Modified polysaccharides for food packaging applications: A review.

Development of new food packaging materials is crucial to reduce the use of single-use plastics and to limit their destructive impact on the environment. Polysaccharides provide an alternative solution to this problem. This paper summarizes and discusses recent research results on the potential of modifying polysaccharides as materials for film and coating applications. Modifications of polysaccharides significantly affect their properties, as well as their application usability. Although modifications of biopolymers for packaging applications have been widely studied, polysaccharides have attracted little attention despite being a prospective, environmentally friendly, and economically viable packaging alternative. Therefore, this paper discusses approaches to the development of biodegradable, polysaccharide-based food packaging materials and focuses on modifications of four polysaccharides, such as starch, chitosan, sodium alginate and cellulose. In addition, these modifications are presented not only in terms of the selected polysaccharide, but also in terms of specific properties, i.e. hydrophilic, barrier and mechanical properties, of polysaccharides. Such a presentation of results makes it much easier to select the modification method to improve the unsatisfactory properties of the material. Moreover, very often it happens that the applied modification improves one and worsens another property, which is also presented in this review.

Effect of Time on the Properties of Bio-Nanocomposite Films Based on Chitosan with Bio-Based Plasticizer Reinforced with Nanofiber Cellulose.

The deterioration of the performance of polysaccharide-based films over time, particularly their hydrophilicity and mechanical properties, is one of the main problems limiting their applications in the packaging industry. In the present study, we proposed to improve the performance of chitosan-based films through the use of: (1) nanocellulose as an additive to reduce their hydrophilic nature; (2) bio-based plasticizer to improve their mechanical properties; and (3) chestnut extract as an antimicrobial agent. To evaluate their stability over time, the properties of as-formed films (mechanical, hydrophilic, barrier and antibacterial) were studied immediately after preparation and after 7, 14 and 30 days. In addition, the morphological properties of the films were characterized by scanning electron microscopy, their structure by FTIR, their transparency by UV-Vis and their thermal properties by TGA. The films showed a hydrophobic character (contact angle above 100°), barrier properties to oxygen and carbon dioxide and strong antibacterial activity against Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria. Moreover, the use of nanofillers did not deteriorate the elongation at breaks or the thermal properties of the films, but their addition reduced the transparency. In addition, the results showed that the greatest change in film properties occurred within the first 7 days after sample preparation, after which the properties were found to stabilize.

Cerium(IV) chitosan-based hydrogel composite for efficient adsorptive removal of phosphates(V) from aqueous solutions.

The excess presence of phosphate(V) ions in the biosphere is one of the most serious problems that negatively affect aqueous biocenosis. Thus, phosphates(V) separation is considered to be important for sustainable development. In the presented study, an original cerium(IV)-modified chitosan-based hydrogel (Ce-CTS) was developed using the chemical co-precipitation method and then used as an adsorbent for efficient removal of phosphate(V) ions from their aqueous solutions. From the scientific point of view, it represents a completely new physicochemical system. It was found that the adsorptive removal of phosphate(V) anions by the Ce-CTS adsorbent exceeded 98% efficiency which is ca. 4-times higher compared with the chitosan-based hydrogel without any modification (non-cross-linked CTS). The best result of the adsorption capacity of phosphates(V) on the Ce-CTS adsorbent, equal to 71.6 mg/g, was a result of adsorption from a solution with an initial phosphate(V) concentration 9.76 mg/dm3 and pH 7, an adsorbent dose of 1 g/dm3, temperature 20 °C. The equilibrium interphase distribution data for the Ce-CTS adsorbent and aqueous solution of phosphates(V) agreed with the theoretical Redlich-Peterson and Hill adsorption isotherm models. From the kinetic point of view, the pseudo-second-order model explained the phosphates(V) adsorption rate for Ce-CTS adsorbent the best. The specific effect of porous structure of adsorbent influencing the diffusional mass transfer resistances was identified using Weber-Morris kinetic model. The thermodynamic study showed that the process was exothermic and the adsorption ran spontaneously. Modification of CTS with cerium(IV) resulted in the significant enhancement of the chitosan properties towards both physical adsorption (an increase of the point of zero charge of adsorbent), and chemical adsorption (through the presence of Ce(IV) that demonstrates a chemical affinity for phosphate(V) anions). The elaborated and experimentally verified highly effective adsorbent can be successfully applied to uptake phosphates(V) from aqueous systems. The Ce-CTS adsorbent is stable in the conditions of the adsorption process, no changes in the adsorbent structure or leaching of the inorganic filling were observed.

Modulation of physicochemical properties and antimicrobial activity of sodium alginate films through the use of chestnut extract and plasticizers.

Due to the growing demand for robust and environmentally friendly antimicrobial packaging materials, biopolymers have recently become extensively investigated. Although biodegradable biopolymers usually lack mechanical properties, which makes it inevitable to blend them with plasticizers. The purpose of this study was to investigate plasticization efficiency of bio-based plasticizers introduced into sodium alginate compositions containing chestnut extract and their effect on selected film properties, including primarily mechanical and antibacterial properties. The films were prepared by the casting method and sodium alginate was cross-linked with calcium chloride. Six different plasticizers, including three commercially available ones (glycerol, epoxidized soybean oil and palm oil) and three synthesized plasticizers that are mixtures of bio-based plasticizers, were used to compare their influence on the film properties. Interactions between the polymer matrix and the plasticizers were investigated using Fourier transform infrared spectroscopy. The morphological characteristics of the films were characterized by scanning electron microscopy. Thermal properties, tensile strength, elongation at break, hydrophilic, and barrier properties of the obtained films were also determined. To confirm the obtaining of active films through the use of chestnut extract and to study the effect of the proposed plasticizers on the antibacterial activity of the extract, the obtained films were tested against bacteria cultures. The final results showed that all of the obtained films exhibit a hydrophilic character and high barrier effect to oxygen, carbon dioxide and water vapor. In addition, sodium alginate films prepared with chestnut extract and the plasticizer proposed by us, showed better mechanical and antimicrobial properties than the films obtained with chestnut extract and the commercially available plasticizers.

Applicability of Composite Magnetic Membranes in Separation Processes of Gaseous and Liquid Mixtures-A Review.

Recent years have shown a growing interest in the application of membranes exhibiting magnetic properties in various separation processes. The aim of this review is to provide an in-depth overview of magnetic membranes that can be successfully applied for gas separation, pervaporation, ultrafiltration, nanofiltration, adsorption, electrodialysis, and reverse osmosis. Based on the comparison of the efficiency of these separation processes using magnetic and non-magnetic membranes, it has been shown that magnetic particles used as fillers in polymer composite membranes can significantly improve the efficiency of separation of both gaseous and liquid mixtures. This observed separation enhancement is due to the variation of magnetic susceptibility of different molecules and distinct interactions with dispersed magnetic fillers. For gas separation, the most effective magnetic membrane consists of polyimide filled with MQFP-B particles, for which the separation factor (αrat O2/N2) increased by 211% when compared to the non-magnetic membrane. The same MQFP powder used as a filler in alginate membranes significantly improves water/ethanol separation via pervaporation, reaching a separation factor of 12,271.0. For other separation methods, poly(ethersulfone) nanofiltration membranes filled with ZnFe2O4@SiO2 demonstrated a more than four times increase in water flux when compared to the non-magnetic membranes for water desalination. The information gathered in this article can be used to further improve the separation efficiency of individual processes and to expand the application of magnetic membranes to other branches of industry. Furthermore, this review also highlights the need for further development and theoretical explanation of the role of magnetic forces in separation processes, as well as the potential for extending the concept of magnetic channels to other separation methods, such as pervaporation and ultrafiltration. This article provides valuable insights into the application of magnetic membranes and lays the groundwork for future research and development in this area.

Chitosan-based films with alternative eco-friendly plasticizers: Preparation, physicochemical properties and stability.

Chitosan-based films modified with synthesized (propylene glycol monoacetate, propylene glycol esters of fatty acids, and epoxidized propylene glycol esters) and commercial eco-friendly plasticizers (epoxidized soybean oil and epoxidized palm oil) were prepared by a casting technique, with the aim to obtain environmentally friendly materials for packaging applications. To assess the applicability of alternative plasticizers, their properties were compared to the two most common plasticizers, i.e. glycerol and sorbitol. The chemical structure of newly synthesized plasticizers was verified by gas chromatography with mass detector, infrared spectroscopy and 1H NMR; and their acid, epoxy, iodine, and saponification values were determined. Plasticized chitosan-based films were characterized in terms of hydrophilic, barrier, thermal, mechanical properties, zeta potential and morphology, confirming their flexibility and homogeneity. The research confirmed that the alternative plasticizers introduced by us are more effective than commercially available ones, exhibiting lower hydrophilicity and superior mechanical properties compared to samples plasticized with traditional plasticizers. Moreover, these properties were found to be even better after ageing for 10 months.

Neat Chitosan Porous Materials: A Review of Preparation, Structure Characterization and Application.

This review presents an overview of methods for preparing chitosan-derived porous materials and discusses their potential applications. This family of materials has garnered significant attention owing to their biocompatibility, nontoxicity, antibacterial properties, and biodegradability, which make them advantageous in a wide range of applications. Although individual porous chitosan-based materials have been widely discussed in the literature, a summary of all available methods for preparing materials based on pure chitosan, along with their structural characterization and potential applications, has not yet been presented. This review discusses five strategies for fabricating porous chitosan materials, i.e., cryogelation, freeze-drying, sol-gel, phase inversion, and extraction of a porogen agent. Each approach is described in detail with examples related to the preparation of chitosan materials. The influence of the fabrication method on the structure of the obtained material is also highlighted herein. Finally, we discuss the potential applications of the considered materials.

Numerical Study of Drift Influence on Diffusion Transport through the Hybrid Membrane.

Sodium alginate membranes filled with iron oxide nanoparticles consist of a mixture of organic and inorganic phases. This design offers the possibility to combine the polymer's easy processability and superior separation performance. For a better understanding of the mechanisms of mixture separation, we analyze the diffusion motion of a particle in the hybrid membrane environment. We model structures of two-dimensional heterogenic membranes, which resemble real membrane structures, and then we simulate a random walk on them. We investigate how the additional action of drift changes the motion properties of the diffusing particles through the polymeric membrane filled with inorganic powder. We test the effect of two parameters: the distribution of obstacles (filling) in the membrane and the value of drift on the nature of diffusion. It appears that the synergy between drift, the diffusion, and the membrane structure affect the occurrence of the superdiffusive and subdiffusive character of particle motion as measured by the time-averaged mean square displacement. An important point is the observation that the strong drift supports subdiffusive motion as it increases the chances of particle trapping. Moreover, there exists the optimal value of drift, for which the transport through a membrane speeds up and does not cause trapping.

Antibacterial and Biodegradable Polysaccharide-Based Films for Food Packaging Applications: Comparative Study.

One of the major objectives of food industry is to develop low-cost biodegradable food packaging films with optimal physicochemical properties, allowing for their large-scale production and providing a variety of applications. To meet the expectations of food industry, we have fabricated a series of solution-cast films based on common biodegradable polysaccharides (starch, chitosan and alginate) to be used in food packaging applications. Selected biopolymers were modified by the addition of glycerol and oxidized sucrose (starch), glycerol (chitosan), and glycerol and calcium chloride (alginate), as well as being used to form blends (starch/chitosan and starch/alginate, respectively). A chestnut extract was used to provide antibacterial properties to the preformed materials. The results of our studies showed that each modification reduced the hydrophilic nature of the polymers, making them more suitable for food packaging applications. In addition, all films exhibited much higher barrier properties to oxygen and carbon dioxide than commercially available films, such as polylactic acid, as well as exhibiting antimicrobial properties against model Gram-negative and Gram-positive bacteria (Escherichia coli and Staphylococcus epidermidis, respectively), as well as yeast (Candida albicans).

Mixed Manganese Dioxide on Magnetite Core MnO2@Fe3O4 as a Filler in a High-Performance Magnetic Alginate Membrane.

The process of ethanol dehydration via pervaporation was performed using alginate membranes filled with manganese dioxide and a mixed filler consisting of manganese dioxide on magnetite core MnO2@Fe3O4 particles. The crystallization of manganese dioxide on magnetite nanoparticle surface resulted in a better dispersibility of this mixed filler in polymer matrix, with the preservation of the magnetic properties of magnetite. The prepared membranes were characterized by contact angle, degree of swelling and SEM microscopy measurements and correlated with their effectiveness in the pervaporative dehydration of ethanol. The results show a strong relation between filler properties and separation efficiency. The membranes filled with the mixed filler outperformed the membranes containing only neat oxide, exhibiting both higher flux and separation factor. The performance changed depending on filler content; thus, the presence of optimum filler loading was observed for the studied membranes. The best results were obtained for the alginate membrane filled with 7 wt.% of mixed filler MnO2@Fe3O4 particles. For this membrane, the separation factor and flux equalled to 483 and 1.22 kg·m-2·h-1, respectively.

Boron Removal by Sorption on Modified Chitosan Hydrogel Beads.

An excess concentration of boron in irrigation and drinking water can negatively affect the yield of plants and the human nervous system, respectively. To meet the recommended levels, hybrid biosorbent hydrogel beads based on chitosan and manganese (II-IV) were employed for the removal of boron from aqueous media. The results showed that the biosorbent effectively removed boric acid from the aqueous medium at neutral pH over a sorption time of 2 h and the liquid/hydrogel ratio of 20 mL/g, achieving a maximum sorption capacity near 190 mg/g. The modeling of the sorption equilibrium data indicated that the Freundlich isotherm equation gave the best fit out of the isotherm models examined. A pseudo-second-order model was found to best describe the sorption kinetics. The favorable attachment of manganese to the chitosan structure enabled the sorption of boron and was confirmed by FTIR, RS, XRD, SEM and ICP-OES methods. Boron desorption from the spent biosorbent was successfully achieved in three cycles using a NaOH solution. In general, the results of this research indicate that this method is one of the possibilities for improving water quality and may contribute to reducing pollution of the aquatic environment.

Environmentally Friendly Melt-Processed Chitosan/Starch Composites Modified with PVA and Lignin.

Chitosan/starch-based composites were prepared by thermomechanical processing as an alternative to the traditional solution method, with the aim of fabricating environmentally friendly materials on a larger scale. Different contents and types of lignin and poly(vinyl alcohol), PVA were incorporated into chitosan/starch compositions to improve their mechanical properties. It was demonstrated that the presence of both lignin and PVA increases the values of tensile strength and elongation at break of the composites. Moreover, it was observed that by the selection of a type of lignin and PVA, it was possible to tailor the internal microstructure of the samples. As observed in scanning electron microscope (SEM) micrographs, the introduction of lignin and PVA resulted in the formation of a smooth surface and homogeneous samples.

Collation Efficiency of Poly(Vinyl Alcohol) and Alginate Membranes with Iron-Based Magnetic Organic/Inorganic Fillers in Pervaporative Dehydration of Ethanol.

Hybrid poly(vinyl alcohol) and alginate membranes were investigated in the process of ethanol dehydration by pervaporation. As a filler, three types of particles containing iron element, i.e., hematite, magnetite, and iron(III) acetyloacetonate were used. The parameters describing transport properties and effectiveness of investigated membranes were evaluated. Additionally, the physico-chemical properties of the resulting membranes were studied. The influence of polymer matrix, choice of iron particles and their content in terms of effectiveness of membranes in the process of ethanol dehydration were considered. The results showed that hybrid alginate membranes were characterized by a better separation factor, while poly(vinyl alcohol) membranes by a better flux. The best parameters were obtained for membranes filled with 7 wt% of iron(III) acetyloacetonate. The separation factor and pervaporative separation index were equal to 19.69 and 15,998 g⋅m-2⋅h-1 for alginate membrane and 11.75 and 14,878 g⋅m-2⋅h-1 for poly(vinyl alcohol) membrane, respectively.

Characterization of the Structure and Transport Properties of Alginate/Chitosan Microparticle Membranes Utilized in the Pervaporative Dehydration of Ethanol.

The structure and transport properties of alginate/chitosan microparticle membranes used in ethanol dehydration processes were investigated. The membranes were characterized based on images obtained from high-resolution microscopy. The following parameters were determined: the observed total amount of void space, the average size of the void domains, their length and diameter, the fractal dimension, and the generalized stochastic fractal parameters. The total amount of void space was determined to be between 54% and 64%. The average size of the void domains is smaller for alginate membranes containing neat (CS) and phosphorylated (CS-P) chitosan particles when compared to those membranes filled with glycidol-modified (CS-G) and glutaraldehyde crosslinked (CS-GA) chitosan particles. Furthermore, the transport of ethanol and water particles through the studied membranes was modelled using a random walk framework. It was observed that the results from the theoretical and experimental studies are directly correlated. The smallest values of water to ethanol diffusion coefficient ratios (i.e., 14) were obtained for Alg (sodium alginate) membranes loaded with the CS and CS-P particles, respectively. Significantly larger values (27 and 19) were noted for membranes filled with CS-G and CS-GA particles, respectively. The simulation results show that the size of channels which develop in the alginate matrix is less suited for ethanol molecules compared to water molecules because of their larger size. Such a situation facilitates the separation of water from ethanol. The comparison of the structural analysis of the membranes and random walk simulations allows one to understand the factors that influence the transport phenomena, in the studied membranes, and comment on the effect of the length, diameter, number of channels, and variations in the pore diameters on these transport parameters.

A Simple Methodology to Estimate the Diffusion Coefficient in Pervaporation-Based Purification Experiments.

A procedure to estimate the diffusion coefficient in solution⁻diffusion models of hydrophilic membranes used in pervaporation-based purification experiments is presented. The model is based on a series solution of the general permeation problem. It considers a membrane that can be filled with water or with the feed solution before the measurement. Furthermore, the length of the tubing between the permeation cell and the place of cold traps is also addressed. To illustrate the parameter estimation procedure, we have chosen the data for the separation of water and ethanol by chitosan membranes. It is shown that the diffusion coefficient can be estimated effectively from the time course of the transported mass and by the analysis of certain well defined time lags of the permeation curve.

The Use of Lanthanum Ions and Chitosan for Boron Elimination from Aqueous Solutions.

Boron is an essential element for plants and living organisms; however, it can be harmful if its concentration in the environment is too high. In this paper, lanthanum(III) ions were introduced to the structure of chitosan via an encapsulation technique and the obtained hydrogel (La-CTS) was used for the elimination of the excess of B(III) from modelling solutions. The reaction between boric acid and hydroxyl groups bound to the lanthanum coordinated by chitosan active centres was the preponderant mechanism of the bio-adsorption removal process. The results demonstrated that La-CTS removed boric acid from the aqueous solution more efficiently than either lanthanum hydroxide or native chitosan hydrogel, respectively. When the initial boron concentration was 100 mg/dm3, the maximum adsorption capacity of 11.1 ± 0.3 mg/g was achieved at pH 5 and the adsorption time of 24 h. The successful introduction of La(III) ions to the chitosan backbone was confirmed by Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy, Fourier-Transform Infrared Spectroscopy, X-Ray Diffraction, X-ray Photoelectron Spectroscopy, and Inductively Coupled Plasma Optical Emission Spectroscopy. Due to its high-performance boron adsorption-desorption cycle and convenient form, La-CTS seems to be a promising bio-adsorbent for water treatment.

Chitosan Hydrogel Beads Supported with Ceria for Boron Removal.

In this study, a chitosan hydrogel supported with ceria (labelled Ce-CTS) was prepared by an encapsulation technique and used for the efficient removal of excess B(III) from aqueous solutions. The functionalisation of chitosan with Ce(IV) and the improvement in the adsorptive behaviour of the hydrogel were determined by SEM-EDS, FTIR, XRD, and inductively coupled plasma optical emission spectrometer (ICP-OES) analyses and discussed. The results demonstrate that Ce-CTS removes boric acid from aqueous solutions more efficiently than either cerium dioxide hydrate or raw chitosan beads, the precursors of the Ce-CTS biosorbent. The maximum adsorption capacity of 13.5 ± 0.9 mg/g was achieved at pH 7 after 24 h. The equilibrium data of boron adsorption on Ce-CTS fitted the Freundlich isotherm model, while the kinetic data followed the Elovich pseudo-second-order model, which indicated that the process was non-homogeneous. The dominant mechanism of removal was the reaction between boric acid molecules and hydroxyl groups bound to the ceria chelated by chitosan active centres. Due to its high efficiency in removing boron, good regeneration capacity and convenient form, Ce-CTS may be considered a promising biosorbent in water purification.

The influence of filler type on the separation properties of mixed-matrix membranes.

Chitosan-based membranes filled with different metal oxide particles were prepared and their performance in ethanol dehydration process depending on the type of oxide and loading was discussed. For membrane preparation three oxides: TiO2, Cr2O3 or Fe3O4 were selected. From experimental data suitable ethanol and water transport coefficients were evaluated. As shown in the results, applied fillers in different ways affect the separation properties. Presence of TiO2 significantly affects the normalized total flux, increasing its value. On the other hand, addition of Fe3O4 influences most of all the separation factor, which is the among all investigated membranes. For membranes containing chromium(III) oxide as a filler, improvement in the separation properties is observed only in the case when the Cr2O3 content equals to 5 wt%. Above this concentration significant deterioration of separation properties is observed. The best performance has mixed-matrix membranes (MMMs) with magnetite, where the values of PSI are equal to 16.3 and 296.8 kg/m-2 h µm for pristine and 15 wt% filler content, respectively.

New type of alginate/chitosan microparticle membranes for highly efficient pervaporative dehydration of ethanol.

A new type of composite alginate membranes filled with chitosan (CS) and three different modified chitosan submicron particles, i.e. phosphorylated (CS-P), glycidol (CS-G) or glutaraldehyde (CS-GA) crosslinked ones, were prepared, and the pervaporation of water/ethanol mixture was investigated. The influence of various chitosan particles and their content on the transport properties of membranes was discussed. It was found that the addition of chitosan particles into the alginate matrix has a prominent effect on the ethanol/water separation efficiency. All tested membranes are characterized simultaneously by a high flux and selectivity, exhibiting advantageous properties, and outperforming numerous conventional materials. The best results were achieved for alginate membranes filled with phosphorylated chitosan particles at 10 wt%, for which separation factor, flux and PSI were equal to 136.2, 1.90 kg m-2 h-1 and 256.9 kg m-2 h-1, respectively.

Structure-diffusion relationship of polymer membranes with different texture.

Two-dimensional diffusion in heterogenic composite membranes, i.e., materials comprising polymer with dispersed inorganic fillers, composed of ethylcellulose and magnetic powder is studied. In the experimental part, the morphology of membranes is described by the following characteristics: the amount of polymer matrix, the fractal dimension of polymer matrix, the average size of polymer matrix domains, the average number of obstacles in the proximity of each polymer matrix pixel. The simulation work concentrates on the motion of a particle in the membrane environment. The focus is set on the relationship between membranes morphology characterized by polymer matrix density, its fractal dimension, the average size of domains, and the average number of near obstacles and the characteristics of diffusive transport in them. The comparison of diffusion driven by Gaussian random walk and Lévy flights shows that the effective diffusion exponent at long time limits is subdiffusive and it does not depend on the details of the underlying random process causing diffusion. The analysis of the parameters describing the membrane structure shows that the most important factor for the diffusion character is the average size of a domain penetrated by diffusing particles. The presented results may be used in the design and preparation of membrane structures with specific diffusion properties.