Preparation and functional properties of fish gelatin–chitosan blend edible films

With the goal of improving the physico-chemical performance of fish gelatin-based films, composite films were prepared with increasing concentrations of chitosan (Ch) (100G:0Ch, 80G:20Ch, 70G:30Ch, 60G:40Ch and 0G:100Ch, gelatin:Ch), and some of their main physical and functional properties were characterised. The results indicated that the addition of Ch caused significant increase (p < 0.05) in the tensile strength (TS) and elastic modulus, leading to stronger films as compared with gelatin film, but significantly (p < 0.05) decreased the elongation at break. Ch drastically reduced the water vapour permeability (WVP) and solubility of gelatin films, as this decline for the blend film with a 60:40 ratio has been of about 50% (p < 0.05). The light barrier measurements present low values of transparency at 600 nm of the gelatin–chitosan films, indicating that films are very transparent while they have excellent barrier properties against UV light. The structural properties investigated by FTIR and DSC showed a clear interaction between fish gelatin and Ch, forming a new material with enhanced mechanical properties.     

Preparation and characterization of proteinous film from lentil (Lens culinaris): Edible film from lentil (Lens culinaris)

This study was conducted to extract protein from lentil seed and prepare edible film from the protein and to determine mechanical, optical and barrier properties of lentil protein concentrate (LPC) film. The film was prepared from LPC (5 g/100 ml water) and glycerine (50%, w/w of LPC). Hunter color value (L, a and b), tensile strength, percentage elongation at break (E), puncture strength, water vapor permeability (WVP), moisture content after conditioning at 50% RH and 25 °C for 48 h and total soluble matter after immersion in water, were measured. In regarding to WVP, in spite of difference in film thickness and relative humidity of experiment in different studies, lentil protein film is comparable with other protein films. Characteristics of the lentil protein-based edible films were comparable with other edible protein films. LPC film had more red and less yellow color; it seems that the film had good mechanical properties and water vapor permeability in concomitant with good solubility.     

Molecular and structural characteristics of cod gelatin films modified with EDC and TGase

Cod gelatin films before and after cross-linking of gelatin with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) or transglutaminase (TGase) have been characterized by Fourier transform infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC) analysis. For comparison, a film prepared from unmodified pig gelatin has been also analysed. The difference spectra showed that cod gelatin during the film formation involved first of all water-to-amide hydrogen bonds, and the film from pig gelatin contained water-to-amide, amide-to-amide and water-to-water hydrogen bonds. A higher number of hydrogen bonds in the structure of the film from pig gelatin contributed to much better recovering of the helical structure in this film than in the film from cod gelatin, as the peaks at about 1663 cm^?1 in the amide I band and at about 1537 cm^?1 in the amide II band in the second-derivative spectra revealed. The recovered helical structure, in turn, resulted in a significantly higher melting enthalpy value in the case of the film from the pig gelatin. After modification of cod gelatin with EDC or TGase, the inter-chain cross-linkages formed in the films led to the conformation of gelatin with no indications of helical ordering. An increase of melting temperature of gelatin films by 7 °C on EDC and by 10 °C on the TGase modifications was related to the formation of covalent cross-links, and a decrease of glass temperature by 28 °C and 7 °C on EDC and TGase cross-linking, respectively, demonstrated the plasticizing effect of water.     

Quick dissolvable,edible and heatsealable blend films based on konjac glucomannan – Gelatin

A novel quick dissolvable, edible and heatsealable blend film of konjac glucomannan and gelatin was prepared successfully by using the solvent-casting technique with different blending ratios of the two polymers. The structure of the blend films was investigated by using differential scanning calorimeter, Fourier transform infrared spectrum and transparence analysis, etc., the physical properties of the films such as mechanical property, heat-sealing, water–vapor transmission ratio and water-solubility were also examined. The results indicated that the blend system of konjac glaucomannan and gelatin had a conditional miscibility. A new crystal occurred and hydrogen bonding interaction was strengthened when the KGM content in the blend films was around 40 wt%. The blend film had the best miscibility, a good tensile strength, heatseal and the least water–vapor transmission ratio at the same ratio. All the blend films showed a wonderful water-solubility and could dissolve not more than 30 s. Taking the degradability into account, the blend film K4 might be a perfect material for edible inner packaging.     

Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film

Multilayer films composed of PLA and agar/κ-carrageenan/clay (Cloisite® Na⁺) nanocomposite films were prepared, and the effect of lamination of PLA layers on the performance properties such as optical, mechanical, gas barrier, water resistance, and thermal stability properties was determined. The tensile strength (TS) of the agar/κ-carrageenan/clay nanocomposite films (67.8 ± 2.1 MPa) was greater than that of PLA films (43.3 ± 3.6 MPa), and the water vapor permeability (WVP), water uptake ratio (WUR), and water solubility (WS) of the nanocomposite films were higher than those of PLA films. The film properties of the multilayer films exhibited better properties of the component film layers. Especially, the WVP and water resistance of the bionanocomposite film were improved significantly, while the OTR of the PLA film decreased profoundly after lamination with PLA layers. Thermal stability of the bionanocomposite also increased after lamination with PLA layers.     

Functional stability of gelatin–lignosulphonate films and their feasibility to preserve sardine fillets during chilled storage in combination with high pressure treatment

The physico-chemical and functional stability of gelatin (G) and gelatin–lignosulphonate (GLS) films stored during 4 weeks at 21 °C, (i) in container or (ii) in contact with oil, was examined. Addition of lignosulphonate dramatically increased ABTS radical scavenging and ferric ion reducing capacities, which remained practically unaltered after the storage period. GLS films exhibited reduced elongation at break, irrespective of storage medium, and retained their water resistance. The feasibility of using GLS film to improve the quality of sardine fillets during chilled storage, alone or in combination with high pressure treatment (300 MPa/10 min/7 °C), was evaluated. The combined use of GLS film with high pressure reduced microbial growth, total volatile basic compounds (TVB) and thiobarbituric acid reactive substances (TBARS) during chilled storage. No noteworthy high pressure-induced colour changes were observed in the sardine muscle using this treatment alone, although an increase in yellowness due to the combined treatment was detected.Industrial RelevanceAddition of lignosulphonate dramatically increased antioxidant properties (ABTS radical scavenging and ferric ion reducing) of gelatin films, which remained practically unaltered during 4 weeks of storage at room temperature. Application of those films confers stability during storage of chilled sardine, especially in combination with high pressure treatment. These novel packaging was promising for fish preservation.     

Characterization of ‘wet’ alginate and composite films containing gelatin,whey or soy protein

The following study explored how the addition of various proteins (gelatin, soy protein isolate (SPI) and heated/unheated whey protein isolate (WPI)), at two different concentration levels (1% and 2%), affected the mechanical, microstructural and optical properties of calcium cross-linked ‘wet’ alginate films. Additionally, the water holding capacity and textural profile analysis (TPA) properties were determined for the alginate–protein gels. Adding all types of protein significantly (P < 0.05) decreased the force to puncture the ‘wet’ alginate–protein composite films compared to the control alginate film. The tensile test showed significant differences in tensile strength between the various films but interestingly there was no significant difference in the percent elongation at breaks between any of the films. Micrograph images showed that the SPI and heated WPI formed relatively larger protein clumps/regions in the alginate films whereas the gelatin and unheated WPI appeared to be more integrated into the alginate film. The heated WPI films were the least transparent of all the films, followed by the SPI films. Few TPA differences existed between the alginate–protein gels. However, the alginate–gelatin gels did have significantly less water loss than the other alginate–protein gels suggesting that alginate and gelatin may be the most compatible of all the alginate–protein combinations tested.     

Water barrier properties of treated-papers and application to sponge cake storage

Water barrier properties of three treated papers and of one plastic film were compared and the potential of these packaging films to prevent moisture loss from a sponge cake during storage in standard conditions (25 °C and 50% relative humidity gradient) was evaluated. Sorption isotherms were established at 25 °C for both sponge cake and papers, from which diffusivity values in papers were determined for the whole range of A_w. Permeability of packaging films was determined in standard conditions. Water sorption was close for all papers, regardless of their treatment, whereas water diffusivity was reduced by coating or calendering. Water vapor permeability in papers was controlled by diffusivity which was characterized by a two-phases (vapor then bulk water state) mechanism. Calendered-coated papers and plastic film were both adapted to prevent moisture loss from intermediate moisture foods such as a sponge cake during usual storage time.     

Gelatin-based films containing hydrophobic plasticizers and saponin from Yucca schidigera as the surfactant

The aim of this study was to evaluate the incorporation of hydrophobic plasticizers (acetyltributyl citrate – ATB, tributyl citrate – TB and acetyltriethyl citrate – ATC) in a matrix of gelatin, using the saponin extracted from Yucca schidigera (yucca) as emulsifier, in the production of biodegradable emulsified films using the casting technique. High levels of hydrophobic plasticizers were incorporated, reaching up to 75% of plasticizer in relation to the protein (w/w) for ATB and TB, and up to 60% for ATC. The minimum values of water vapor permeability were 0.08, 0.07 and 0.06 g mm m^?2 h^?1 kPa^?1 for ATB, TB and ATC respectively, with no significant differences (p > 0.05). The water solubility of the films ranged from 21% to 59.5%. Although the WVP decreased, both scanning electron microscopy and laser scanning confocal microscopy indicated that the incorporation of the hydrophobic plasticizers did not occur homogeneously in the film matrix.     

Effect of processing parameters on the properties of transglutaminase-treated soy protein isolate films

The effects of processing parameters, including the applied amount of microbial transglutaminase (MTGase), the pH of film-forming solution, air-drying temperature, as well as the additional pre-incubation, on the properties of MTGase-treated soy protein isolate (SPI) films were investigated. The treatment with low concentration of MTGase (4–10 units per gram of SPI, U g^− 1) significantly increased the tensile strength (TS) values of SPI films, while high concentration of MTGase (over 20 U g^− 1) resulted in significant decrease in the TS values (P ≤ 0.05). The elongation at break (EB) values of corresponding films gradually decreased, and the contact angle values persistently increased with the enzyme concentration. At alkaline pH range, the TS and EB values of MTGase-treated SPI films were significantly higher than that at pH 7.0 (P ≤ 0.05). Meanwhile, the contact angle values significantly decreased with increasing pH from 7.0 to 10.0 (P ≤ 0.05). The TS, EB and contact angle values of MTGase-treated films gradually but insignificantly decreased with increasing the air-drying temperature from 18 to 50 °C (P > 0.05). The properties of MTGase-treated films were also affected by the additional pre-incubation of film-forming solutions with MTGase before casting. Furthermore, the aggregation of SPI or its components induced by MTGase has been proved to mainly account for the influence of processing parameters on the properties of SPI films (MTGase-treated). Thus, low concentration of enzyme, alkaline pH range and low air-drying temperature, at which conditions the MTGase-induced aggregation of SPI in film-forming solutions could be in some extent inhibited or delayed, might facilitate the improvement of the properties of SPI films by MTGase, especially the mechanical and surface hydrophobic properties.Industrial relevanceThe development of biodegradable protein film has attracted a lot of attention worldwide. The enzymatic cross-linking induced by transglutaminase has been confirmed to improve mechanical and surface hydrophobic properties of cast films from most of food proteins, including soy proteins. Results of this study show that, the improvement of properties of cast films of soy proteins by transglutaminase treatment is largely dependent upon many processing parameters, e.g., enzyme concentration, the pH of film-forming solution and temperature.     

Correlations between structural,barrier, thermal and mechanical properties of plasticized gelatin films

The aims of this work were to develop gelatin films using glycerol as plasticizer (0–100% based on protein mass) and to establish relationships between glycerol content and structural, barrier, thermal and mechanical film properties. These correlations were established since WVP exhibited a minimum for films containing 20 g glycerol/100 g gelatin, while flexibility increased from 2.2% to 180.9% and T_g shifted from 137.5 to 21.3 °C, for films without glycerol and plasticized films with 80 g glycerol/100 g gelatin, respectively. Furthermore, a satisfactory fit between T_g experimental data and predicted values by Couchman and Karasz's equation was found, with glycerol ranging from 0 to 60 g/100 g gelatin. T_g values correlated inversely with film moisture content, and both mechanical and thermal properties showed a strong dependence since elastic modulus and T_g followed a similar trend. Films exhibited similar X-ray patterns regardless of the glycerol concentration, showing a displacement in the position of the peak located at around 2θ = 8°, which shifted towards lower 2θ values with glycerol content.The abovementioned correlations between film physical properties and glycerol content, would allow to select the optimum conditions to develop, process and manage gelatin films according to specific requirements.Industrial relevanceThe methodology used in this work is of considerable importance for the film development and could be used in industrial applications. The management of film formulations and the function that each component plays could allow to obtain tailormade films. A series of relationships between film properties based on gelatin was found, as well as between these properties and glycerol content of the films. An inflexion point in the behavior and microstructure of these materials was established due to glycerol concentration. The addition of higher quantities of glycerol than that corresponds to the abovementioned point, would not be recommendable since the properties are not modified and moreover, it is not profitable. These results would allow better management of film formulations and an appropriate selection of plasticizer concentration in accordance with the specific requirements of potential users.     

Modulation of mechanical and surface hydrophobic properties of food protein films by transglutaminase treatment

The effects of microbial transglutaminase (MTGase) treatment on the mechanical and hydrophobic properties of cast films from various food proteins were investigated. SDS–PAGE analyses confirmed that the MTGase treatment led to the formation of insoluble film network for most of food proteins. This enzymatic treatment significantly (P < 0.05) increased tensile strength (TS) values of cast films of all food proteins by 13–33% (except whey proteins). Meanwhile, the influence on the elongation at break (EB) values was mainly dependent upon the molecular nature of proteins. For most of food proteins, both increases in TS and EB values of films were obtained after the MTGase treatment. Furthermore, the surface hydrophobicity of most of protein films was also significantly improved. These results suggest that the enzymatic treatment by MTGase could be used as an effective technique to improve mechanical and surface hydrophobic properties of protein films.     

Effect of hydrophobic plasticizers on functional properties of gelatin-based films

The aim of this study was the production and characterization of gelatin-based films using hydrophobic plasticizers derived from citric acid and soy lecithin as emulsifier. The films were characterized as to their mechanic properties, permeability to water vapor, opacity, morphology and possible interactions using Fourier transform infrared spectroscopy. Tensile strength values (TS) varied from 36 to 103 MPa, however, the increase in the concentration of plasticizers (acetyltributyl citrate and tributyl citrate) reduced TS by 57% and no relation was observed between plasticizer quantities and the elongation in the quantities tested. Permeability to water vapor varied between 0.17 and 0.34 (g mm/m² h kPa), slightly increasing with the increase in concentration of plasticizers. The effectiveness in the use of soy lecithin emulsifier in the homogenization between the compounds could be proven by microscopic observation using confocal laser microscopy.     

Effects of flaxseed oil concentration on the performance of a soy protein isolate-based emulsion-type film

Biodegradable edible films have the potential to either replace or reduce the amount of synthetic packaging utilized by the food industry. The overall goal of this research was to investigate the effect of flax seed oil concentration (1–10%) on the mechanical, moisture barrier and swelling properties of soy protein isolate (SPI) (5.0% w/w SPI, 40% w/w glycerol) emulsion-based films. Film forming solutions showed a bimodal oil droplet distribution with peak sizes occurring at < 10 and ~ 100 μm. As the oil content increased, the size distribution shifted towards smaller droplet sizes. An equal size ratio was noted at the 5.0% oil content level. All film forming solutions were pseudoplastic in nature, where viscosity increased from 18 to 58 mPa (at 1 s^− 1) as a function of oil content (3% to 10%). Tensile strength of formed films reached a maximum at 5.35 MPa at the 5% w/w oil level, whereas tensile elongation increased from 11.3% to 22.2% with increasing oil content. Puncture strength and deformation, as well as water vapour permeability was relatively independent of the oil content. Moisture content and swelling properties of formed films were found to both decrease from 22.8% to 18.7%, and from 3114% to 1209%, respectively as the oil content was raised from 1 to 10%, and films became darker, redder and more yellow in colour as the percentage of flax seed oil increased.     

The effect of high hydrostatic pressure on the flow behaviour of skim milk–gelatin mixtures

The flow behaviour of aqueous solutions of gelatin, and skim milk–gelatin mixtures treated by high-pressure processing (HPP) were investigated. HPP was carried out at 5 °C for 15 min, at 150 MPa, 300 MPa, 450 MPa and 600 MPa, and the gelatin concentrations were varied from 0 to 1 wt.%. Viscosity measurements showed that the HPP treatment did not affect the flow behaviour of gelatin alone, nor that of the skim milk–gelatin mixtures made with < 0.4 wt.% gelatin. However, at gelatin concentration > 0.4 wt.%, the mixtures treated with 300 and 450 MPa exhibited a peculiar flow behaviour, where at intermediate shear rates the viscosity was higher than that of the non-treated mixture or the mixtures treated at 150 MPa and 600 MPa. Particle size measurements showed that for gelled mixtures (> 0.4 wt.% gelatin) 300 MPa HPP treatment resulted in an increase in the particle size, while at all other pressure treatments (> 150 MPa), a shift in particle size distribution to lower sizes was observed. Confocal microscopy showed that these skim milk–gelatin mixtures were phase-separated with a gelatin continuous phase, this was confirmed by dynamic rheological measurements which showed that qualitatively the viscoelastic properties of the mixtures were the same. A mechanism of the effect of high-pressure treatment on the casein micelle in skim milk–gelatin mixtures is proposed.Industrial relevanceThis fundamental work, dealing with the effect of high pressure on the physicochemical properties skim milk–gelatin mixtures could be relevant to the industry in several ways. Firstly, skim milk–gelatin mixtures are widely used in the dairy industry, particularly in yoghurt manufacture, where gelatine is used as a stabiliser. In addition the application of High Hydrostatic Pressure to such a system is also relevant, as this technology could be used as a substitute to the conventional heat treatment processes. Secondly, an important finding of this study is that under certain conditions of high pressure and gelatine concentration, an increase in viscosity is observed at intermediate shear-rate (between 10 and 100 s^?1). This is highly relevant to Industry if the system requires subsequent pumping. Thirdly, from a sensory view point, this range of shear rates (10 and 100 s^?1) is comparable to that experienced by a food bolus during swallowing. Thus, this effect of high pressure on the viscosity can influence sensory attribute of the skim milk–gelatin food system.     

Rennet-induced coagulation of enzymatically cross-linked casein micelles

The enzymatic cross-linking of casein micelles with transglutaminase had an adverse influence on rennet-induced coagulation. Incubation with transglutaminase at 30 °C progressively reduced the levels of monomeric caseins and increased rennet flocculation time (RFT) in a Berridge test. For incubation up to 3 h at 30 °C, the reciprocal of the RFT was linearly correlated with the level of residual monomeric κ-casein, indicating that at complete cross-linking flocculation is absent. After treatment for 4–24 h at 30 °C, no residual monomeric κ-casein was detected and no rennet-induced flocculation of the casein micelle suspension was observed. Monitoring rennet-induced coagulation by diffusing wave spectroscopy revealed that transglutaminase-induced inhibition of rennet-induced coagulation of casein micelles is primarily due to an inhibition of the secondary phase of rennet coagulation, i.e., the gelation and gel-firming phase of the casein micelle coagulation. The gelation and fusion of κ-casein-depleted para-casein micelles as in normal milk appears to be absent if the casein macropeptide remains attached to the casein micelle.     

Nano-TiO2 particles and high hydrostatic pressure treatment for improving functionality of polyvinyl alcohol and chitosan composite films and nano-TiO2 migration from film matrix in food simulants

This study investigated the impact of nano-TiO₂ and high hydrostatic pressure (HHP) treatment on microstructure, water vapor and gas barrier, antibacterial and mechanical properties of polyvinyl alcohol (PVA)–chitosan (CHI) biodegradable films and determined the migration behavior of TiO₂ nanoparticles from the films to food simulants. Apart from the effect of filler, TiO₂ nanoparticles also could improve the antibacterial activity of the films and play a role as a plasticizer in the films. HHP treatment promoted the interaction between PVA and chitosan molecules, resulting in the formation of more compacted network structures in PVA–CHI films. The migration of TiO₂ from the films was investigated in food simulants including distilled water, acetic acid, ethanol and olive oil, in which the trace amount of TiO₂ (< 4.20 × 10^− 3‰) was only detected in olive oil. HHP treatment at 200–400 MPa significantly reduced migration of TiO₂ nanoparticles from the films.Industrial relevanceResults from this study provide a new application direction of high hydrostatic pressure (HHP) in the field of food packaging materials for improving the functionality of materials. Due to the non-thermal characteristic, HHP in combination with nano-TiO₂ not only improved the mechanical and barrier properties of the biodegradable PVA–CHI composite films (polyvinyl alcohol and chitosan based materials), but also enhanced the antibacterial activity of the films. The HHP treated PVA–CHI–TiO₂ films are very stable in food simulants, such as olive oils. Therefore, the utilization of HHP and nano-TiO₂ is promising in the preparation of food packaging materials with desirable functionalities.     

Ethanol stability of casein micelles cross-linked with transglutaminase

The influence of transglutaminase (TGase)-induced cross-linking on the ethanol stability of skimmed milk was investigated. The stability of milk against ethanol-induced coagulation increased in sigmoidal fashion with milk pH (5.0–7.5) for all samples; ethanol stability also increased upon incubation (0–24 h) with 0.05 g L⁻¹ TGase at 30 °C. In untreated milk, addition of ethanol induced a collapse of the polyelectrolyte brush of κ-casein on the micelle surface, thereby facilitating micellar aggregation. Dynamic and static light scattering measurements indicated that in TGase-treated milk, the ethanol-induced collapse of the polyelectrolyte brush was far less than in untreated milk, suggesting that the increased ethanol stability of TGase-treated casein micelles is caused by the cross-linking of the polyelectrolyte brush on the micellar surface.     

Sodium lactate loaded chitosan-polyvinyl alcohol/montmorillonite composite film towards active food packaging

A sodium lactate loaded chitosan-polyvinyl alcohol/montmorillonite (NaL-CS/PVA/MMT) barrier film with antibacterial activity was developed by coating method and the effectiveness and diffusion behavior were investigated. An intercalated structure was achieved for CS/PVA/MMT film and the interfacial interactions among CS, PVA and MMT were intermolecular hydrogen bonds. An appropriate increase of MMT contents (15 wt% and below) could achieve a remarkable enhancement in tensile strength and Young's modulus, meanwhile, the water vapor, oxygen and carbon dioxide barrier properties of the films were also significantly improved. The NaL-CS/PVA/MMT film exhibited good antibacterial activity against E. coli and well controlled release of NaL. Moreover, the diffusions of NaL from films were dependent on the pH value of aqueous solution and ionic strength, and the initial diffusions (M_t/M_∞ < 2/3) could be well described by Fickian equation. The NaL-CS/PVA/MMT film may have potential as a good barrier film with antibacterial activity towards food packaging.     

Effects of drying conditions on some physical properties of soy protein films

The influence of drying conditions (air temperature and relative humidity) on mechanical properties, solubility in water, and color of two kinds of soy protein isolate film: a commercial one (CSPI) and other obtained under laboratory conditions (LSPI) were evaluated using the response surface methodology (RSM). Soy protein films were prepared by casting using glycerol as plasticizer. The films were dried in a chamber with air circulation under controlled conditions of relative humidity (24%, 30%, 45%, 60%, 66%) and air temperature (34, 40, 55, 70, 76 °C). It was verified that mechanical properties of films made from LSPI and CSPI are influenced in a very different way by the drying conditions due to a diverse initial protein conformation in both materials, as was revealed by DSC and SDS–Page studies. The solubility of the LSPI film was affected by temperature and relative humidity, being lowest (～50%) for films obtained at high RH and temperatures ranging from 45 to 76 °C. For CSPI films, in contrast, solubility did not depend on the drying process and it remained relatively constant (～40%). The optimal drying conditions determined by RSM were: 70 °C and 30% RH for CSPI films and 60 °C and 60% RH for LSPI films. Dried under these conditions, CSPI films presented a higher tensile strength, lower elongation at break, lower solubility and better water and oxygen permeability than LSPI ones.