filtered at flow rates up to 100 mL/h·cm2 due to the release of less than 1 ppm of Ag+ ions by the foams. No bacterial regrowth was observed after further dilution of the treated water, to arrive below the safety threshold of Ag+ for drinking water (0.1 ppm), demonstrating the excellent bactericide performance of the ME/Ag filters.

New seaweed-based biomaterials have been prepared using a simple method based on the selective dissolution in trifluoroacetic acid (TFA) of specific polymers and bioactive substances from red, green, and brown seaweeds. Depending on the seaweed's origin, the properties were found to be different, especially the mechanical ones. Furthermore, the samples were fully biodegradable in seawater in one month. Moreover, the antioxidant capacity of the biomaterials was highly increased respect to the pristine materials, demonstrating a selective extraction during the process of solubilization. Finally, biocompatibility and anti-inflammatory experiments demonstrated the non-toxicity of the biomaterials prepared from brown seaweed and a similar anti-inflammatory effect to commercial available drugs, confirming the potential application of the prepared biomaterials for the fabrication of biomedical devices.

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.

Superhydrophobic and wear abrasion resistant high impact polystyrene (HIPS)/silica nanocomposite coatings for metal surfaces have been produced by spray. An environmentally friendly perfluorinated acrylic copolymer (PFAC) primer coating layer was applied first, in order to enhance adhesion with the substrate and prolong abrasion resistance. The best nanocomposite composition was found to be 50% silica nanoparticles with respect to HIPS by weight. This coating displayed the lowest friction coefficient compared to other nanocomposites with lower or higher silica concentrations. Tribological experiments on the best performing nanocomposites indicated that wear tracks or marks had no debris, cracks or complete material removal. Furthermore, Taber® abrasion tests confirmed tribological findings and showed that the best nanocomposites resisted superhydrophobic degradation up to 35 continuous linear abrasion cycles (15 kPa). Nanocomposites made with general purpose polystyrene instead of HIPS could only resist up to 15 Taber® abrasion cycles. The reason was attributed to the mechanical energy dissipation capability of rubber domains in HIPS. Thermal annealing of the coatings had a deterministic effect on the durability of the coatings against wear induced loss of superhydrophobicity. Annealed and non-annealed coatings were characterized by Fourier transform infrared and X-ray photoelectron spectroscopy. Due to ease of fabrication, resultant mechanical robustness, use of non-toxic materials, and low-cost industrial scale availability of HIPS, nanoparticles and the primer polymer, these coatings can be effortlessly transformed into larger scale non-wettable protective treatments for metals.

A new type of water repellent treatment for woven cotton fabrics is demonstrated by using environmentally friendly non-toxic polymers. As a result of the treatment, cotton fabrics also demonstrated resistance to water penetration due to hydrostatic pressure build-up. The treatment is achieved by sequentially coating the fibers with a polymer nanocomposite comprising a C-6 perfluorinated acrylic copolymer and silica nanoparticles and acetoxy-cure silicone (PDMS) resin. Water droplets were easily repelled with corresponding roll-off angles well below 20°. Even impinging small droplets (8 µL) could be repelled with droplet roll-off angle of 17°. Additionally, treated fabrics were also able to hold a hydrostatic head pressure of 2.56 kPa (equal to 26 cm water column height) before leak. Performance of the hydrophobic cotton fabrics was tested by ultrasonic washing and wear abrasion tests. Hydrophobic fabrics resisted wear abrasion under 17.5 kPa up to 30 abrasion cycles. Moreover, the treatment was made in such a way that the open porous structured was preserved allowing breathability. The ease of application technique, industrial scale availability of the low-cost polymers and the non-toxic ingredients would allow this fabric treatment to be implemented in large scale textile treatment facilities.

Water insoluble monohydrochloride monohydrate free ciprofloxacin (Cipro) antibiotic was incorporated in polyvinylpyrrolidone (PVP) polymer matrix by using acetic acid co-solvent in water. The resultant solutions were cast into fully transparent antimicrobial films. Proper concentrations of acetic acid eliminated in situ crystallization of the antibiotic and the resultant phase separation upon solvent evaporation. The solutions could also be electrospun into nanofiber mats (non-transparent). Presence of residual PVP-bound acetic acid in dry PVP films induced unprecedented levels of plasticity (stretching capacity) and softness to the films. Additionally, PVP-bound acetic acid also acted as an antiseptic. Antibacterial properties of the films and fiber mats were confirmed on Escherichia coli and Bacillus subtilis (growth and viability). Films and nanofiber mats demonstrated promising wound resorption characteristics by using in vivo full-thickness excisional skin wound healing mice model. Nanofiber mats were resorbed much faster than transparent films. Wound exudate absorption in the films and resorption rate of the nanofiber mats were dependent on the starting acetic acid concentrations. The fact that PVP/Cipro solutions in aqueous acetic acid can be used either to produce transparent soft films or nanofiber mats renders this process highly suitable for the fabrication of new-generation potential dressings for wound management and care.

Microcrystalline cellulose (MCC) and polyamide 66 (PA66) have been separately dissolved in solutions containing trifluoroacetic acid (TFA) as a common solvent, mixed after their dissolution and cast. After solvent evaporation, self-organized membranes have been formed with three dimensional (3D) porous, interconnected morphology, the porosity of which depends on the relative ratio of cellulose and PA66, and is lost when the initial MCC content exceeds 50% by weight. Thermal and chemical analysis and X-ray diffraction results indicate that the addition of cellulose induces the amorphisation of PA66, while possible chemical interaction exists between the amorphous parts of PA66 and the cellulose. The various membranes produced with different 3D porosities have been characterized in terms of dielectric constant and salt permeability and their relation to cellulose-PA66 ratio has been determined.

Cost-effective oil absorbents for the remediation of oil spills have been developed following a facile process involving the modification of polyurethane foam surfaces with mixtures of silicon oxide nanoparticles and polydimethylsiloxane. Polyurethane foams with different pore sizes and connectivity are tested, and it was found that the proposed treatment, applied by dip coating and spray coating, strongly improves the intrinsic foams’ performance in terms of selectivity and oil absorption capacity. The modified foams reach oil absorption capacities up to 60 g/g and simultaneous negligible water uptake. The treatment is stable after multiple absorption cycles, and therefore, the foams can be reused without significant decrease in their performance, being possible, after five cycles of absorption and recovery of oil, to reach overall oil absorption capacities up to 250 g/g.

Climatic stressors due to global change induce important modifications to the chemical composition of plant cuticles and their biophysical properties. In particular, plant cuticles can become heavier, stiffer and more inert, improving plant protection.

To explore the potential of long chain polyhydroxyalkanoates as non-toxic food packaging materials, the characterization of polyesters prepared from a natural occurring polyhydroxylated C16 carboxylic acid (9,10,16-trihydroxyhexadecanoic or aleuritic acid) has been addressed. Such monomer has been selected to elucidate the reactivity of primary and secondary hydroxyl groups and their contribution to the structure and properties of the polyester. Resulting polyaleuritate films have been produced using an open mold in one-step, solvent-free self-polycondensation in melt state and directly in air to evaluate the effect of oxygen in their final physical and chemical properties. These polymers are amorphous, insoluble, and thermostable, being therefore suitable for solvent, and heat resistant barrier materials. Structurally, most of primary hydroxyls are involved in ester bonds, but there is some branching arising from the partial participation of secondary O-H groups. The oxidative cleavage of the vicinal diol moiety and a subsequent secondary esterification had a noticeable effect on the amorphization and stiffening of the polyester by branching and densification of the ester bond network. A derivation of such structural modification was the surface compaction and the reduction of permeability to water molecules. The addition of Ti(OiPr)4 as a catalyst had a moderate effect, likely because of a poor diffusion within the melt, but noticeably accelerated both the secondary esterification and the oxidative processes. Primary esterification was a high conversion bulk reaction while oxidation and secondary esterification was restricted to nearby regions of the air exposed side of cast films. The reason was a progressive hindering of oxygen diffusion as the reaction progresses and a self-regulation of the altered layer growth. Despite such a reduced extent, the oxidized layer noticeably increased the UV-vis light blockage capacity. In general, characterized physical properties suggest a high potential of these polyaleuritate polyesters as food preserving materials.

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.

Woven cotton fabrics were treated with a polyurethane modified aminosilicone fluid commonly used as a fabric softener. The aminoethylaminopropyl polydimethylsiloxane was modified with an aqueous dispersion of polycarbonate diol polyurethane using isopropyl alcohol as co-solvent resulting in stable micro-emulsions with an average droplet size of 1.5 μm. Polycarbonate polyurethane was chosen due to its good hydrolytic stability and low water absorption levels. Fabrics were treated either by immersion in emulsions or by spray coating. Treated fabrics had static water contact angles exceeding 143o with droplet shedding angles of less than 50o depending on the droplet volume. Treated textiles were breathable with vapor permeability levels of 5.6 mg (m day Pa)−1 that was similar to untreated fabrics. Good droplet shedding action was achieved based on the inherent fiber roughness. Accelerated ageing tests corresponding to 5 years using CIEL*a*b standards (7.5 × 106 lx∙hours exposure) indicated that no ageing occurred, with the overall color parameter of ΔE < 2.0 indicating invisible color changes to the naked eye. This sustainable approach can be easily scaled and may be a valuable treatment alternative for delicate fabrics commonly encountered in Heritage preservation; but also for many other cotton-based textiles.

Polyvinylpyrrolidone (PVP) has probably been one of the most utilized pharmaceutical polymers with applications ranging from a blood plasma substitute to nanoparticle drug delivery, since its synthesis in 1939. It is a highly biocompatible, non-toxic and transparent film forming polymer. Although high solubility of PVP in aqueous environment is advantageous, it still poses several problems for some applications in which sustained targeting and release are needed or hydrophobic drug inclusion and delivery systems are to be designed. In this study, we demonstrate that a common dietary phenolic antioxidant, p-coumaric acid (PCA), can be combined with PVP covering a wide range of molar ratios by solution blending in ethanol, forming new transparent biomaterial films with antiseptic and antioxidant properties. PCA not only acts as an effective natural plasticizer but also establishes H-bonds with PVP increasing its resistance to water dissolution. PCA could be released in a sustained manner up to a period of 3 days depending on the PVP/PCA molar ratio. Sustained drug delivery potential of the films was studied using methylene blue and carminic acid as model drugs, indicating that the release can be controlled. Antioxidant and remodeling properties of the films were evaluated in vitro by free radical cation scavenging assay and in vivo on a murine model, respectively. Furthermore, the material resorption of films was slower as PCA concentration increased, as observed from the in vivo full-thickness excision model. Finally, the antibacterial activity of the films against common pathogens such as Escherichia coli and Staphylococcus aureus and the effective reduction of inflammatory agents such as matrix metallopeptidases were demonstrated. All these properties suggest that these new transparent PVP/PCA films can find a plethora of applications in pharmaceutical sciences including skin and wound care.

After a skin injury, many complex metabolic events are triggered to ensure proper wound healing. Particularly for chronic, non-healing wounds or burns several risk factors such as persistent bacterial infections and fast dehydration can counteract the healing process. Intelligent wound dressings should help accelerate the healing process, while maintaining the wound bed clean and disinfected for several days at a time. Ideally, they should be self-adherent to both moist and dry skin surfaces and be transparent enough to allow prolonged wound inspection. These requirements pose challenges both in terms of materials science and pharmaceutics. Herein, we describe fabrication of a transparent bilayer construct for the sequential release and delivery of a cutaneous antiseptic and a widely used antibiotic, potentially suitable for wound dressing applications. The fabrication is a scalable waterborne and ecofriendly solution casting process. The first layer (for direct wound contact) is polyvinylpyrrolidone (PVP) containing a commercial antiseptic, Neomercurocromo® (Neo), while the second layer is a blend of hyaluronic acid (HA) and PVP containing ciprofloxacin. We show that the bilayer films have satisfactory self-adhering strength to human skin and that PVP and HA can interact via hydrogen bonds causing sustained release of the antibiotic over a period of 5 days. Biocompatibility was demonstrated on human foreskin fibroblast HFF-1 cells. Antibacterial activity was evaluated against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa while the wound resorption behavior was assessed through an in vivo full-thickness excisional wound healing mice model. These observations indicate that such bilayer constructs can be potentially implemented as wound care products for diverse range of skin wounds, including large area skin infections.

e-caprolactone-p-coumaric acid copolymers at different mole ratios (e-caprolactone:p-coumaric acid 1:0, 10:1, 8:1, 6:1, 4:1, and 2:1) were synthesized by melt-polycondensation and using 4-dodecylbenzene sulfonic acid as catalyst. Chemical analysis by NMR and GPC showed that copolyesters were formed with decreasing molecular weight as p-coumaric acid content was increased. Physical characteristics, such as thermal and mechanical properties, as well as water uptake and water permeability, depended on the mole fraction of p-coumaric acid. The p-coumarate repetitive units increased the antioxidant capacity of the copolymers, showing antibacterial activity against the common pathogen Escherichia coli. In addition, all the synthesized copolyesters, except the one with the highest concentration of the phenolic acid, were cytocompatible and hemocompatible, thus becoming potentially useful for skin regeneration applications.

All-cellulose composites with a potential application as food packaging films were prepared by dissolving microcrystalline cellulose in a mixture of trifluoroacetic acid and trifluoroacetic anhydride, adding cellulose nanofibers, and evaporating the solvents. First, the effect of the solvents on the morphology, structure, and thermal properties of the nanofibers was evaluated by atomic force microscopy (AFM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA), respectively. An important reduction in the crystallinity was observed. Then, the optical, morphological, mechanical, and water barrier properties of the nanocomposites were determined. In general, the final properties of the composites depended on the nanocellulose content. Thus, although the transparency decreased with the amount of cellulose nanofibers due to increased light scattering, normalized transmittance values were higher than 80% in all the cases. On the other hand, the best mechanical properties were achieved for concentrations of nanofibers between 5 and 9 wt.%. At higher concentrations, the cellulose nanofibers aggregated and/or folded, decreasing the mechanical parameters as confirmed analytically by modeling of the composite Young’s modulus. Finally, regarding the water barrier properties, water uptake was not affected by the presence of cellulose nanofibers while water permeability was reduced because of the higher tortuosity induced by the nanocelluloses. In view of such properties, these materials are suggested as food packaging films, We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)

Secretory organs likely evolved with land plants in Silurian-Devonian time, but it is questionable if they were passed on to living cycadaleans upon the extinction of seed ferns (Triassic-Jurassic?). They are defined as ducts of schizo-, lysig- or rhexigenous origin that exuded a heterogeneous lipoid mixture that fossilized as secretory products (droplets). In this study we detailed (1) the physical properties and distributions based on the compression-preserved Neuropteris ovata var. simonii and Laveineopteris rarinervis frond sections (Late Pennsylvanian Sydney Coalfield, Canada). Examined were also 1300 cuticular slides representing a number of plant groups, complemented by published data to infer biomass accumulation as potential kerogen in the geological column. In addition, (2) from select pinnules of the two species mentioned, nine secretory products and four surrounding cuticles were analyzed by micro-FTIR to evaluate statistically (PCA) the chemotaxonomic potential, and the kerogen chemistry. Further studies in support of (1) or (2) included methods of NICI, SEM, TEM and AFM, and by EDS. Results indicate that the secretory organs occurred in the entire N. ovata frond, its associate petiole and trunk, and in great abundance on the pinnules of both species in a random fashion. Secretory products show layering effects, surfaces can be intact, convoluted, folded, or damaged. At 100,000 magnification, microstructures are not observable. The exact chemical composition is unknown because of insolubility. IR spectra show peaks of functional groups frequently found in isocyanates, disubstituted alkynes, nitriles, polyynes, thiocyanates, and allenes, in part underpinned by EDS results. These compounds were presumably derived from the diagenetic alteration of resin-like terpenoid- or phenolic-related structures. That is particularly the case for the polyynes (i.e. ‘polyacetylenes’), synthesized by living plants with a variety of biological functions, including pigments and flavorings, toxins, and chemical repellents. The chemical information of the lipoid exudate, together with their morphological information and distribution will contribute to (i) the progress of chemotaxonomy and systematics of plant fossils, and (ii) a better understanding of the genesis of kerogens from plant-derived materials, particularly resinous remains.

Amorphous cellulose and poly(methyl methacrylate) (PMMA) blends in the form of free standing transparent hybrid films were prepared by dissolving both polymers in trifluoroacetic acid (TFA). Ultraviolet–visible (UV–vis) measurements indicated that the transparency of the films was always maintained regardless of cellulose-PMMA proportions. In addition, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements were carried out in order to characterize the chemical composition, intermolecular interactions and the crystallinity of the hybrid films. Thermo-gravimetric analysis (TGA), differential scanning calorimeter (DSC) and tensile test measurements demonstrated that amorphous cellulose improved the thermal and mechanical properties of PMMA considerably. Scanning electron microscope (SEM) and atomic force microscopy (AFM) measurements showed that hybrid films had no micron scale phase separation or segregation, resulting in highly uniform and homogenous miscibility between amorphous cellulose and PMMA. The wetting characteristics of the hybrid films were also studied by water contact angle measurements. Hybrid films showed better water barrier properties in comparison to commercial paper packaging. Furthermore, the hybrid films exhibited relative high dissolution resistance to common organic solvents, which dissolve PMMA completely. Considering the recent interest in polymer blends based on natural and synthetic macromolecules, these new transparent hybrids can have various potential applications particularly in general packaging and biomedical technologies.

Keratin extracted from wool fibers has recently gained attention as an abundant source of renewable, biocompatible material for tissue engineering and drug delivery applications. However, keratin extraction and processing generally require a copious use of chemicals, not only bearing consequences for the environment but also possibly compromising the envisioned biological outcome. In this study, we present, for the first time, keratin-PVP biocomposite fibers obtained via an all-water co-electrospinning process and explored their properties modulation as a result of different thermal crosslinking treatments. The protein-based fibers featured homogenous morphologies and average diameters in the range of 170–290 nm. The thermomechanical stability and response to a wet environment can be tuned by acting on the curing time; this can be achieved without affecting the 3D fibrous network nor the intrinsic hydrophilic behavior of the material. More interestingly, our protein-based membranes treated at 170 °C for 18 h successfully sustained the attachment and growth of primary human dermal fibroblasts, a cellular model which can recapitulate more faithfully the physiological human tissue conditions. Our proposed approach can be viewed as pivotal in designing tunable protein-based scaffolds for the next generation of skin tissue growth devices.

We compared the proliferation and differentiation of mouse neuroblastoma Neuro 2A cell line on single layer graphene and glass substrates. Quantitative and qualitative analysis of the cell proliferation and differentiation were performed, considering also the effect of a common adhesion factor, namely polylysine. We observed that on graphene substrates the cells proliferate faster with respect to glass; additionally, the presence of the adhesion factor enhances the difference and, remarkably, boosts the cell differentiation on the graphene-based interface. To understand the mechanism underlying a different cell behavior on the same adhesion coating, we carried out a physicochemical investigation of the studied interfaces (glass and graphene, bare and polylysine coated) by several techniques. In particular, we employed infrared spectroscopy to gain information on polylysine conformation, and atomic force microscopy force-distance curves to study adhesion properties at the surface. The results indicate that polylysine has an enhanced binding affinity for graphene, as well as a different molecular arrangement on graphene with respect to glass. These properties act as surface cues to trigger the cell response.

All-PLA blends have been fabricated by an easily scalable and green melt-blending of linear-PLLA and 3-armed star-shaped PDLLA at different proportions (100:0, 95:5, 90:10, 80:20, and 50:50, w:w). The fabrication process, carried out in a hot-press, consisted of three steps: an initial heating of the thoroughly blended polymer mixtures at 170 °C for 5 min, a second heating at 170 °C for 5 min with a pressure of 200 Pa, and a final cooling at room temperature during 20 min keeping the same pressure. This methodology resulted in very homogenous amorphous samples, as revealed by XRD and DSC. The incorporation of star-PDLLA toughened the polylactide matrix by a clear ductilization, opening opportunities for the expanded use of the developed blends in different applications, due to their increased processability. DSC analysis revealed indeed that by increasing star-PDLLA content it is possible to gradually reduce the Tg, as well as the capability of crystallization of the linear-PLLA component. Such properties determine a plasticizing effect on the final blends. The increased content of the star component turned the films from transparent to translucent and decreases the thermal decomposition temperatures, which remain in any case very well above room temperature. The water vapor transmission rates varied with the star-PDLLA content between values characteristic for isolating to breathable films, thus allowing the use of these blends in different applications such as food packaging and biomedical devices. Finally, no important changes of water contact angle and water uptake were observed between the different blends. Despite the negligible effect of seawater on the biodegradation of commercial PLA, star-PDLLA-containing blends showed high biodegradation rates at short-times in marine environments, reinforcing the environmentally friendly character of polylactide.