CMC-based Films Research Articles

Preparation and investigation of the structural and mechanical properties of biodegradable gelatin- based films

Biodegradable gelatin-based films have been obtained in the presence of carboxymethylcellulose (CMC) additives intended for use as packaging of food products and drug carriers. By methods of scanning electron microscopy and measurement of film roughness, it was found that films obtained from a mixture of CMC and gelatin have the greatest roughness. It is shown that the introduction of CMC into the composition of gelatin films leads to a sharp decrease in the strength and modulus of elasticity of the films, however, the deformation has maximum values at a mass ratio of CMC / gelatin equal to 0.7. This is explained by the formation of associates due to H-bonds and electrostatic interactions between functional groups of gelatin proteins and polysaccharide macromolecules, stabilized by hydrophobic interactions between their nonpolar sites. The barrier properties of films based on CMC and gelatin have been studied. It is shown that CMC-based films have the highest air permeability and the lowest water resistance, which is due to the texture of the film material. Based on IR spectroscopy data, it was found that films obtained from a mixture of CMC and gelatin are the most stable. Glycerin was used to regulate the deformation of the films.

Effects of Chitosan and Cellulose Derivatives on Sodium Carboxymethyl Cellulose-Based Films: A Study of Rheological Properties of Film-Forming Solutions.

Bio-based packaging materials and efficient drug delivery systems have garnered attention in recent years. Among the soluble cellulose derivatives, carboxymethyl cellulose (CMC) stands out as a promising candidate due to its biocompatibility, biodegradability, and wide resources. However, CMC-based films have limited mechanical properties, which hinders their widespread application. This paper aims to address this issue by exploring the molecular interactions between CMC and various additives with different molecular structures, using the rheological method. The additives include O-carboxymethylated chitosan (O-CMCh), N-2-hydroxypropyl-3-trimethylammonium-O-carboxymethyl chitosan (HTCMCh), hydroxypropyltrimethyl ammonium chloride chitosan (HACC), cellulose nanocrystals (CNC), and cellulose nanofibers (CNF). By investigating the rheological properties of film-forming solutions, we aimed to elucidate the influencing mechanisms of the additives on CMC-based films at the molecular level. Various factors affecting rheological properties, such as molecular structure, additive concentration, and temperature, were examined. The results revealed that the interactions between CMC and the additives were dependent on the charge of the additives. Electrostatic interactions were observed for HACC and HTCMCh, while O-CMCh, CNC, and CNF primarily interacted through hydrogen bonds. Based on these rheological properties, several systems were selected to prepare the films, which exhibited excellent transparency, wettability, mechanical properties, biodegradability, and absence of cytotoxicity. The desirable characteristics of these selected films demonstrated the strong biocompatibility between CMC and chitosan and cellulose derivatives. This study offers insights into the preparation of CMC-based food packaging materials with specific properties.

Controlled release of water-soluble astaxanthin from carboxymethyl cellulose/gelatin and octenyl succinic anhydride starch/gelatin blend films

The effect of increasing concentrations (0, 0.25, 0.5, 1%) of commercial water-soluble AstaSana astaxanthin (AST) on the physicochemical properties, release kinetics and antioxidant activity of binary 75/25 carboxymethyl cellulose/gelatin (CMC75/GEL25) and octenyl succinic anhydride starch/gelatin (OSA75/GEL25) blend films was investigated. The microscopic observations showed that the obtained blends were phase-separated systems. Regardless of the AST concentration, the CMC-based films were more opaque, stronger, and less stretchable than the OSA-based films. The AST-supplemented films exhibited an intensive red color. The starch granules (from the AST formulation) contributed to high roughness and opacity of the films. The presence of AST contributed to a significant decrease of the puncture strength and oxygen permeability of the CMC-based film. The AST-supplemented films did not differ in terms of the water vapour barrier properties. Due to the low quantity of astaxanthin in the systems, the Fourier-transform infrared spectra of the control and AST-supplemented films were similar. The increase in the AST concentration was accompanied by reduced solubility and increased swelling of the OSA-based films, while an opposite result was observed for the CMC-based films. According to the Korsmeyer-Peppas with time lag model, the AST release kinetics exhibited quasi-Fickian behaviour. Due to their weaker solubility, the OSA75/GEL25 films offered at least 7 times slower release of AST than the CMC-based carrier. The times required for 25% AST release from the CMC75/GEL25 and OSA75/GEL25 films were 1.20–1.74 and 12.60–20.04 min, respectively. A high positive correlation (R2 = 0.78–0.91) was found between the AST release and antiradical activity of the films.

CMC-based functional film incorporated with copper-doped TiO2 to prevent banana browning

Titanium dioxide (TiO2) and Cu-doped TiO2 (Cu–TiO2) were synthesized using a sol-gel method and used as nanofillers to prepare CMC-based functional packaging films. The Cu–TiO2 was spherical particles with a size range of 66.1 ± 9.0 nm TiO2 and Cu–TiO2 nanoparticles had good compatibility with CMC and were evenly distributed in the CMC polymer matrix to form a composite film. The TiO2-added film did not show significant antibacterial activity, but the Cu–TiO2-added film exhibited high antibacterial activity against foodborne pathogenic bacteria (L. monocytogenes and E. coli) under visible light. When bananas were packaged with the CMC-based films, the CMC/Cu–TiO2 film effectively delayed the banana's browning. With strong antibacterial and ethylene scavenging capabilities under visible light, the CMC/Cu–TiO2 film has a high potential for active food packaging applications, especially in extending the shelf life of fruit.

Mathematical Modeling of Water-Soluble Astaxanthin Release from Binary Polysaccharide/Gelatin Blend Matrices

Water-soluble AstaSana astaxanthin (AST) was loaded into 75/25 blend films made of polysaccharides (carboxymethyl cellulose (CMC), gum Arabic (GAR), starch sodium octenyl succinate (OSA), water-soluble soy polysaccharides (WSSP)) and gelatin (GEL) at levels of 0.25, 0.5, and 1%, respectively. Due to the presence of starch granules in the AST formulation, the supplemented films exhibited increased surface roughness as compared to the AST-free films. Apart from the CMC/GEL carrier, the migration of AST to water (25 °C, 32 h) was incomplete. Excluding the CMC-based carrier, the gradual rise in the AST concentration decreased the release rate. The Hopfenberg with time lag model provided the best fit for all release series data. Based on the quarter-release times (t25%), the 0.25% AST-supplemented OSA/GEL film (t25% = 13.34 h) ensured a 1.9, 2.2, and 148.2 slower release compared to the GAR-, WSSP- and CMC-based carriers, respectively. According to the Korsmeyer–Peppas model, the CMC-based films offered a quasi-Fickian release of AST (n < 0.5) with the burst effect (t100% = 0.5–1 h). In general, the release of AST from the other films was multi-mechanistic (n > 0.5), i.e., controlled at least by Fickian diffusion and the polymer relaxation (erosion) mechanism. The 1% AST-added WSSP/GEL system provided the most linear release profile.

Carboxymethyl cellulose-based multifunctional film combined with zinc oxide nanoparticles and grape seed extract for the preservation of high-fat meat products

CMC-based functional films incorporated with grape seed extract (GSE, 5 wt% of CMC) and zinc oxide nanoparticles (ZnONPs, 1, 2, and 3 wt% of CMC) were fabricated via the solution casting method. The addition of GSE provided an excellent antioxidant activity to the CMC-based films, exhibiting nearly 95% and 25% scavenging activity against ABTS and DPPH oxidative free radicals. It also gave the film 100% UV protection. On the other hand, the addition of ZnONPs increased the mechanical and water vapor barrier properties with potent antibacterial activity against foodborne pathogens, E. coli, and L. monocytogenes. High-fat beef was packaged in the CMC-based film and stored refrigerated for 15 days to investigate quality changes. The number of psychrotrophic bacteria in the meat wrapped with CMC/ZnO3%/GSE film was 5.9 Log CFU/g, within the acceptable range. In addition, the film virtually prevented lipid oxidation in the meat when refrigerated, reducing it by 88%. Therefore, the CMC/ZnO3%/GSE film can be used as a sustainable material in active packaging applications of high-fat meat products such as beef.

Active Carboxymethylcellulose-Based Edible Films: Influence of Free and Encapsulated Curcumin on Films' Properties.

Carboxymethylcellulose (CMC)-based films can act as a protective barrier in food surfaces and a carrier of bioactive compounds, such as curcumin. However, incorporating curcumin in hydrophilic matrixes can be a challenge, and new strategies need to be explored. In this work, CMC-based films containing free curcumin and curcumin-loaded nanohydrogels (composed of lactoferrin and glycomacropeptide) were produced and characterized. The incorporation of curcumin-loaded nanohydrogels showed a significant decrease in films’ thickness (from 0.0791 to 0.029 mm). Furthermore, the water vapor permeability of CMC-based films was significantly decreased (62%) by incorporating curcumin-loaded nanohydrogels in the films. The water affinity’s properties (moisture, solubility, and contact angle) of films were also affected by incorporating encapsulated curcumin. The addition of nanohydrogels to CMC-based films reduced the tensile strength values from 16.46 to 9.87 MPa. Chemical interactions were analyzed using Fourier transform infrared spectroscopy. The release profile of curcumin from CMC-based films was evaluated at 25 °C using a hydrophilic food simulant and suggests that the release mechanism of the curcumin happens by Fick’s diffusion and Case II transport. Results showed that protein-based nanohydrogels can be a good strategy for incorporating curcumin in edible films, highlighting their potential for use in food applications.

Production of oral films based on pre-gelatinized starch, CMC and HPMC for delivery of bioactive compounds extract from acerola industrial waste

The residue from the processing of acerola, due to the concentration of active compounds, and antioxidant potential has aroused interest in its application. In this context, this study aimed to produce and characterization oral films based on carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC) and pre-gelatinized starch with the incorporation of ethanolic extract of dehydrated acerola industrial waste (EEDAIW) using tape-casting technique. The rheological properties of filmogenic solutions of CMC, HPMC, and starch were assessed. Oral films were characterized in relation to color parameters, mechanical properties, surface pH, contact angle, Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy, and stability in relation to total phenolic compounds. It was found that apparent viscosity decreased with the deformation rate and the expected behavior of pseudoplastic fluids, regardless of the polymer used. In general, the addition of EEDAIW in the films led to a reduction in the tensile strength of the films and an increase in the contact angle values; however, the surface pH of the films remained close to the oral pH (6.8). From the FTIR, it was found that even after the addition of EEDAIW, all films showed predominant absorption bands, characteristic of the polymer used. It was found that after 84 days, CMC-based films had a higher concentration of total phenolic compounds when compared to HPMC and starch oral films.

Hydrophilic Films Based on Carboxymethylated Derivatives of Starch and Cellulose.

The carboxymethylated derivatives of starch (CMS) and cellulose (CMC) were used for film preparation. The infrared spectroscopy revealed that crosslinking via ester bridges with citric acid occurred between the two polysaccharide derivatives. The effect of polysaccharide derivatives ratio on physicochemical properties of prepared films was evaluated. Generally, the values of tested parameters (moisture absorption, surface roughness, and mechanical and thermal properties) were between the values noted for neat CMS or CMC-based films. However, the physicochemical properties of the system with equal CMS/CMC weight ratio diverged from this trend, i.e., the highest tensile strength, the highest Young’s modulus (ca. 3.4 MPa and ca. 4.9 MPa, respectively), with simultaneously the lowest moisture absorption (18.5% after 72 h) have been noted. Such systems could potentially find application in agriculture or pharmacy.

Utilization of cinnamaldehyde and zinc oxide nanoparticles in a carboxymethylcellulose-based composite coating to improve the postharvest quality of cherry tomatoes

Carboxymethylcellulose (CMC)-based film packaging enriched with plant-sourced cinnamaldehyde (CIN) and zinc oxide nanoparticles (ZnONPs) of simple synthesis were prepared in this work. Then, the physico-mechanical and barrier properties and antifungal activities of CMC-based films, including pristine CMC, CIN/CMC, ZnONPs/CMC, ZnONPs/CIN/CMC were investigated. The results indicated that the ZnONPs incorporation produced a nanocomposite film with low transparency, good flexibility and high mechanical resistance. Furthermore, the water barrier capacity and antifungal performance of CMC-based films were significantly improved with the addition of CIN. CMC-based composite film incorporating with both CIN and ZnONPs, in turn, exhibited satisfactory mechanical characterizations, excellent barrier capacities against water and oxygen molecules and anti-Aspergillus niger activity. Moreover, ZnO/CIN/CMC nanocomposite film was significantly effective at inhibiting the weight loss and firmness of cherry tomatoes and in decreasing the total acidity content of these fruits after storage. Our results suggested that the ZnO/CIN/CMC nanocomposite film packaging can improve the cherry tomatoes quality by suppressing physiological the metabolic activities of the fruits during postharvest storage period.

Enhancement of a zwitterionic chitosan derivative on mechanical properties and antibacterial activity of carboxymethyl cellulose-based films

A type of zwitterionic chitosan derivative, N-2-hydroxylpropyl-3-trimethylammonium-O-carboxymethyl chitosan (HTCMCh), was synthesized and introduced into carboxymethyl cellulose (CMC)-based films as a film strength enhancer and antibacterial agent. The influencing factors include degree of substitution (DS) and mHTCMCh/mCMC. Their influences on mechanical properties, thermal stability, antibacterial activities, microstructures, transmittance, and wettability of the CMC-based films were studied. It was found that HTCMCh improves the tensile strength (by 9.0–130.9%), Young's modulus (47.8–351.6%), and elongation at break (90.8–280.8%) of CMC/HTCMCh films simultaneously, depending on the DS and mass content of HTCMCh. However, the HTCMCh shows little influence on microstructure and thermal stability of CMC/HTCMCh films. Satisfactorily, CMC/HTCMCh films show strong antibacterial activities against E. coli and S. aureus and are nontoxic to fibroblast HFF-1 cells. Pork packaging experiments demonstrated that CMC/HTCMCh10%,0,58 film could significantly inhibit bacterial growth, indicating that the HTCMCh-doped CMC films could be used as food packaging materials.

Development and characterization of carboxymethyl cellulose based probiotic nanocomposite film containing cellulose nanofiber and inulin for chicken fillet shelf life extension

Bioactive packaging is an alternative new technology for preserving the quality and safety of food products with providing health benefits. In this way, the Lactobacillus plantarum, cellulose nanofiber (CNF) and inulin incorporated carboxymethyl cellulose (CMC) based probiotic nanocomposite film was prepared. The fabricated film samples were characterized by FTIR, FE-SEM, XRD and DSC analyses, that the obtained results indicated the good compatibility between CMC, CNF, and inulin. As a result, the CMC-based probiotic films containing CNF and inulin exhibited satisfactory water barrier and mechanical properties. Additionally, the viability of probiotic bacteria in the CMC-based films was significantly (p < 0.05) increased (36%) by addition of inulin as a prebiotic ingredient during storage time. Probiotic film sample showed antibacterial activity against nine pathogens and also extended the chicken fillet shelf life when wrapped on the meat. In conclusion, the application of CNF and inulin incorporated CMC-based probiotic nanocomposite film as a bioactive food packaging system opens up a new horizon for improving the shelf life of food products and providing the health benefits for consumers.

Carboxymethyl cellulose-based films: Effect of organosolv lignin incorporation on physicochemical and antioxidant properties

Organosolv lignin was incorporated in carboxymethyl cellulose (CMC)-based films as a reinforcing and bioactive agent. Films were produced by the casting method using compatible and environmentally friendly solvents. The incorporation of lignin in CMC-based films was evaluated in term of morphology, physicochemical, barrier, mechanical and antioxidant properties. Solubility tests showed that lignin improved the water resistance of the films for approx. 60%. This behavior was also observed for the water vapor permeability, achieving a 20% reduction. Morphological characteristics suggested low compatibility between organosolv lignin and CMC matrix, revealed by the small aggregates homogeneously distributed in the film, through scanning electron microscopy, related to the self-assembly behavior of lignin. CMC/lignin-based films also presented higher thermal stability. Fourier transform infrared spectroscopy showed that incorporation of lignin led to small changes in the film's structure. Finally, organosolv lignin proved to be a promising material for the development of active CMC-based films due to its demonstrated antioxidant activity that can be useful to pack food products that suffer from undesirable oxidation reactions.

Production of bioactive films of carboxymethyl cellulose enriched with green coffee oil and its residues

Carboxymethyl cellulose (CMC)-based films were developed by incorporating green coffee oil (GCO) obtained by cold pressing and hydroalcoholic extracts of its residues. The effect of cake (CE) and sediment extracts (SE) in different proportions (20–40%) and GCO on chemical, morphological, physical, mechanical, optical, and antioxidant properties of the films was investigated. Eight fatty acids and four major phenolic compounds were identified by High-Resolution Direct-Infusion Mass Spectrometry in GCO and residue extracts. FTIR indicated interactions among CMC, phenolic compounds, and fatty acids. Films enriched with residue extracts presented heterogeneous microstructure. The tensile strength of the films decreased from 58 to 3 MPa with the extracts concentration, while elongation increased from 28 to 156% (p < 0.05). The water vapor permeability (averaging 3.94 × 10−8 g mm/cm2 h Pa) was not significantly affected by the extracts and GCO. The surface color was influenced by the type and concentration of extracts (p < 0.05), the film with SE40% had remarkable UV–vis barrier properties. The incorporation of GCO residue extracts imparted high antioxidant capacity to the CMC-based films, especially with CE40% (643.8 µmol Trolox eq./g dried film; 51.3 mg GAE/g dried film). General observations indicated the potential of these films, mainly the ones containing CE, like active packaging material for food applications.

Production and characterization of CMC-based antioxidant and antimicrobial films enriched with chickpea hull polysaccharides

In the present study, polysaccharides from chickpea hull (CHPS) were incorporated into carboxymethyl cellulose (CMC) for the development of CMC-based films. The physical and mechanical properties, color, transmittance, antioxidant and antimicrobial activities were investigated, and differential scanning calorimetry (DSC), Fourier transform-infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA) were applied to study the potential interaction, structure and thermal stabilization of the prepared films. The results revealed that some physical and mechanical properties of films, like moisture content, elongation at break and water vapor permeability, were decreased. While thickness, swelling ratio, water solubility and tensile strength were significantly increased (p < 0.05) compared with control film. Furthermore, the films exhibited potential antioxidant effects on DPPH and ABTS free radicals. The results of scanning electron microscopy showed rough and heterogeneous morphology for CMC-CHPS films while control film exhibited smooth, homogenous and compact structure. FT-IR results reflected good interaction of chemical groups and bonds between CMC and CHPS. DSC results showed that glass transition temperature increased significantly (p < 0.05) from 82.68 to 90.39 °C compared with control of 78.21 °C. Thermal stability of all films was improved, indicating that the films could be used as biocomposite materials for packaging of food products.

Effects of chitosan quaternary ammonium salt on the physicochemical properties of sodium carboxymethyl cellulose-based films

The effects of N-(2-hydroxyl)-propyl-3-trimethylammonium chitosan chloride (HTCC) on the physicochemical properties of sodium carboxymethyl cellulose (CMC)-based films were investigated. The prepared HTCC/CMC film-forming solutions (FFSs) with varying mass ratios exhibited shear-thinning behavior and typical pseudo-plasticity. The highest apparent viscosity and lowest crossover frequency was obtained for the HTCC/CMC FFS with a mass ratio of 10%, due to the formation of the strongest intermolecular interactions, which also led to the best mechanical properties. Furthermore, the effects of temperature and degree of substitution of HTCC on the composite film properties were also investigated. Structural property assessment by FTIR, SEM, and DSC showed a clear interaction between HTCC and CMC, leading to the formation of a new composite material with enhanced physicochemical properties. The data demonstrate the importance of HTCC in CMC-based films for food and drug packaging.

Functionalization of halloysite nanotubes for the preparation of carboxymethyl cellulose-based nanocomposite films

Halloysite nanotubes (Hal) were treated with acid to prepare uniformly charged acid treated Hal (Hal-A). After acid treatment, the surface charge (zeta potential) of Hal changed from +0.08mV to −32.65mV. Functionalized Hal-A were prepared through adsorbing metal ions by immersing the Hal-A into saturated solutions of three different metal salts, silver nitrate, zinc nitrate, and copper acetate. The number of metal ions attached to the Hal-A and their functionality were dependent on the type of metal ions. The functionalized Hal-A exhibited strong antimicrobial activity against food-borne pathogenic bacteria, L. monocytogenes and E. coli. The CMC-based film showed a significant increase in mechanical, water vapor barrier, and thermal stability properties after forming a composite with Hal. In particular, CMC-based films incorporated with the functionalized Hal-A showed strong antimicrobial activity against both L. monocytogenes and E. coli.

Production and physicochemical properties of carboxymethyl cellulose films enriched with spent coffee grounds polysaccharides

Extracts rich in polysaccharides were obtained by alkali pretreatment (PA) or autohydrolysis (PB) of spent coffee grounds, and incorporated into a carboxymethyl cellulose (CMC)-based film aiming at the development of bio-based films with new functionalities. Different concentrations of PA or PB (up to 0.20% w/v) were added to the CMC-based film and the physicochemical properties of the final films were determined. Scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, as well as determinations of optical and mechanical properties, moisture content, solubility in water, water vapor permeability, contact angle and sorption isotherms were performed. The addition of PA or PB resulted in important changes in the properties of the CMC-based film, mainly in color and opacity. The polysaccharides incorporation significantly improved the light barrier of the film and provided an enhancement or at least a preservation in the physicochemical properties.

Effects of PEG loading on electromechanical behavior of cellulose-based electroactive composite

Electroactive behavior of carboxymethylcellulose (CMC)-based actuators was investigated in this study. CMC-based films were firstly fabricated by using 1-butyl-3-methylimidazolium bromide. Characterization studies of the CMC films were conducted by using Fourier transform infrared, X-ray diffraction analysis, thermogravimetric analysis, scanning electron microscopy, and tensile testing. CMC-based actuator films were produced by gold coating on both surfaces of CMC-based films. Polyethylene glycol (PEG) at different loadings (1, 1.5 and 2 g) was used to improve electroactive behavior of CMC based actuators. Maximum tip displacements were obtained under DC excitation voltages of 1, 3, 5 and 7 V. CMC based actuator loaded with 1.5 g PEG exhibited the largest tip displacement among other actuators for each excitation voltage. The PEG loading did not lead to considerable differences in tensile strength of CMC-based films. However, Young’s modulus decreased with PEG loading.

Physicochemical and Antimicrobial Properties of Biopolymer-Candelilla Wax Emulsion Films Containing Potassium Sorbate – A Comparative Study

Thecomparativestudieswereperformedinorderto assess the most suitable matrix polymer for potassium sorbate (KS). Thepreservative(1.0, 2.0,3.0,4.0 %w/w) was included into edible films made from different biopolymers: carboxymethyl cellulose (CMC), oxidized potato starch (OPS), soy protein isolate (SPI), gelatin (GEL), sorbitol, candelilla wax, and emulsifier. The incorporation of KS dra- matically reduced the toughness of all tested films. The plas- ticizing action of KS was the weakest in CMC-based films, which exhibited the highest initial stiffness and the lowest stretchability. With the exception of GEL films, KS addition caused an increase in water vapor permeability of the films. Moreover, except for CMC films, increased KS content in the films led to increase in the stickiness, moisture content, and solubility. CMC-based films, regardless of the concentration of KS, had unchanged hygroscopicity and were completely water-soluble.In mostcases, KS reduced transmissionof light through the films. OPS, SPI, and GEL films, in contrast to CMC-based ones, exhibited sorbitol crystallization; however, the addition of KS successfully overcame this disadvantage. The antimicrobial effectivenessofall testedfilmsincreased by increasing the KS concentration. The kind of carrier used affected antimicrobial effectiveness of KS, and SPI films tended to have the weakest antibacterial and antifungal activity, especially at low KS content. The data given here may provide a useful guide in establishing the best compro- mise between conflicting film property demands. Taken to- gether, our findings suggest that the CMC films could be the best carrier for KS.