Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films

Poly(lactic acid) (PLA) is a biodegradable polymer that exhibits high elastic modulus, high mechanical strength, and feasible processability. However, high cost and fragility hinder the application of PLA in food packaging. Therefore, this study aimed to develop flexible PLA/acetate and PLA/chitosan films with improved thermal and mechanical properties without the addition of a plasticizer and additive to yield extruder compositions with melt temperatures above those of acetate and chitosan. PLA blends with 10, 20, and 30 wt% of chitosan or cellulose acetate were processed in a twin-screw extruder, and grain pellets were then pressed to form films. PLA/acetate films showed an increase of 30 °C in initial degradation temperature and an increase of 3.9 % in elongation at break. On the other hand, PLA/chitosan films showed improvements in mechanical properties as an increase of 4.7 % in elongation at break. PLA/chitosan film which presented the greatest increase in elongation at break proved to be the best candidate for application in packaging.     

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of T_g (glass transition temperature), T_m (melting point temperature), and T_max (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.     

Influence of the Concentrations of Chitosan and Glycerol on Edible Film Properties Showed by Response Surface Methodology

The individual and interactive effects of glycerol and chitosan concentrations on edible film properties were investigated using response surface methodology. The results of ANOVA indicated that all the independent variables exhibited significant effect on the film properties. Chitosan concentration had a positive effect on CO₂ permeability and negative effect on O₂ while the glycerol concentration had a positive effect on permeability to both gases. Regarding water vapor permeability, the chitosan concentration had a negative effect, whereas the glycerol had no influence. Moreover, both chitosan and glycerol concentration influenced the elongation at break point (%A), and only glycerol concentration had a significant effect on tensile strength. Optimization by desirability approach was carried out on the independent variables to get the optimum levels within the experimental conditions. It was found that 1.5 % of chitosan and 25 % of glycerol (wt/wt of chitosan) retarded respiration and showed a strong permeability to water vapor.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.     

Chitin and Chitosan Extracted from Shrimp Waste Using Fish Proteases Aided Process: Efficiency of Chitosan in the Treatment of Unhairing Effluents

Extraction and depolymerisation of chitin and chitosan from shrimp waste material was carried out using fish proteases aided process. A high deproteinization level (80 %) was recorded with an Enzyme/Substrate ratio of 10 U/mg. The demineralization of shrimp waste was completely achieved within 6 h at room temperature in HCl 1.25 M, and the residual content of calcium in chitin was below 0.01 %. The degree of N-acetylation, calculated from the ¹³C CP/MAS-NMR spectrum, was 85 %. The chitin obtained was converted to chitosan by N-deacetylation. X-ray diffraction patterns also indicated two characteristics crystalline peaks approximately at 10° and 20° (2θ). Chitosan was then evaluated in the treatment of unhairing effluents from the tanning industry. A result showed that chitosan as a coagulant has good performance in alkaline pH and at concentration of 0.5 g/L. Within these conditions, chitosan could decrease turbidity value, total suspended solids (89 % at 1.5 g/L), biological oxygen demand (33.3 % at 1.5 g/L) and chemical oxygen demand (58.7 % at 1.5 g/L).     

Thermal Stability and Degradation of Chitosan Modified by Acetophenone

N-(Methylphenylmethylidenyl) chitosan (MPMC) polymer was synthesized by chemical modification of chitosan. The chemical structure of the modified polymer was characterized by IR, ¹H NMR and elemental analysis. Thermogravimetric reveals that the thermal stability of chitosan polymer is greater than MPMC polymer. The activation energies of thermal degradation of chitosan and MPMC polymers determined using Arrhenius relationship. Thermal degradation of MPMC polymer was studied and the products of degradation were identified by GC–MS technique. It seems that the mechanism of degradation of MPMC polymer is characterized by elimination of low-molecular weight radicals. Combination or recombination of H^· or OH⁻ with these radicals and random scission mechanism along the backbone chain are the main source of the degradation products.     

Adsorption Kinetics of Dyes in Single and Binary Systems Using Cyanoguanidine-Crosslinked Chitosan of Different Deacetylation Degrees

The crosslinking of chitosan with cyanoguanidine shows some advantages, such as the improved the stability in acid solutions and the decrease of adsorbent cost. In this work, cyanoguanidine-crosslinked chitosan and pure chitosan were prepared to apply in the adsorption of Food Yellow 4 (FY4) and Food Blue 2 (FB2), in single and binary systems. Effects of pH and deacetylation degree (DD) of chitosan in adsorption were evaluated. The adsorbents were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The kinetic data were analyzed by pseudo-first order, pseudo-second order and Avrami models. The conditions of pH 3 and DD 95% were the more suitable to reach the highest adsorption capacities in all experimental assays. Under these conditions, the adsorption capacities for FY4 were approximately of 392 and 200 mg g^?1 and, for FB2 were approximately of 370 and 184 mg g^?1, respectively, in the single and binary systems. The Avrami model was suitable to represent the kinetic curves in all conditions, and the highest adsorption capacities were found for FY4 in binary aqueous system, being for the pure chitosan of 229 mg g^?1 and crosslinked chitosan of 218 mg g^?1. The Langmuir and extended Langmuir models presented a good fit to the equilibrium data in both systems. It was found that, the chitosan crosslinked with cyanoguanidine improved the chemical stability of chitosan as adsorbent.     

Alkali Treated 3D Chitosan Scaffolds with Enhanced Strength and Stability

Journal of Polymers and the Environment - 3D chitosan scaffolds treated with alkali showed enhanced mechanical properties and stability in aqueous conditions. Chitosan is a preferred polymer for...     

Preparation and Properties of Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) Blends Induced by Gamma Irradiation

Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) blends have been prepared by casting solution method. The effect of different irradiation doses (2.5, 5, 10, 15, and 20 kGy) of gamma rays on the physical properties of the CMC/SA blend containing different ratios of SA (20, 30, and 40 %) such as gel fraction (%) and swelling (%) of CMC/SA blends were investigated. It was found that the gel fraction increases with increasing irradiation dose up to 20 kGy while the swelling of CMC/SA blend films tends to increase with increasing SA content and reduced with increasing irradiation doses. Mechanical and thermal properties of the blend films were improved when CMC content increased and with increasing irradiation dose up to 20 kGy. Morphology of the blend was examined by SEM, which indicates compatibility between CMC and SA. The blend rich in SA content possessed good antimicrobial activity against Gram +ve Bacteria (Bacillus subtilis).     

Physical Characterization of Biodegradable Films Based on Chitosan,Polyvinyl Alcohol and <Emphasis Type="Italic">Opuntia</Emphasis> Mucilage

This study aimed to develop and characterize biodegradable films containing mucilage, chitosan and polyvinyl alcohol (PVA) in different concentrations. The films were prepared by casting on glass plates using glycerol as plasticizer. Mechanical properties, water vapor and oxygen barrier, as well as the interaction with water, were measured. The compatibility of the film-forming components and the uniformity of the films were determined by zeta potential and SEM, respectively. The glycerol and mucilage allowed obtaining more hydrophilic films. The barrier properties of the films made from 100 % chitosan were similar to composed films containing PVA up to 40 %. The results of this study suggest that the interaction between chitosan and mucilage could increase water vapor permeability. The films prepared from either 100 % chitosan or PVA showed a more hydrophobic behavior as compared to the composed films. The films were homogenous since no boundary or separation of components was observed, indicating a good compatibility of the components in the films.     

Ultrastructural, Morphological, and Antifungal Properties of Micro and Nanoparticles of Chitosan Crosslinked with Sodium Tripolyphosphate

Recent studies have demonstrated the antibacterial effect of micro and nanoparticles of chitosan (CS) crosslinked with sodium tripolyphosphate (TPP), and incorporating metallic ions, bringing that the size, shape, and zeta potential are related to the antimicrobial potential. However, there are few studies on the antifungal activity and the effect of TPP on the antimicrobial potential. Micro and nanoparticles were prepared from CS by ionotropic gelation with TPP, and structurally characterized by transmission and scanning electron spectroscopy, and Fourier transformed infrared spectroscopy. Depending on the concentration of CS and TPP, spherical particles were obtained from 80 nm to 20 μm. Subsequently, particles were evaluated for their antifungal potential against Aspergillus parasiticus assessing radial growth, spore germination, and morphological changes. An increase in the antifungal potential compared with CS in solution was observed, inhibiting the development of the fungus causing clear morphological changes in both, hyphae and spores. Particle size and the availability of functional groups of CS/TPP (amino group and phosphate), suggest a possible synergistic effect between CS and TPP.     

Eco-Synthesis of PVA/Chitosan Hydrogels for Biomedical Application

A drug delivery system based on physically cross-linked poly vinyl alcohol (PVA)/chitosan blend hydrogels for the release of sparfloxacin antibiotic as a model for drugs was described. Eco-synthesis in current work is based on synthesizing a hydrogel without using chemical crosslinking agents like in the conventional method. In addition all materials are used are non- toxic, safe, non-carcinogenic and can be accepted by the human body without danger. The swelling behavior was tested to be dependent on pH as temperature as well as time and number of freezing thawing cycles. The physical properties of the hydrogels, such as swelling percent, dissolution percent, gel fraction and mechanical properties was assessed. The antimicrobial activity of hydrogels having different compositions was evaluated for both gram positive and gram negative bacteria. Furthermore, the release of antibiotic from hydrogels prepared using the freeze—thawed process was studied. Results obtained disclose that the swelling percent of the hydrogels is pH- dependent and increases by increasing the chitosan percent and decreases with increasing the time and number of freezing cycle. With respect to the antimicrobial activity of the prepared hydrogels, display a positive effect for both gram positive and gram negative bacteria. Freeze-thawed hydrogels could serve as drug delivery system to release sparfloxacin in acidic medium. Indeed, the release percent of sparfloxacin relies on both pH and temperature.     

Effect of Nano-SiO<Subscript>2</Subscript> and Bark Flour Content on the Physical and Mechanical Properties of Wood–Plastic Composites

The aim of this study is to evaluate the impact of nano-SiO₂ and bark flour (BF) on the natural fiber–plastic composites engineering properties made from high density polyethylene (HDPE) and beech wood flour (WF). For this purpose, WF and BF in 60 mesh size and weight ratio of (50, 0 %), (30, 20 %), (10, 40 %) and (0, 50 %) respectively were mixed with HDPE. In order to increase the interfacial adhesion between the filler and the matrix, the maleic anhydride grafted polyethylene was constantly used at 3 wt% for all formulations as a coupling agent. The nano-SiO₂ particles with weight ratio of 0, 1, 2, and 4 % were also utilized to enhance the composites properties. The materials were mixed in an internal mixer (HAAKE) and then the bark and/or wood–plastic composite samples were made utilizing an injection molding machine. The physical tests including water absorption and thickness swelling, and mechanical tests including bending characteristics and un-notched impact strength were carried out on the samples based on ASTM standard. The results indicated that as the BF content increased in the composite, mechanical and physical properties were reduced, but the given properties were increased with the addition of nano-SiO₂. The addition of nano-SiO₂ had a negative impact on the physical properties, but when it was up to 2 %, it increased the impact strength.     

Enhancement of Sedimentation Velocity of Heavy Metals Loaded Hydroxyapatite Using Chitosan Extracted from Shrimp Waste

In this study, synthesize hydroxyapatite (HA) suspensions sedimentation was used after usual terms as support for adsorption of heavy metals ions. Thus, the effectiveness of chitosan, produced from shrimp waste, in the flocculation of turbid suspensions resulting from the treatment of water contaminated with heavy metals was studied by adsorption on HA. Different particles sizes of HA were mainly controlled in this work (an average of granule size ranging from 1.6 to 63 μm). The results of Cu²⁺ and Zn²⁺ adsorption on HA showed relatively fast kinetics, with removal extent of 88–95 % by varying the initial total metal concentration. High removal rates were obtained for Cu²⁺. Chitosan was found to be able to eliminate by flocculation more than 98 % of turbid suspensions generated by metals adsorption on HA after only 30 min of sedimentation. Effects of pH and dose of chitosan on the coagulation–flocculation process were also studied. The optimal dose of chitosan was found between 0.2 and 2 mg/L which corresponds to an optimal pH ranging from 6 to 7.     

Preparation and Properties of a Chitosan–Hyaluronic Acid-Polypyrrole Conductive Hydrogel Catalyzed by Laccase

Electro conductive hydrogels, consisting of chitosan (CS), hyaluronic acid (HA), and polypyrrole (PPy), were prepared via an in situ enzymic polymerization of pyrrole in the CS–HA hydrogel, using laccase as the catalyst. This CS–HA–PPy composite hydrogel showed good conductivity. The chemical structure and morphology of this conductive hydrogel were studied by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction technique. For CS–HA–PPy and CH–HA hydrogel, the temperature at which fastest decomposition occurred was 260 and 244 °C, respectively. That means the thermal stability of CS–HA–PPy is better than CS–HA hydrogel. The conductive hydrogel also showed excellent swelling and deswelling behaviors.     

Removal of Oil from Water by Calcium Alginate Hydrogel Modified with Maleic Anhydride

Calcium alginate hydrogel was prepared and used as a biosorbent for the removal of oil from aqueous solutions. Calcium alginate hydrogel was further chemically modified by esterification with maleic anhydride. The changes in the physicochemical properties of maleic anhydride modified calcium alginate were investigated via multiple techniques (FTIR, SEM, BET and DSC/TGA). Adsorption batch experiments were carried out to compare the oil adsorption capacities of native and modified calcium alginates. Adsorption experiments were carried out as a function of solution pH, temperature and ionic strength to determine the optimal conditions for the adsorption of oil. Equilibrium and kinetic studies were conducted for the modified alginate. Results revealed that the maleic anhydride modification of calcium alginate improved its adsorption capacity towards oil. Higher adsorption capacities of modified alginate were attained at lower temperatures (20 °C), higher ionic strengths (1.0 M NaCl) and within the pH range of 5–9. The oil adsorption data obtained for modified alginate could be better described by the first order kinetic model (R²?=?0.981) and the BET equilibrium isotherm (R²?=?0.984). The maximum monolayer adsorption capacity predicted by the BET model for the modified calcium alginate was found to be 143.0 mg/g.     

Performance of Cow Dung Reinforced Biodegradable Poly(Lactic Acid) Biocomposites for Structural Applications

In this work, performance of cow dung (CD) reinforced poly(lactic acid) (PLA) biocomposites was investigated for the potential use in load bearing application. CD of average 4 mm size was blended with PLA at different CD ratios (0–50 wt%) and their effects on the biocomposite properties were studied. The results showed an improvement in the flexural properties, while the tensile and impact strength dropped by 20 and 28% with the addition of 50% CD. The decline in the tensile and impact strength was due to micro-cracking and voids formation at higher CD content. Also, the incorporation of CD slightly decreased the thermal stability of the biocomposite. However, dynamic mechanical properties of the biocomposites generally improved. SEM analysis of tensile and impact fractured surfaces indicated that the CD had a reasonable adhesion with matrix. Moreover, the SEM micrographs of soil burial studies showed an accelerated degradation of higher CD wt% biocomposites.