Extraction of vanillin using ionic-liquid-based aqueous two-phase systems

To explore proper extractive solvents and to design an optimized separation process it is highly imperative to understand the molecular-based phenomena governing the solutes partitioning. Moreover, the development of new techniques for the biomolecules separation and purification, while maintaining their functional characteristics unchanged, is still ongoing. Therefore, in this work, the partition coefficients of vanillin, a compound with well-known organoleptic properties, were determined using improved ionic-liquid-based aqueous two-phase systems (ATPS). Three main parameters were evaluated through the vanillin partitioning process: the ionic liquid (IL) cation and anion structure, the temperature of equilibrium and the available concentration of vanillin in the global system. In all systems and conditions tested, vanillin preferentially migrates for the IL-rich phase. In addition, the three studied parameters largely influence the vanillin partitioning. In an attempt to elucidate the thermodynamics of the partitioning process, the standard molar thermodynamic functions of transfer of vanillin were also determined based on the temperature dependence data. These data indicate that the partition of vanillin results from an interplay between enthalpic and entropic contributions where both the IL anion and more complex cations play an essential role. Moreover, viscosities and densities of both aqueous phases were experimentally measured at the mass fraction compositions for which the partition coefficients were determined. The results gathered in this work indicate that IL-based ATPS can be further employed in the extraction and purification of vanillin from different matrices, as confirmed by the large partition coefficients obtained and improved low viscosity systems. (C) 2010 Elsevier B.V. All rights reserved.BIIPP projec - QREN 11551FCT - SFRH/BPD/41781/200

Poly(glycidyl methacrylate)/bacterial cellulose nanocomposites: preparation, characterization and post-modification

Nanocomposites composed of poly(glycidyl methacrylate) (PGMA) and bacterial cellulose (BC) were prepared by the in-situ free radical polymerization of glycidyl methacrylate (GMA) inside the BC network. The resulting nanocomposites were characterized in terms of structure, morphology, water-uptake capacity, thermal stability and viscoelastic properties. The three-dimensional structure of BC endowed the nanocomposites with good thermal stability (up to 270 °C) and viscoelastic properties (minimum storage modulus = 80 MPa at 200 °C). In addition, the water-uptake and crystallinity decreased with the increasing content of the hydrophobic and amorphous PGMA matrix. These nanocomposites were then submitted to post-modification via acid-catalysed hydrolysis to convert the hydrophobic PGMA into the hydrophilic poly(glyceryl methacrylate) (PGOHMA) counterpart, which increased the hydrophilicity of the nanocomposites and consequently improved their water-uptake capacity. Besides, the post-modified nanocomposites maintained a good thermal stability (up to 250 °C), viscoelastic properties (minimum storage modulus = 171 MPa at 200 °C) and porous structure. In view of these results, the PGMA/BC nanocomposites can be used as functional hydrophobic nanocomposites for post-modification reactions, whereas the PGOHMA/BC nanocomposites might have potential for biomedical applications requiring hydrophilic, swellable and biocompatible materials.info:eu-repo/semantics/publishedVersio

Physicochemical surface properties of bacterial cellulose/polymethacrylate nanocomposites: an approach by inverse gas chromatography

Nanocomposites of poly(glycidyl methacrylate) and bacterial cellulose (BC), or poly(poly(ethylene glycol) methacrylate) and BC were produced via the in-situ polymerization of methacrylic monomers, inside the BC 3D network. The nanocomposites surface properties were evaluated by inverse gas chromatography (IGC). The dispersive component of surface energy (γsd) varied between 35.64 - 83.05 mJ m-2 at 25 °C. The surface of the different nanocomposites has a predominant basic character (Kb/Ka = 4.20-4.31). Higher specific interactions with polar probes were found for the nanocomposite bearing pendant epoxide groups, that apart from the low surface area (SBET = 0.83 m2 g-1) and monolayer capacity (nm = 2.18 μmol g-1), exhibits a high value of γsd (88.19 mJ m-2 at 20 °C). These results confirm the potential of IGC to differentiate between nanocomposites with different surface functional groups and to predict their potential interactions with living tissues, body fluids and other materials.info:eu-repo/semantics/publishedVersio

Composites based on acylated cellulose fibers and low-density polyethylene: Effect of the fiber content, degree of substitution and fatty acid chain length on final properties

Low-density polyethylene was filled with unmodified and fatty acid (hexanoic, dodecanoic, octadecanoic and docosanoic acids) esterified cellulose fibers. The thermal and mechanical properties, morphology and the water absorption behavior of the ensuing composites were investigated. The chemical modification of the cellulose fibers with fatty acids clearly improved the interfacial adhesion with the matrix and hence the mechanical properties of the composites and decreased their water uptake capacity. The performance of the composites was strongly affected by the degree of substitution (DS) and the fatty chain length as indicated by the fact that esterified cellulose fibers with low DS gave composites with better mechanical properties. (C) 2008 Elsevier Ltd. All rights reserved

Bio-based synthesis of oxidation resistant copper nanowires using an aqueous plant extract

Copper nanowires have recently emerged as promising nanomaterials for transparent conducting electrodes applications, however, their production commonly involves the use of harmful reagents. In this study, we describe for the first time a simple and cost-effective bio-based synthesis of copper nanowires using an aqueous plant extract (Eucalyptus globulus) as the reducing/stabilizing agent and oleic acid and oleylamine as surfactants. Well-dispersed crystalline copper nanowires (λmáx = 584–613 nm) were obtained with average diameters in the nanometric range (44 and 145 nm) and lengths in the micrometric range (from 5 to dozens of micrometres) using extract concentrations between 10 and 50 mg mL−1. Moreover, the aspect ratio of these nanowires can be adjusted (from around 14–20 to 160–400) by changing the experimental conditions, namely the use of oleic acid. Phenolic compounds were found to have a key role in this bioreduction process allowing to obtain practically only nanowires (without other morphologies). Nevertheless, the use of oleic acid/oleylamine is essential to manipulate their size and aspect ratio. Most importantly, these bio-based copper nanowires were found to be resistant under storage in ethanol and when submitted to air exposure, both for 2 weeks, certainly due to the adsorption of antioxidant biomolecules (phenolic) at their surface, thus avoiding the use of other polymeric protective layers. The conductivity of the CuNWs was found to be 0.009 S cm−1. As a result, this study opens a new standpoint in this field, “closing the door” to the use of hazardous reagents and synthetic polymeric protective layers, on the production of stable copper nanowires with potential application as conductive materials.publishe

Biobased films of nanocellulose and mango leaf extract for active food packaging: supercritical impregnation versus solvent casting

Antioxidant and antimicrobial free-standing films composed of nanofibrillated cellulose (NFC) and a polyphenolic-rich extract, viz. mango leaf extract (MLE), were produced via supercritical solvent impregnation (SSI) and conventional solvent casting film-processing methodologies. The CO2-assisted impregnation of NFC with MLE created robust films with thermal stability up to 250 °C, good mechanical performance (Young's modulus > 4.7 GPa), UV-light barrier properties, antioxidant capacity with maximum inhibition percentage of ca. 84%, and antimicrobial activity against Staphylococcus aureus (growth inhibition ≈ 37%) and Escherichia coli (growth inhibition ≈ 91%). The comparison of the NFC/MLE films prepared by SSI with those fabricated via solvent casting shows a clear advantage of the SSI methodology. Particularly, the antioxidant and antimicrobial activities are visibly higher in the films fabricated by the CO2-assisted impregnation of MLE into NFC. In fact, for the SSI films, the MLE components are mostly adsorbed at the surface and not in the bulk of the biopolymeric matrix, which translates into faster migrations and, hence, higher active properties. All these findings evinced the potential performance of the NFC/MLE films prepared by the eco-friendly SSI as UV-blocking, antioxidant, and antimicrobial bio-based materials for application as sustainable active food packaging.publishe

Antioxidant and antimicrobial films based on brewers spent grain arabinoxylans, nanocellulose and feruloylated compounds for active packaging

In this study, brewers spent grain (BSG) arabinoxylans-based nanocomposite films were prepared by solvent casting of arabinoxylans (AX) suspensions containing different amounts of nanofibrillated cellulose (NFC, 5, 10, 25, 50 and 75% mass fraction). The obtained nanocomposite films were homogeneous and presented thermal stability up to 230 °C and good mechanical properties (Young's modulus up to 7.5 GPa). Additionally, the films with 50% NFC were loaded with ferulic acid or feruloylated arabinoxylo-oligosaccharides enriched fraction from BSG (75 mg per g of film). This combination enhanced the UV–Vis barrier properties and imparted additional functionalities to the films, namely (i) antioxidant activity up to 90% (DPPH scavenging activity), (ii) antibacterial activity against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria, and (iii) antifungal activity towards the polymorphic fungus Candida albicans. Therefore, these fully biobased nanocomposite films show potential for application as active food packaging systems.publishe

Switchable adhesive films of pullulan loaded with a deep eutectic solvent-curcumin formulation for the photodynamic treatment of drug-resistant skin infections

Antimicrobial photodynamic therapy (aPDT) is a potent tool to surpass the global rise of antimicrobial resistance; still, the effective topical administration of photosensitizers remains a challenge. Biopolymer-based adhesive films can safely extend the residence time of photosensitizers. However, their wide application is narrowed by their limited water absorption capacity and gel strength. In this study, pullulan-based films with a switchable character (from a solid film to an adhesive hydrogel) were developed. This was accomplished by the incorporation of a betaine-based deep eutectic solvent (DES) containing curcumin (4.4 μg.cm−2) into the pullulan films, which tuned the films’ skin moisture absorption ability, and therefore they switch into an adhesive hydrogel capable of delivering the photosensitizer. The obtained transparent films presented higher extensibility (elongation at break up to 338.2%) than the pullulan counterparts (6.08%), when stored at 54% of relative humidity, and the corresponding hydrogels a 4-fold higher adhesiveness than commercial hydrogels. These non-cytotoxic adhesives allowed the inactivation (∼5 log reduction), down to the detection limit of the method, of multiresistant strains of Staphylococcus aureus in ex vivo skin samples. Overall, these materials are promising for aPDT in the treatment of resistant skin infections, while being easily removed from the skin

Gluconacetobacter sacchari: An efficient bacterial cellulose cell-factory

The production of bacterial cellulose (BC) membranes by Gluconacetobacter saccbari, in Hestrin and Schramm (HS) based media containing glucose, sucrose, fructose, mannitol or glycerol as carbon sources, was studied for the first time. The highest BC production (2.7 g/L in 96 h) was obtained using glucose. The yields obtained are comparable with those obtained with other cellulose producing bacteria, and BC ultrastructure of the material was entirely similar. These results demonstrate the high potential of G. sacchari as a BC producing strain. (C) 2011 Elsevier Ltd. All rights reserved.FCTPOPH/FSESFRH/BPD/63250/200

Silylation of bacterial cellulose to design membranes with intrinsic anti-bacterial properties

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