Recovery and Purification of Cutin from Tomato By-Products for Application in Hydrophobic Films.

Tomato pomace is a low-cost, renewable resource that has been studied for the extraction of the biopolyester cutin, which is mainly composed of long-chain hydroxy fatty acids. These are excellent building blocks to produce new hydrophobic biopolymers. In this work, the monomers of cutin were extracted and isolated from tomato pomace and utilized to produce cutin-based films. Several strategies for the depolymerization and isolation of monomeric cutin were explored. Strategies differed in the state of the raw material at the beginning of the extraction process, the existence of a tomato peel dewaxing step, the type of solvent used, the type of alkaline hydrolysis, and the isolation method of cutin monomers. These strategies enabled the production of extracts enriched in fatty acids (16-hydroxyhexadecanoic, hexadecanedioic, stearic, and linoleic, among others). Cutin and chitosan-based films were successfully cast from cutin extracts and commercial chitosan. Films were characterized regarding their thickness (0.103 ± 0.004 mm and 0.106 ± 0.005 mm), color, surface morphology, water contact angle (93.37 ± 0.31° and 95.15 ± 0.53°), and water vapor permeability ((3.84 ± 0.39) × 10-11 mol·m/m2·s·Pa and (4.91 ± 1.33) × 10-11 mol·m/m2·s·Pa). Cutin and chitosan-based films showed great potential to be used in food packaging and provide an application for tomato processing waste.

Overview of Membrane Science and Technology in Portugal.

Membrane research in Portugal is aligned with global concerns and expectations for sustainable social development, thus progressively focusing on the use of natural resources and renewable energy. This review begins by addressing the pioneer work on membrane science and technology in Portugal by the research groups of Instituto Superior Técnico-Universidade de Lisboa (IST), NOVA School of Science and Technology-Universidade Nova de Lisboa (FCT NOVA) and Faculdade de Engenharia-Universidade do Porto (FEUP) aiming to provide an historical perspective on the topic. Then, an overview of the trends and challenges in membrane processes and materials, mostly in the last five years, involving Portuguese researchers, is presented as a contribution to a more sustainable water-energy-material-food nexus.

Decolorization of a Corn Fiber Arabinoxylan Extract and Formulation of Biodegradable Films for Food Packaging.

Corn fiber from the corn starch industry is a by-product produced in large quantity that is mainly used in animal feed formulations, though it is still rich in valuable components, such as arabinoxylans, with proven film-forming ability. During arabinoxylans' recovery under alkaline extraction, a dark-colored biopolymer fraction is obtained. In this work, a purified arabinoxylan extract from corn fiber with an intense brownish color was decolorized using hydrogen peroxide as the decolorizing agent. Biodegradable films prepared by casting the decolorized extract exhibited a light-yellow color, considered more appealing, envisaging their application in food packaging. Films were prepared with glycerol as plasticizer and citric acid as cross-linker. Although the cross-linking reaction was not effective, films presented antioxidant activity, a water vapor permeability similar to that of non-decolorized films, and other polysaccharides' and mechanical properties that enable their application as packaging materials of low-water-content food products.

Block Copolymer-Based Magnetic Mixed Matrix Membranes-Effect of Magnetic Field on Protein Permeation and Membrane Fouling.

In this study, we report the impact of the magnetic field on protein permeability through magnetic-responsive, block copolymer, nanocomposite membranes with hydrophilic and hydrophobic characters. The hydrophilic nanocomposite membranes were composed of spherical polymeric nanoparticles (NPs) synthesized through polymerization-induced self-assembly (PISA) with iron oxide NPs coated with quaternized poly(2-dimethylamino)ethyl methacrylate. The hydrophobic nanocomposite membranes were prepared via nonsolvent-induced phase separation (NIPS) containing poly (methacrylic acid) and meso-2,3-dimercaptosuccinic acid-coated superparamagnetic nanoparticles (SPNPs). The permeation experiments were carried out using bovine serum albumin (BSA) as the model solute, in the absence of the magnetic field and under permanent and cyclic magnetic field conditions OFF/ON (strategy 1) and ON/OFF (strategy 2). It was observed that the magnetic field led to a lower reduction in the permeate fluxes of magnetic-responsive membranes during BSA permeation, regardless of the magnetic field strategy used, than that obtained in the absence of the magnetic field. Nevertheless, a comparative analysis of the effect caused by the two cyclic magnetic field strategies showed that strategy 2 allowed for a lower reduction of the original permeate fluxes during BSA permeation and higher protein sieving coefficients. Overall, these novel magneto-responsive block copolymer nanocomposite membranes proved to be competent in mitigating biofouling phenomena in bioseparation processes.

Purification of Arabinoxylans from Corn Fiber and Preparation of Bioactive Films for Food Packaging.

Corn fiber, a by-product of the starch industry, is presently incorporated in animal feed. However, it has arabinoxylans as added-value components (besides ferulic acid) that should be valorized. In this work, the raw material, a fraction enriched in arabinoxylans from corn fiber, previously produced by alkaline extraction from corn fiber and pre-concentrated by ultrafiltration, was further purified. The use of ultrafiltration operated in diafiltration mode (dia-ultrafiltration) was evaluated for the purification of the arabinoxylans fraction. The objective was to maximize the removal of the small contaminants from the fraction and to maximize the permeability and/or the permeate flux, by selecting the relevant operating conditions involved in this process. The removal of contaminants (%) was estimated when their apparent rejection stabilized. Edible films were produced, from the resultant purified arabinoxylans fraction, using glycerol as plasticizer (30% dry basis). Additionally, films with the incorporation of ferulic acid were developed, in order to obtain barriers with antioxidant activity. The films were characterized in terms of mechanical properties, antioxidant activity and permeability to water vapor. The films prepared presented a good potential to be used as packaging for food products with low water content.

Chitosan Composites in Packaging Industry-Current Trends and Future Challenges.

Chitosan-based composites play an important role in food packaging applications and can be used either as films or as edible coatings. Due to their high costs and lower performance (i.e., lower barrier against water vapor, thermal, and mechanical properties) when compared to the traditional petroleum-based plastics, the use of such biopolymers in large-scale is still limited. Several approaches of chitosan composites in the packaging industry are emerging to overcome some of the disadvantages of pristine polymers. Thus, this work intends to present the current trends and the future challenges towards production and application of chitosan composites in the food packaging industry.

Influence of Magnetic Nanoparticles on PISA Preparation of Poly(Methacrylic Acid)-b-Poly(Methylmethacrylate) Nano-Objects.

This article presents the synthesis of poly(methacrylic acid)-b-poly(methyl methacrylate) diblock copolymer via polymerization-induced self-assembly in the presence of iron-oxide nanoparticles. Detailed phase diagrams with and without inorganic nanoparticles were constructed. Scanning transmission electron microscopy and energy dispersive X-ray photometry studies confirme the decoration of the polymeric nanoparticles with the iron-oxide nanoparticles. These hybrid nanoparticles were used to prepare porous thin film membranes by spin coating. Finally, the magneto-responsive properties of the membranes were assessed using water filtration tests in the presence and absence of a magnetic field.

Development and characterisation of hybrid polysaccharide membranes for dehydration processes.

The purpose of this work is the development and characterisation of new hybrid polysaccharide (FucoPol) membranes. These membranes were prepared by incorporation of a SiO2 network homogeneously dispersed by using a sol-gel method with GPTMS as a crosslinker silica precursor. They were further crosslinked with CaCl2 for reinforcement of mechanical properties and improvement of their permeation performance. They were characterised in terms of their structural, mechanical and thermal properties. They presented a dense and homogeneous structure, resistant to deformation, with a Tg of 43 °C and a thermal decomposition between 240 and 251 °C. The hybrid FucoPol membranes were tested for ethanol dehydration by pervaporation and also for nitrogen dehydration. They exhibited high water selectivity values, similar to PERVAP® 4101, however they lost their stability when exposed to solutions of 10.0 wt.% water in ethanol. In contrast, these membranes were stable when applied in N2 dehydration, leading to reproducible performance and very high water selectivities.

Comparison of different coating techniques on the properties of FucoPol films.

Plasma deposition, liquid flame spray (LFS) and atomic layer deposition (ALD) were used to form inorganic coatings in new exopolysaccharide (FucoPol) biodegradable films. Coated films were characterised in terms of surface, optical and barrier properties in order to evaluate their potential use in food packaging. FucoPol films presented dense and homogeneous surface with instant water contact angle of 95̊. Plasma deposition of perfluorohexane (PFH) on FucoPol surface has not shown significant improvement in the hydrophobic behaviour over the time. The FucoPol coating of SiO2 nanoparticles deposited by LFS and plasma deposition of PFH have shown higher instant water contact angle (135°) caused by coating surface roughness, but this hydrophobic behaviour was not stable over time. FucoPol films coated only with TiO2 deposited by ALD and combination of that with plasma deposition of PFH have shown stable water contact angle during time (90̊ and 115̊, respectively), transparency in the same order of magnitude and significantly lower permeability to water vapour (3.45×10-11mol/m s Pa and 3.45×10-11mol/m s Pa when compared to uncoated films with 5.32×10-11mol/m s Pa). Moreover, films coated with TiO2-PFH have also shown a permeability to oxygen of 1.70×10-16molm/m2sPa which is 67% lower than uncoated films.

Concentration of Tea Extracts by Osmotic Evaporation: Optimisation of Process Parameters and Effect on Antioxidant Activity.

In this work, the concentration process of three different tea extracts (medicinal Rosil No. 6, Black, and Forest Fruit teas) using the osmotic evaporation (OE) process, was studied. The effect of the OE process on the content of phenolic compounds and antioxidant activity was evaluated. The concentration process was carried out in a hollow-fibre membrane contactor with an effective surface area of 0.54 m². The tea extract was circulated through the shell side of the contactor, while a concentrated osmotic solution (CaCl2 5 M) was circulated inside the fibres. The flux, the driving force, and the mass transfer coefficient were evaluated. A decrease of the water flux over time was observed and was attributed only to the decrease of the driving force, caused by the dilution of the osmotic solution. Using a surface area/feed volume ratio of 774 m²·m-3, it is possible to reach a tea concentration of 40% (w/w) in 5 h, with a constant water flux and without losing the phenolic content and antioxidant potential in most teas.

Development and characterization of bilayer films of FucoPol and chitosan.

Bilayer films of FucoPol and chitosan were prepared and characterized in terms of optical, morphologic, hygroscopic, mechanical and barrier properties, to evaluate their potential application in food packaging. Bilayer films have shown dense and homogeneous layers, and presented enhanced properties when comparing to monolayer FucoPol films. Though, a high swelling degree in contact with liquid water (263.3%) and a high water vapour permeability (0.75×10(-11)mol/msPa), typical of polysaccharide films, was still observed. However, they presented a low permeability to O2 and CO2 (0.47×10(-16)molm/m(2)sPa and 5.8×10(-16)molm/m(2)sPa, respectively). Tensile tests revealed a flexible and resistant film with an elongation at break of 38% and an elastic modulus of 137MPa. The studied properties, in particular the excellent barrier to gases, impart these bilayer films potential to be used in packaging of low moisture content products, as well as in multilayered hydrophobic/hydrophilic/hydrophobic barriers for food products with a broader range of water content.

Polysaccharide-Based Membranes in Food Packaging Applications.

Plastic packaging is essential nowadays. However, the huge environmental problem caused by landfill disposal of non-biodegradable polymers in the end of life has to be minimized and preferentially eliminated. The solution may rely on the use of biopolymers, in particular polysaccharides. These macromolecules with film-forming properties are able to produce attracting biodegradable materials, possibly applicable in food packaging. Despite all advantages of using polysaccharides obtained from different sources, some drawbacks, mostly related to their low resistance to water, mechanical performance and price, have hindered their wider use and commercialization. Nevertheless, with increasing attention and research on this field, it has been possible to trace some strategies to overcome the problems and recognize solutions. This review summarizes some of the most used polysaccharides in food packaging applications.

Biodegradable films produced from the bacterial polysaccharide FucoPol.

FucoPol, an exopolysaccharide produced by Enterobacter A47, grown in bioreactor with glycerol as carbon source, was used with citric acid to obtain biodegradable films by casting. The films were characterized in terms of optical, hygroscopic, mechanical and barrier properties. These films have shown to be transparent, but with a brown tone, imparting small colour changes when applied over coloured surfaces. They were hydrophilic, with high permeability to water vapour (1.01×10(-11)mol/msPa), but presented good barrier properties to oxygen and carbon dioxide (0.7×10(-16)molm/m(2)sPa and 42.7×10(-16)molm/m(2)sPa, respectively). Furthermore, films have shown mechanical properties under tensile tests characteristic of ductile films with high elongation at break, low tension at break and low elastic modulus. Although the obtained results are promising, films properties can be improved, namely by testing alternative plasticizers, crosslinking agents and blends with other biopolymers. Taking into account the observed ductile mechanical properties, good barrier properties to gases when low water content is used and their hydrophilic character, it is foreseen a good potential for FucoPol films to be incorporated as inner layer of a multilayer packaging material.

Supported ionic liquid membranes for removal of dioxins from high-temperature vapor streams.

Dioxins and dioxin-like chemicals are predominantly produced by thermal processes such as incineration and combustion at concentrations in the range of 10-100 ng of I-TEQ/kg (I-TEQ = international toxic equivalents). In this work, a new approach for the removal of dioxins from high-temperature vapor streams using facilitated supported ionic liquid membranes (SILMs) is proposed. The use of ceramic membranes containing specific ionic liquids, with extremely low volatility, for dioxin removal from incineration sources is proposed owing to their stability at very high temperatures. Supported liquid membranes were prepared by successfully immobilizing the ionic liquids tri-C(8)-C(10)-alkylmethylammonium dicyanamide ([Aliquat][DCA]) and 1-n-octyl-3-methylimidazolium dicyanamide ([Omim][DCA]) inside the porous structure of ceramic membranes. The porous inorganic membranes tested were made of titanium oxide (TiO(2)), with a nominal pore size of 30 nm, and aluminum oxide (Al(2)O(3)), with a nominal pore size of 100 nm. The ionic liquids were characterized, and the membrane performance was assessed for the removal of dioxins. Different materials (membrane pore size, type of ionic liquid, and dioxin) and different operating conditions (temperature and flow rate) were tested to evaluate the efficiency of SILMs for dioxin removal. All membranes prepared were stable at temperatures up to 200 °C. Experiments with model incineration gas were also carried out, and the results obtained validate the potential of using ceramic membranes with immobilized ionic liquids for the removal of dioxins from high-temperature vapor sources.

Proton NMR relaxometry study of Nafion membranes modified with ionic liquid cations.

Proton nuclear magnetic resonance (NMR) relaxometry was used to study the ionic mobility and levels of confinement within Nafion membranes modified by incorporation of selected ionic liquid (IL) cations. These studies were performed aiming at understanding the effect of using different types of ionic liquid cations, and their degree of incorporation, in the values of the spin-lattice relaxation times (T(1)) obtained at different values of frequency and thus detect the influence of confinement level on the ions mobility. The frequency dependence of the proton spin-lattice relaxation rate, R(1) = 1/T(1), for the modified Nafion/IL cation membranes was compared with that obtained for an unmodified Nafion membrane, allowing for distinguishing different contributions of the motions of the molecules depending on the frequency tested. The experimental R(1) results were analyzed in terms of models that consider the sum of the most effective relaxation contributions, to estimate the translational self-diffusion coefficient of the moving molecular species in the modified membranes. The stability of these membranes with temperature in terms of the spin-lattice relaxation was compared with results obtained by thermogravimetric analysis.