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Interest in producing films from renewable and biodegradable polymers, such as polysaccharides, has increased in recent years with the aim of reducing the environmental pollution caused by petroleum-based plastics. Additionally, combining the thermoplastic property of starch with the antioxidant and antimicrobial activities of chitosan is of great interest to develop active materials for food packaging. This study aims the preparation of thermoplastic blended starch-chitosan films mechanically reinforced with reduced graphene oxide (rGO). Blending the starch with chitosan and rGO showed that films had a hydrophobic surface (100°), low water solubility (weight loss less than 10%), and improved antioxidant activity. Furthermore, blended film prepared with 75% starch and 25% chitosan with rGO achieved the maximum value of electrical conductivity (6.51 × 10

The incorporation of carbon-based nanomaterials into biopolymer matrix, to provide mechanical reinforcement and to obtain electrically conductive bionanocomposites, requires the homogeneous dispersion of the fillers. Herein, it is investigated the influence of surfactant structures on the dispersibility of multiwalled carbon nanotubes (MWNT) within starch matrix. Three different ionic surfactants, sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB) and sodium cholate (SC), are employed to disperse the MWNT. Films with MWNT-SC show better dispersibility and an increase of about 75% of tensile strength and 60% of Young's modulus compared with films using MWNT-SDS and MWNT-CTAB. Nevertheless, MWNT functionalized with CTAB impart the highest values of antioxidant activity (scavenging activity around 30% in 1.5 h) and electrical conductivity (σ =14.75 S/m) to starch matrix. The properties of starch-based films can be tailored according to the physical adsorption of each surfactant on MWNT surface and/or the interfacial interaction of the surfactant with starch chains.

Longan (Dimocarpus longan Lour.) is a seasonal tropical fruit used by Chinese medicine in both fresh and dried pulp forms. Their polysaccharides have been reported to have biological activity. However, their composition and immune activity have not yet been disclosed. To fulfil this aim, hot water-soluble polysaccharides of fresh and dried longan pulp were fractionated according to their molecular weight by ultrafiltration (10, 50, 100 kDa cut off). The main polysaccharides recovered were 1,6-linked glucans branched at O-3 (4–8%), O-2 (1%), O-2,4 (0.1%), and O-3,4 (0.1%). The drying process promotes the solubility of the polysaccharides. These glucans from fresh and dried longan pulp have immunomodulatory activity, shown by in vitro phagocytosis, NO, TNF-α, and IL-6 macrophages production assays. They showed also to inhibit the inflammatory response induced by LPS. The immunological activity of these glucans seems to have different responses dependent on their molecular weight, related to the immune regulatory pathways.

Chitosan-genipin films present a bluish-green color due to the conjugated double bonds formed when monomeric or dimeric genipin residues bridge chitosan. This phenomenon limits their use when colorless materials are required. In this work, a two-step oxidation strategy was developed aiming to remove color from chitosan-genipin films while preserving their functional properties. A combined system using the recombinant CotA laccase from Bacillus subtilis mediated by 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) followed by a H 2 O 2 oxidation step was settled. ABTS boosted the laccase performance resulting in light brown chitosan-genipin films that were further decolorized upon immersion in a 5% H 2 O 2 solution at pH 11.0 and 40 °C for 30 min. The applied methodology leads to films that sustain both acidic stability and antioxidant capacity of the pristine films. Overall, the combined CotA laccase-ABTS/hydrogen peroxide developed methodology efficiently produce active and decolorized chitosan-genipin films with potential for application as eco-friendly transparent material which may have application as food packaging.

The small amount of proteins in starch-rich food industry byproducts can be an advantage to crosslink with genipin and tailor the performance of biobased films. In this work, genipin was combined with non- purified starch recovered from industrial potato washing slurries and used for films production. Starch recovered from potato washing slurries contained 0.75% protein, 2 times higher than starch directly obtained from potato and 6 times higher than the commercial one. Starch protein-genipin networks were formed with 0.05% and 0.10% genipin, gelatinized at 75 °C and 95 °C in presence of 30% glycerol. Bluish colored films were obtained in all conditions, with the higher surface roughness (Ra, 1.22 μm), stretchability (elongation, 31%), and hydrophobicity (water contact angle, 127°) for 0.10% genipin and starch gelatinized at 75 °C. Therefore, starch-rich byproducts, when combined with genipin, are promising for surpassing the starch-based films hydrophilicity and mechanical fragilities while providing light barrier properties.

Chitosan-genipin (Ch-Ge) films have been proposed as wine preservative due to their capacity to uptake iron ions. The wine is an aqueous acidic solution of water and ethanol, whose acidity derives from tartaric acid. This acid has been shown to form negatively charged iron-tartrate complexes able to interact with the positively charged amine groups of chitosan, removing the iron ions from solutions. Nevertheless, it is possible that these films can uptake iron ions in the presence of other carboxylic acids. To understand the iron-binding capacity of Ch-Ge films, aqueous solutions of different carboxylic acids were prepared in the presence of iron ions and Ch-Ge films. It was observed that the Ch-Ge films only presented sorption capacity at pH 3.5 in the presence of α-hydroxypolycarboxylic acids, through electrostatic interactions. These results allow proposing a broad application of Ch-Ge films to beverages and other liquids containing malic, tartaric or citric acids.

Hollow multilayer nanocapsules were successfully prepared through layer-by-layer assembly of two bioactive polysaccharides, chitosan and fucoidan. The stepwise adsorption of 10 chitosan/fucoidan layers and the consequent formation of a multilayer film on polystyrene nanoparticles (used as templates) were followed through ζ-potential measurement and the removal of the polystyrene core was confirmed by FTIR analysis. The chitosan/fucoidan nanocapsules morphology and size were evaluated by SEM and TEM, that showed that after the core removal, the nanocapsules maintained their spherical shape and a decrease of size occurred. A cationic bioactive compound, poly-L-lysine (PLL), was chosen to evaluate the loading and release behaviour of the nanocapsules. The chitosan/fucoidan nanocapsules showed a good capacity for the encapsulation and loading of PLL, which shows to be influenced by the initial PLL concentration and the method of encapsulation used. The results of fitting the linear superimposition model to the experimental data of PLL release suggest an anomalous behaviour, with one main polymer relaxation. The PLL release was found to be pH-dependent: at pH 2 relaxation is the governing phenomenon and at pH 7 Fick's diffusion is the main mechanism of PLL release. Chitosan/fucoidan nanocapsules is a promising delivery system for water soluble bioactive compounds, such as PLL, showing a great potential of application in food and pharmaceutical industries, The authors Ana I. Bourbon, Miguel A. Cerqueira, Elia Maricato, and Claudia Nunes are recipient of fellowships from the Fundacao para a Ciencia e Tecnologia, POPH-QREN and FSE (FCT, Portugal) through grants, SFRH/BD/73178/2010, SFRH/BPD/72753/2010, SFRH/BD/87245/2012 and SFRH/BPD/46584/2008, respectively. The authors thank the FCT Strategic Project PEst-OE/EQB/LA0023/2013 and the project "BioInd-Biotechnology and Bioengineering for improved Industrial and Agro-Food processes, REF. NORTE-07-0124-FEDER-000028 Co-funded by the Programa Operacional Regional do Norte (ON.2-O Novo Norte), QREN, FEDER. Also, thanks are due to Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), European Union, QREN, FEDER and COMPETE for funding the QOPNA research unit (project PEst-C/QUI/UI0062/2013; FCOMP-01-0124-FEDER-037296). The authors would like to acknowledge to Rui Fernandes from IBMC, University of Porto for assistance in TEM analysis and to Edith Ariza from SEMAT/UM by the support in SEM analysis.

The characterization of several commercial dextrins and the analysis of the potential of dextrin derived hydrogels for biomedical applications were performed in this work. The structural characterization of dextrins allowed the determination of the polymerization and branching degrees, which ranged from 6 to 17 glucose residues and 2 to 13%, respectively. Tackidex, a medical grade dextrin was choosen for further characterization. The combination of hydrogel with a dextrin nanogel and urinary bladder matrix was achieved without compromising the mechanical properties or microstructure. The encapsulation of cells, preserving its viability, confirms the biocompatibility of the injectable hydrogels, which have therefore great potential for biomedical applications., D.M.S. was supported by the grant SFRH/BD/64571/2009 from Fundacao para a Ciencia e Tecnologia (FCT), Portugal. We thank FCT funding through EuroNanoMed ENMED/0002/2010. The authors acknowledge the funding from QREN ("Quadro de Referencia Estrategica Nacional") and ADI ("Agencia de Inovacao") through the project Norte-07-0202-FEDER-038853.QOPNA research unit is funded by Fundacao para a Ciencia e a Tecnologia (FCT, Portugal, European Union, QREN, FEDER, and COMPETE (project PEst-C/QUI/UI0062/2013; FCOMP-01-0124-FEDER-037296), and the Portuguese National Mass Spectrometry Network, and Project PTDC/QUI-QUI/100044/2008. Ana S. P. Moreira and Claudia Nunes thanks FCT the grants (SFRH/BD/80553/2011; SFRH/BPD/46584/2008). The authors thank Prof. Dmitry V. Evtuguin for the use of SEC equipment.

Chitosan has been studied as a renewable polymer to form edible films allowing the incorporation of functional compounds. The aim of this work was to evaluate the effects in the chitosan films properties of the incorporation of grape pomace extracts: 0.15% of hot water extract (mainly polysaccharides), 0.15 and 0.3% of chloroform extract (wax), and 0.3 and 0.75% of n-hexane extract (oil). The evaluation of the surface morphology revealed that the films with the aqueous extract had the most homogeneous and smoother topography. The incorporation of higher proportion of wax and oil led to changes in mechanical properties of the films, namely lower resistance and stiffness. The chitosan-based films with 0.75% oil demonstrated a 75% decrease of solubility in water, due to their hydrophobicity, as confirmed by the contact angle and surface free energy measurements. The hydrophobic films showed higher antioxidant capacity in organic medium (ABTS and DPPH assays) whereas the most hydrophilic films showed an improvement in FRAP and reducing power assays. Therefore, all the chitosan-based films prepared by incorporation of these grape pomace extracts are promising for food shelf life extension. (C) 2014 Elsevier Ltd. All rights reserved.

The relevance of microalgae biotechnology for producing high-value compounds with biomedical application, such as polysaccharides, has been increasing. Despite this, the knowledge about the composition and structure of microalgae polysaccharides is still scarce. In this work, water-soluble polysaccharides from Nannochloropsis oculata were extracted, fractionated, structurally analysed, and subsequently tested in terms of immunostimulatory activity. A combination of sugar and methylation analysis with interaction data of carbohydrate-binding proteins using carbohydrate microarrays disclosed the complex structural features of the different polysaccharides. These analyses showed that the water-soluble polysaccharides fractions from N. oculata were rich in (β1→3, β1→4)-glucans, (α1→3)-, (α1→4)-mannans, and anionic sulphated heterorhamnans. The immunostimulatory assay highlighted that these fractions could also stimulate murine B-lymphocytes. Thus, the N. oculata water-soluble polysaccharides show potential to be further explored for immune-mediated biomedical applications.

The study carried out in this work concerns the structural characterization of pectic polysaccharides from plum (Prunus domestica L.) and pear (Pyrus communis L.) cell walls and commercial pectic polysaccharides, obtained from Citrus. The α-(1 → 4)-d-galacturonic acid backbone was submitted to a selective hydrolysis with endo-polygalacturonase (EPG) and the fractions with low molecular weight (

The use of chitosan films has been limited due to their high degradability in aqueous acidic media. In order to produce chitosan films with high antioxidant activity and insoluble in acid solutions caffeic acid was grafted to chitosan by a radical mechanism using ammonium cerium (IV) nitrate (60 mM). Genipin was used as cross-linker. This methodology originated films with 80% higher antioxidant activity than the pristine film. Also, these films only lost 11% of their mass upon seven days immersion into an aqueous solution at pH 3.5 under stirring. The films surface wettability (contact angle 105°), mechanical properties (68 MPa of tensile strength and 4% of elongation at break), and thermal stability for temperatures lower than 300 °C were not significantly influenced by the covalent linkage of caffeic acid and genipin to chitosan. Due to their characteristics, mainly higher antioxidant activity and lower solubility, these are promising materials to be used as active films.