Thermomechanical properties of biodegradable films based on blends of gelatin and poly(vinyl alcohol)

The aim of this work was to study the effect of the poly(vinyl alcohol) (PVA) concentration on the thermal and viscoelastic properties of films based on blends of gelatin and PVA using differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA). One glass transition was observed between 43 and 49 °C on the DSC curves obtained in the first scanning of the blended films, followed by fusion of the crystalline portion between 116 and 134 °C. However, the DMA results showed that only the films with 10% PVA had a single peak in the tan δ spectrum. However, when the PVA concentration was increased the dynamic mechanical spectra showed two peaks on the tan δ curves, indicating two T_gs. Despite this phase separation behavior the Gordon and Taylor model was successfully applied to correlate T_g as a function of film composition, thus determining k=7.47. In the DMA frequency tests, the DMA spectra showed that the storage modulus values decreased with increasing temperature. The master curves for the PVA–gelatin films were obtained applying the TTS principle (T_r=100 °C). The WLF model was thus applied allowing for the determination of the constants C₁ and C₂. The values of these constants increased with increasing PVA concentrations in the blend: C₁=49–66 and C₂=463–480. These values were used to calculate the fractional free volume of the films at the T_g and the thermal expansion coefficient of the films above the T_g.     

Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde

Both gelatin and poly(vinyl alcohol) (PVA) can be cross linked with glutaraldehyde (GLU). In the case of gelatin, the GLU reacts with each ε-NH2 functional group of adjacent lysine residues, while for PVA, the GLU reacts with two adjacent hydroxyl groups, forming acetal bridges. Thus it can be considered possible to cross link adjacent macromolecules of gelatin and PVA using GLU. In this context, the aims of this work were the development of biodegradable films based on blends of gelatin and poly(vinyl alcohol) cross linked with GLU, and the characterization of some of their main physical and functional properties. All the films were produced from film-forming solutions (FFS) containing 2 g macromolecules (PVA + gelatin)/100 g FFS, 25 g glycerol/100 g macromolecules, and 4 g GLU (25% solution)/100 g FFS. The FFS were prepared with two concentrations of PVA (20 or 50 g PVA/100 g macromolecules) and two reaction temperatures: 90 or 55 °C, applied for 30 min. The films were obtained after drying (30 °C/24 h) and conditioning at 25 °C and 58% of relative humidity for 7 days, and were then characterized. The results for the color parameters, mechanical properties, phase transitions and infrared spectra showed that some chemical modifications occurred, principally for the gelatin. However, in general, all the characteristics of the films were either typical of films based on blends of these macromolecules without cross linking, or slightly higher. A greater improvement in the properties of this material was probably not observed due to the crystallinity of the PVA, which has a melting point above 90 °C. The presence of microcrystals in the polymer chain probably reduced macromolecular mobility, hindering the reaction. Thus more research is necessary to produce biodegradable films with improved properties.     

壳聚糖、纳米壳聚糖对聚乙烯醇膜结构与性能的影响

研究添加同一质量分数壳聚糖(chitosan,CS)、纳米壳聚糖(chitosan nanoparticles,NCS)改性聚乙烯醇(polyvinyl alcohol,PVA)膜的性能,利用色差仪与紫外分光光度计探究其光学性能;利用透气性测试仪与透湿性测试仪测试共混膜透气性能与透湿性能;通过等温吸湿实验研究了PVA膜、PVA/CS共混膜、PVA/NCS共混膜的吸湿性能,并将常见的等温吸湿曲线模型与实验数据进行拟合;采用傅里叶变换红外光谱(Fourier transform infrared spectrometer,FT-IR)、差示扫描量热(differential scanning calorimetry,DSC)仪对3种膜的结构与结晶度进行表征。结果表明:CS的加入会使PVA膜对中波紫外线的屏蔽作用增强,NCS的加入会使屏蔽效果更加明显;CS或NCS的加入会使PVA透气性能减弱,透湿性能增强;3种共混膜的等温吸湿曲线与GAB方程的拟合效果最好(R~20.98);FT-IR结果表明,PVA/CS、PVA/NCS共混均匀且共混材料之间形成分子间氢键;DSC结果表明,加入CS或NCS之后PVA分子的结晶速率变慢,结晶度下降,分子结晶的吸热焓值增加。     

茶多酚改性对聚乙烯醇膜吸湿特性及抗氧化活性的影响

研究含不同质量分数茶多酚的聚乙烯醇膜的吸湿特性和抗氧化活性。通过等温吸湿实验研究了含不同质量分数茶多酚（0%、0.5%、1%、1.5%、2%）的聚乙烯醇膜的吸湿特性,并基于常用的等温吸湿模型对实验数据进行拟合表征;通过1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl,DPPH）自由基清除实验分析了薄膜的抗氧化活性。结果表明：含不同质量分数茶多酚的聚乙烯醇膜均具有吸湿性,其等温吸湿曲线整体变化趋势相似,属于Ⅱ型等温吸湿曲线;薄膜的平衡含水率随水分活度的增加而显著增加（P＜0.01）,当水分活度大于0.6时,其平衡含水率增加幅度增大;茶多酚对聚乙烯醇膜的改性增加了其疏水性,在相同水分活度条件下,薄膜的吸湿性能随薄膜中茶多酚质量分数的增加而下降,但5 种聚乙烯醇膜之间差异不显著（P＞0.05）;GAB等温吸湿模型对薄膜吸湿性能的拟合效果最好,R2≥0.996;茶多酚对聚乙烯醇膜的改性使其具有抗氧化活性,DPPH自由基清除率随着薄膜中茶多酚质量分数的增加而显著提高（P＜0.01）,表明经茶多酚改性后的聚乙烯醇膜的抗氧化性能随薄膜中茶多酚质量分数的增加而增强。经茶多酚改性的聚乙烯醇膜具有吸湿和抗氧化功能,预示其作为塑料复合薄膜内层或中间层应用于湿度敏感型、含高脂肪等干燥易氧化食品包装具有较好的前景。     

Effect of high pressure homogenization (HPH) on the rheological properties of tomato juice: Time-dependent and steady-state shear

High pressure homogenization (HPH) is a non-thermal technology that has been widely studied as a partial or total substitute for the thermal processing of food. Although microbial inactivation has been widely studied, there are only a few works in the literature reporting the physicochemical changes caused in fruit products due to HPH, especially those regarding the rheological properties. The present work evaluated the effect of HPH (up to 150 MPa) on the time-dependent and steady-state shear rheological properties of tomato juice. HPH reduced the mean particle diameter and particle size distribution (PSD), and increased its consistency and thixotropy. The rheological results were in accordance with the PSD observed. The rheological properties of the juice were evaluated by the Herschel–Bulkley and Falguera–Ibarz models (steady-state shear) and Figoni–Shoemaker and Weltman models (time-dependent). The parameters of these equations were modelled as a function of the homogenization pressure. The models obtained described the experimental values well, and contributed to future studies on product and process development.     

Influences of degree of hydrolysis and molecular weight of poly(vinyl alcohol) (PVA) on properties of fish myofibrillar protein/PVA blend films

Biodegradable blend films based on fish myofibrillar protein (FMP) and poly(vinyl alcohol) (PVA) were prepared and characterized. PVA with different degrees of hydrolysis (DH) and molecular weights (MW) had the impact on properties of FMP/PVA (1:1, w/w) blend film. The blend films with higher MW of PVA were more tensile resistant, as indicated by the greater tensile strength (TS) and elongation at break (EAB), while the films with PVA of lower DH were more flexible. The blend film with PVA-BP26 (DH: 86–98% mol; MW: 124,000–130,000 g/mol) exhibited the greatest tensile performance and the lowest water vapor permeability (p < 0.05), compared with other films. SEM and FTIR results revealed that FMP and PVA were compatible and their intermolecular interaction was enhanced, providing the blend film with desirable properties. Therefore, incorporation of PVA with appropriated DH and MW could improve the properties of the FMP-based film.     

Development of moisture‐absorbing and antioxidant active packaging film based on poly(vinyl alcohol) incorporated with green tea extract and its effect on the quality of dried eel

Active packaging film with functions of moisture‐absorbing and antioxidant activity was developed based on poly(vinyl alcohol) (PVA) incorporated with green tea extract (GTE). The effects of GTE concentrations of 0, 0.5, 1, 1.5, and 2% on the physical, structural, and antioxidant properties of PVA films were investigated. The PVA film containing 2% GTE had lower moisture absorbing efficiency relatively and better antioxidant activity through DPPH radical‐scavenging ability experiment. A packaging system of GTE‐incorporated PVA films was applied to package dried eel and quality of dried eel was evaluated during storage. The result showed that dried eel packed with GTE‐incorporated PVA films showed lower weight change, peroxide value and TBARS value during storage than that packed without PVA films or with PVA films but no GTE. The PVA film containing 2% GTE showed the best quality protective effectiveness to prevent the dried eel from absorbing moisture and oxidizing of lipid.

Practical applications

Poly(vinyl alcohol) (PVA) is a synthetic polymer that is widely used in packaging applications because of its excellent film forming, biodegradability, good mechanical, and gas barrier properties. The present study evidenced that the PVA films incorporated with GTE showed good quality protective effectiveness to prevent the dried eel packed with these films from absorbing moisture and oxidizing of lipid. This active packaging film could be used as inner layer or intermediate layer in the composite packaging film system to improve the storage quality of moisture‐sensitive and high‐fat food. Based on this concept, the moisture‐absorbing agents and antioxidant can be incorporated into the packaging structures to develop an active multifunctional food packaging material potentially to remove or reduce moisture inside the food packaging system instead of desiccants and preservative added in the food.     

Natural deep eutectic solvents (NADES) based on citric acid and sucrose as a potential green technology: a comprehensive study of water inclusion and its effect on thermal,physical and rheological properties

In this work, NADES based on sucrose and citric acid was synthesised and evaluated. Physical properties such as density, viscosity and thermal profile were evaluated at different temperatures and water contents. Viscosity and density were inversely affected by temperature and water content. Increases in the sucrose fraction resulted in higher viscosity, but no differences in density were observed. The rheological model of Ostwald-de-Waele indicated three distinct rheological behaviours at different temperatures, water content and sucrose fractions. The Arrhenius model showed a good fit for the temperature effect on the apparent viscosity of all NADESs. The NADES decomposition temperature was approximately 393 K. The thermal characterisation revealed that all NADESs presented glass transitions at temperatures below 204.59 K, confirming their formation and stability. Based on these results, the NADES proposed appears as potential green solvent to be used in industrial processes such as extraction, separation and biochemical technology.     

Effect of harvesting stress and storage conditions on protein degradation in fillets of farmed gilthead seabream (Sparus aurata): A differential scanning calorimetry study

A trial was undertaken to evaluate Differential Scanning Calorimetry (DSC) as a fast analytical tool to differentiate gilthead seabream subjected to variable conditions of slaughter stress and post-mortem storage. Fish were subjected to different harvesting stress conditions: profound anaesthesia (PA, low stress) and net crowding (NC, high stress). Fish were slaughtered in an ice-salt water slurry, and subsequently stored on ice (7 days). Additional NC fish were frozen (−20 °C) and subjected to a freeze–thaw cycle. Dorsal muscle was assessed for cathepsins activity, liquid loss and DSC analysis. It is demonstrated that DSC analysis is capable of differentiating fresh, frozen and thawed-re-frozen fish, while liquid loss and cathepsin B activity are good markers to distinguish fresh from frozen fish. Harvesting stress had little effect on myosin and actin enthalpy transitions, as observed by DSC at 49 and 74 °C, respectively, but a lower ΔH actin/myosin ratio was found in PA fish, suggesting that intense exercise prior to slaughter promoted partial denaturation of muscle myosin.     

Celluloses microfibers (CMF)/poly (ethylene-co-vinyl acetate) (EVA) composites for food packaging applications: A study based on barrier and biodegradation behavior

CMF/EVA composites were prepared with different weight percentage of CMF. Swelling parameters, diffusion coefficient and oxygen transmission rate (OTR) of the composites were investigated to analyze the CMF–EVA interaction and application of these composites as food packaging materials. The experiments were carried out in milk, curd and orange juice at normal storage temperatures i.e., −4, 8, 15 and 25 °C. The composite showed an increased barrier property with CMF loading. This in turn also indicates good interfacial interaction between CMF and EVA which was further evaluated using FTIR spectra. SEM and optical microscopic photographs showed a uniform distribution of CMF in EVA. XRD and DSC results indicated increased crystallinity of composites with CMF loading. Biodegradability of composites were studied by inoculating the films with Aspergillus niger (A. niger) and showed increased biodegradation with CMF.