Physicochemical and Engineering Properties of Nanocomposite Films Based on Chitosan and Pseudoboehmite Alumina

Chitosan-based nanocomposite plastic films were developed by adding 0, 1, 3, and 5 % boehmite alumina (BAH) nanoparticles as a percentage of chitosan powder weight. The films were cast via solution. The effect of BAH content on the physicochemical and engineering properties of the resultant films were determined. The swelling, water vapor adsorption capacity, and transparency were significantly reduced with increased BAH content. The stability of the films against microbial degradation under high relative humidity also increased with BAH content. The water vapor permeability (WVP) reduced with increased temperature giving rise to negative activation energy values, which ranged between 2.08 and 3.36 kJ/mol. However, at constant temperature, inclusion of BAH did not have significant effect on water vapor permeability (WVP). WVP was predicted to high accuracy (r ²?=?0.984) using a full quadratic regression model. All the films had similar tensile and thermal behaviors. The implications of the findings are discussed based on prospective applications of the biodegradable film especially for fresh produce packaging.     

Freezing–thawing effects on the properties of dialdehyde carboxymethyl cellulose crosslinked gelatin-MMT composite films

Freezing–thawing is used as a new method to disperse montmorillonite (MMT) in dialdehyde carboxymethyl cellulose (DCMC) crosslinked gelatin-based films. The effects of freezing–thawing on the structure and properties of gelatin-DCMC-MMT films were investigated. The data of XRD indicate that freezing–thawing plays an important role in dispersing MMT into gelatin matrix and reducing the nanoparticles aggregation. The optical properties studies show that gelatin-DCMC-MMT films are very transparent and have excellent barrier properties against UV light. Freezing–thawing process decreases the transparency of films at visible region due to the better dispersion of MMT. The resulting films exhibit similar total soluble matter (TSM) values. However, the films prepared by freezing–thawing method have higher moisture content (MC), may be resulting from the more void volume obtained during the freezing–thawing process. The water vapor permeability (WVP) measurements show that the addition of MMT decreases the WVP of the films. Moreover, the freezing–thawing method can further decrease the WVP of the films. In addition, the films prepared by freezing–thawing are observed with better mechanical properties and thermal stability. The results suggest that the freezing–thawing method is beneficial to dispersing MMT into the gelatin matrix and raising the properties of DCMC crosslinked gelatin-MMT films.     

魔芋葡甘聚糖/油酸修饰纳米ZnO复合抗菌膜的制备与表征

为提高纳米氧化锌（ZnO）在魔芋葡甘聚糖（konjac glucomannan，KGM）中的分散性，以增强纳米复合膜的抗紫外线性能和抗菌性能，通过油酸（oleic acid，OA）对纳米ZnO进行修饰，制备OAZnO溶液，并采用浇铸法制备KGM/OAZnO纳米复合膜，通过流变学分析、傅里叶变换红外光谱分析、X射线衍射分析、微观结构观察、热重分析以及理化性质测定，研究OAZnO的添加对KGM膜结构和理化性质的影响。结果表明，OA提高了纳米ZnO的分散性，傅里叶变换红外光谱分析证实纳米ZnO与KGM分子间形成了较强的氢键，X射线衍射光谱结果表明纳米ZnO中的Zn2＋与KGM链上的—OH形成配位键；同时，适量OAZnO（0.49 mL）使纳米复合膜包装机械性能和阻水性能得到增强，其水蒸气透过率较KGM膜降低了35.62%，拉伸强度提高了79.26%。此外，紫外光谱分析和抗菌实验结果表明KGM/OAZnO纳米复合膜具有较强的紫外阻隔性能和抗菌性能。综上，OAZnO的添加可以提高纳米复合膜综合性能，且OAZnO溶液添加量为0.49 mL时最强，可以作为功能性食品包装膜。     

包载山苍子油的醇溶蛋白纳米粒子对明胶膜结构和性能的影响

本文以明胶、玉米醇溶蛋白和山苍子油为基材,通过流延法制备包载山苍子油的醇溶蛋白纳米粒子/明胶复合膜,研究了纳米粒子与明胶的相互作用,以及不同纳米粒子添加量对复合膜的透光性、微观结构、热稳定性、机械性能、疏水性、抑菌和抗氧化性能的影响。结果表明,纳米粒子与明胶之间发生了氢键相互作用,具有良好的相容性。随着纳米粒子添加量的增大,复合膜的透明度显著降低,其疏水性和抗氧化性显著增强（P<0.05）。复合膜对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌活性,其抑菌圈直径分别为（9.17～10.00） mm和（10.02～11.10） mm。当纳米粒子分散液添加量为30%(v/v)时,复合膜的截面最致密,其热稳定性最好,断裂伸长率最大。本研究为开发含有山苍子油的食品活性包装材料提供了一定的参考依据。     

Mechanical and water vapor barrier properties of extruded and heat-pressed gelatin films

Gelatin-based edible films were produced by extruding hot melt of gelatin-based resins through a die with slot orifice and followed by heat-pressed method. The resins were plasticized with glycerol, sorbitol and the mixture of glycerol and sorbitol (MGS). The effect of type of plasticizer on extruded and heat-pressed (EHP) film-forming capacity was studied, and the mechanical and water barrier properties of resulting EHP gelatin films were compared with those of gelatin films prepared by solution casting method. Stretchable films were formed when glycerol or MGS were used as plasticizer, whereas resins plasticized with sorbitol were extruded in non-stretchable sheets. Glycerol plasticized gelatin film showed the highest flexibility and transparency among the EHP films tested. Tensile strength (TS), elongation (E) and water vapor permeability (WVP) of glycerol plasticized EHP gelatin films were 17.3 MPa, 215.9% and 2.46 ng m/m² s Pa, respectively, and EHP gelatin films had higher E values, lower TS values and higher WVP values compared to the glycerol plasticized cast gelatin films.     

Preparation and properties of dialdehyde carboxymethyl cellulose crosslinked gelatin edible films

Glycerol-plasticized gelatin edible films with a new kind of dialdehyde polysaccharide, dialdehyde carboxymethyl cellulose (DCMC) as crosslinking agent are successful prepared using casting techniques. The mechanical properties, thermal stability, light barrier properties, swelling behavior as well as water vapor permeability (WVP) of the gelatin-DCMC films are investigated. The results indicate that the addition of DCMC causes tensile strength (TS) and thermal stability to increase and elongation at break (EB) to decrease, suggesting the occurrence of crosslinking between gelatin and DCMC. The light barrier measurements present high values of transparency at 280 nm and low values of transparency at 600 nm of the gelatin-DCMC films, indicating that gelatin-DCMC films are very transparent (lower in transparency value) while they have excellent barrier properties against UV light. Moreover, the values of transparency at 280 nm increase with the increased DCMC and glycerol content, suggesting the potential preventive effect of gelatin-DCMC films on the retardation of product oxidation induced by UV light. Furthermore, the addition of DCMC can greatly decrease the water vapor permeability (WVP) and equilibrium swelling ratio (ESR) down to values about 1.5 × 10⁻¹⁰ g m/m² s Pa and 150%, revealing the potential of DCMC in reducing the water sensitivity of gelatin-based films. In common for hygroscopic plasticizer in edible films, the addition of glycerol gives increase of EB and WVP and decrease of thermal stabilities and ESR of the gelatin-DCMC films.     

桔子精油优化鱼鳞明胶膜性能的作用研究

为改善鱼鳞明胶膜的性能,测定添加明胶质量的0%、25%、50%、75%、100%桔子精油的可食膜的厚度、机械性能、水溶性、水蒸汽透过率、色泽、透明度和透光率、热性能、红外光谱和抑菌活性。结果表明:随着精油浓度的增加,鱼鳞明胶膜的厚度、断裂伸长率增加,拉伸强度、透光率、水溶性降低,水蒸汽透过率呈现先增加后降低的趋势;差示扫描量热法(DSC)和傅里叶变换红外光谱(FTIR)分析结果表明,鱼鳞明胶分子与桔子精油的部分成分发生相互作用,在一定程度上改善了明胶膜的热稳定性;桔子精油的添加还赋予了鱼鳞明胶膜抑菌作用。综合评价得出75%质量浓度的桔子精油添加量对鱼鳞明胶膜各项性能优化效果最好,本实验结果可为生产高性能的鱼鳞明胶膜提供理论基础。     

Probing the interaction between 3 flavonoids and pancreatic lipase by methods of fluorescence spectroscopy and enzymatic kinetics

The aim of this study was to evaluate the effects of the addition of surfactants sodium stearoyl lactate (SSL) and sucrose ester (SE) on the functional properties of films produced with polysaccharides mixtures (methylcellulose/glucomannan/pectin in 1/4/1 ratio, respectively) and gelatin. The films were produced by the casting method and characterized for their water vapor permeability (WVP), mechanical (tensile strength and elongation to break point), morphological and optical properties. Films with low WVP were obtained with surfactants. Addition of SE to the films with polysaccharide/gelatin ratio of 90/10 showed improved mechanical properties. Films presented smooth surfaces with micro voids and lumpiness, depending on the surfactant tested. Surfactants increased the opacity of the films by a factor of 1–3%. All film properties were dependent on the surfactant affinity for the biopolymer matrix. SE presented more affinity for biopolymer matrix containing high polysaccharide proportion, and SSL presented more affinity for polymer matrix containing high gelatin proportion. The addition of surfactants decreased the water vapor permeability of the films, increasing their hydrophobic character.     

Properties of Gelatin Film from Horse Mackerel (Trachurus japonicus) Scale

Optimal conditions for extracting gelatin and preparing gelatin film from horse mackerel scale, such as extraction temperature and time, as well as the protein concentration of film‐forming solutions were investigated. Yields of extracted gelatin at 70 °C, 80 °C, and 90 °C for 15 min to 3 h were 1.08% to 3.45%, depending on the extraction conditions. Among the various extraction times and temperatures, the film from gelatin extracted at 70 °C for 1 h showed the highest tensile strength and elongation at break. Horse mackerel scale gelatin film showed the greatly low water vapor permeability (WVP) compared with mammalian or fish gelatin films, maybe due to its containing a slightly higher level of hydrophobic amino acids (total 653 residues per 1000 residues) than that of mammalian, cold‐water fish and warm‐water fish gelatins. Gelatin films from different preparation conditions showed excellent UV barrier properties at wavelength of 200 nm, although the films were transparent at visible wavelength. As a consequence, it can be suggested that gelatin film from horse mackerel scale extracted at 70 °C for 1 h can be applied to food packaging material due to its lowest WVP value and excellent UV barrier properties.     

Properties of film from cuttlefish (Sepia pharaonis) skin gelatin incorporated with cinnamon,clove and star anise extracts

Properties of film from cuttlefish (Sepia pharaonis) ventral skin gelatin without and with partial hydrolysis (1.2% degree of hydrolysis) incorporated with 1% ethanolic extract of cinnamon (CME), clove (CLE) and star anise (SAE) were determined. Films with different herb extracts (without and with oxidation) had higher tensile strength (TS) but lower elongation at break (EAB), compared with the control film (without addition of herb extracts) (p < 0.05). Lower water vapor permeability (WVP) and L^∗-value but higher b^∗- and ΔE^∗-values were observed when the extracts were incorporated (p < 0.05). Electrophoretic study revealed that cross-linking was pronounced in films containing different herb extracts. Oxidized extracts yielded films with higher TS and WVP than those without oxidized herb extracts (p < 0.05). Generally, similar properties were noticeable for films from gelatin with and without partial hydrolysis. Nevertheless, higher mechanical properties were obtained for the latter. FTIR spectra indicated that protein–polyphenol interactions were involved in the film. Thermo-gravimetric analysis revealed that films incorporated with SAE or SAE with oxidation (OSAE) exhibited lower heat susceptibility and weight loss in the temperature range of 50–600 °C, compared with control film. Films with SAE and OSAE had smoother surface for gelatin without hydrolysis; however, coarser surface was observed in film from gelatin with partial hydrolysis. Thus, the incorporation of different herb extracts directly affected the properties of film from cuttlefish skin gelatin with and without hydrolysis.     

Fatty acids and their sucrose esters affect the properties of fish skin gelatin-based film

The effects of fatty acids (FA) [palmitic acid (PA) and stearic acid (SA)] and their sucrose esters (FASE) on the mechanical properties, water vapor permeability (WVP), light transmission, and color of films from bigeye snapper and brownstripe red snapper skin gelatins were investigated. Tensile strength (TS) of films generally decreased with the addition of FA (p<0.05), while gradually increased with increasing FASE amount (p<0.05). WVP of films generally decreased with increasing amount of FA or FASE (p<0.05). However, films containing FASE exhibited the superior WVP barrier property to those added with FA. Marked increase in elongation at break (EAB) was observed when either FA or FASE at a level of 25% substitution was incorporated. Light transmission of films in both UV (200–280 nm) and visible ranges (350–800 nm) decreased with increasing FA amount. Films added with FASE were generally more transparent than those with FA. Chain length of FA or FASE affected the properties of films differently, depending upon gelatin sources. Therefore, the properties of fish skin gelatin-based films, especially water vapor barrier, could be improved by the addition of FA or FASE.     

Preparation and characterization of agar/clay nanocomposite films: the effect of clay type

Abstract: Agar‐based nanocomposite films with different types of nanoclays, such as Cloisite Na⁺, Cloisite 30B, and Cloisite 20A, were prepared using a solvent casting method, and their tensile, water vapor barrier, and antimicrobial properties were tested. Tensile strength (TS), elongation at break (E), and water vapor permeability (WVP) of control agar film were 29.7 ± 1.7 MPa, 45.3 ± 9.6%, and (2.22 ± 0.19) × 10^?9 g·m/m²·s·Pa, respectively. All the film properties tested, including transmittance, tensile properties, WVP, and X‐ray diffraction patterns, indicated that Cloisite Na⁺ was the most compatible with agar matrix. TS of the nanocomposite films prepared with 5% Cloisite Na⁺ increased by 18%, while WVP of the nanocomposite films decreased by 24% through nanoclay compounding. Among the agar/clay nanocomposite films tested, only agar/Cloisite 30B nanocomposite film showed a bacteriostatic function against Listeria monocytogenes.     

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.     

Physicochemical,Antioxidant, In Vitro Release,and Heat Sealing Properties of Fish Gelatin Films Incorporated with β-Cyclodextrin/Curcumin Complexes for Apple Juice Preservation

The antioxidant activity of gelatin film is poor. Curcumin is a natural antioxidant, but its main disadvantage is low aqueous solubility. In this study, curcumin was encapsulated by β-cyclodextrin to prepare βCD/CUR complex. Gelatin films incorporated with βCD/CUR complexes (GL-βCD-CUR films) were fabricated. The effects of curcumin content on their properties were investigated. Results showed that the water solubility of curcumin was improved in βCD/CUR complex. The βCD/CUR complex containing 2.5 mg curcumin had smaller size and more homogeneous distribution. The thicknesses of all films were about 87 μm and there were no significant differences (p > 0.05). The optimal tensile strength (TS) and elongation at break (EAB) of GL-βCD-CUR films were observed at the curcumin content of 2.5 mg. With the increase of curcumin concentration, water vapor permeability (WVP) of gelatin-based films decreased from 2.88 to 2.38 × 10^?10 g m^?1 Pa^?1 s^?1 and water content (WC) decreased from 34.64 to 24.72%, but water solubility (WS) increased from 21.22 to 59.75%. GL-βCD-CUR films exhibited lower light transmission in UV light compared with GL-βCD film. SEM provided that there was a good compatibility between gelatin molecules and βCD/CUR complexes. FTIR proved that no functional groups appeared or disappeared. A significant increase in antioxidant activity and the stability of this activity along with a lower release rate of curcumin in food simulant were observed in gelatin films incorporated with βCD/CUR complexes. The heat sealing property of GL-βCD-CUR films containing 1 or 2.5 mg curcumin was better than that of film containing 5 mg curcumin. The L values of red Fuji (Malus pumila mill) apple juice packed by GL-βCD-CUR films reduced slowly. The slowest decline in total polyphenol content was found in GL-βCD-2.5CUR group. Our results indicated that the incorporation of βCD/CUR complex significantly enhanced the antioxidant activity of gelatin film, and the GL-βCD-CUR film can be used in apple juice preservation.     

Effects of various plasticizers on mechanical and water vapor barrier properties of gelatin films

Different kinds of plasticizers were chosen to study the effects of plasticizer composition, size and shape on the mechanical properties and water vapor permeability (WVP) of gelatin films in this paper. Firstly, oligosaccharides – sucrose, and some organic acids such as oleic acid, citric acid, tartaric acid, malic acid (MA) were added to gelatin. It was found that only MA could improve the ductility of gelatin film, and the visual appearance of MA modified gelatin film was better. Secondly, polyethylene glycols (PEG) with different molecular weights (300, 400, 600, 800, 1500, 4000, 10?000, 20?000) were used to plasticize gelatin films. This showed that PEG of lower molecular weights exhibited better plasticizing effect for gelatin films, and such films had better visual properties. This shows that mannitol (Man) and sorbitol (Sor) could make gelatin films flexible, whereas Man could crystallize from gelatin film. Following this, the plasticization of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) series and ethanolamine (EA), diethanolamine (DEA), triethanolamine (TEA) series was studied. At last, suitable plasticizers (MA, PEG300, sorbitol, EG, DEG, TEG, EA, DEA, TEA) for gelatin were selected to investigate the WVP and water content of these plasticized gelatin films. The mechanical properties of these films were also compared.     

添加单宁对明胶可食膜性质的影响

如何提高明胶膜的机械性能和阻隔性能,一直以来是可食膜研究领域的重要内容。本文以不同剂量(0 mg/g、10 mg/g、20 mg/g、30 mg/g和40 mg/g)单宁添加于明胶液并以浇注法成膜,然后对膜的理化性质进行分析。研究结果发现单宁有效提高了明胶膜的拉伸强度,但降低了其断裂伸长率;当单宁添加量为30 mg/g(明胶干基)时,其拉伸强度最大(22.10 MPa),断裂延伸率最小(40.12%)。与对照膜相比,单宁的添加降低了复合膜水溶性,水蒸气透过率和氧气透过率。在单宁含量添加范围内,水蒸气透过性最低为1.49×10-11 g/(Pa·s·m);水溶性最低为27.76%,氧气透过率最低为21.63 meg/kg。同时,DSC分析表明单宁提高了明胶膜的热稳定性。FT-IR图谱表明单宁与明胶之间发生了以氢键和疏水键为主的物理交联作用。所以,单宁-明胶复合膜在食品包装方面具有潜在的开发价值。     

Effects of nanoclay type on the physical and antimicrobial properties of PVOH-based nanocomposite films

Polyvinyl alcohols-based nanocomposite films with four types of montmorillonite (MMT) nanoclay, including 18-amino stearic acid (I.24TL), methyl, bis hydroxyethyl, octadecyl ammonium (I.34TCN), di-methyl, di-hydrogenated tallow ammonium/siloxane (I.44PSS) organically modified MMT and a natural MMT (Na⁺-MMT) were fabricated by a solution-intercalation, film-casting method, and effects of the nanoclays were evaluated on physical properties, including transmittance, tensile strength (TS), elongation at break (E), water solubility (WS), swelling ratio (SR), water vapor uptake ratio (WVUR), and water vapor permeability (WVP), as well as antimicrobial activity of the polyvinyl alcohols-based films. Transmittance, WS, SR, WVUR, WVP of the nanocomposite films were significantly reduced by nano-composition compared to a pure polyvinyl alcohols film. The WVP decreased by 11.8–20.7%, and WS, SR and WVUR decreased by 19.9–41.8%, 9.1–26.4%, and 4.8–12.8%, respectively. The extent of changes was dependent on nanoclay type. X-ray diffraction patterns revealed that intercalation was formed in nanocomposite films. Overall among all the tested nanoclays, Na⁺-MMT showed more impact on physical properties of polyvinyl alcohols films, and the polyvinyl alcohols film compounded with quaternary ammonium group displayed remarkable antimicrobial activity against Gram-positive bacteria.     

Effects of nisin concentration on properties of gelatin film-forming solutions and their films

The addition of nisin into a gelatin matrix can change properties of the film. The aim of this work was to develop gelatin-based films containing different nisin concentrations in order to study their influence on the film's antimicrobial and physical properties and their rheological properties as a film-forming solution (FFS). The FFS was characterised by rheological assays, and the gelatin-based active films were characterised and assessed by the effects of nisin concentrations on their various properties, including antimicrobial activity. Nisin's concentration affected not only its viscoelastic properties of FFS but also its film solubility in water, film surface roughness and light barrier. The addition of nisin also slightly modified the water contact angle and the mechanical properties of the gelatin films. Finally, the films demonstrated activity against Staphylococcus aureus and Listeria monocytogenes at concentrations above 56 mg of nisin g⁻¹ of gelatin.     

Characterization of gelatin films prepared from under-utilized blue shark (Prionace glauca) skin

Gelatin film from blue shark (Prionace glauca) skin was investigated in order to utilize what is one of the most serious marine wastes in Japan. Film properties from shark skin such as tensile strength (TS), elongation at break (EAB) were evaluated. The TS of gelatin film from shark skin was affected by the protein concentration (1, 2 and 3%) of the film-forming solution (FFS). TS of the film from a 2% protein FFS was the highest. EAB and water vapor permeability (WVP) increased with increasing FFS protein concentration. WVP of shark skin gelatin was evidently low as compared to gelatin films from other fish. An increase in the FFS protein concentration decreased transparency at almost all wavelengths. Furthermore, opacity at 280 nm was characteristically high as compared to films from bony fish skin. The addition of glycerol improved flexibility and enhanced the UV barrier property at 280 nm. However, transparency at the visible range and WVP increased with increasing glycerol content.From the above, it was suggested that shark skin gelatin film technology can be applied to pharmaceutical products or rich-fat food due to its excellent water and UV barrier properties.     

Composite and bi-layer films based on gelatin and chitosan

The aims of this work were: to develop composite, bi-layer and laminated biodegradable films based on gelatin and chitosan, to determine film barrier and mechanical properties and to characterize their microstructure.Gelatin and chitosan concentrations used were 7.5% and 1% (w/w), respectively. Glycerol (0.75%) was added as plasticizer.Physicochemical properties such as moisture content, transparency and color were analyzed. Composite and bi-layer systems showed a compact structure indicating a good compatibility between components.Water vapor permeability (WVP) was independent of film thickness up to 120 μm for gelatin films and 60 μm for chitosan ones. Both, bi-layer and laminated systems resulted effective alternatives to reduce WVP of composite films (at least 42.5%). Bi-layer systems showed better mechanical properties than laminated ones. The resistance at break increased from 54.3 for composite to 77.2 MPa for bi-layer films, whereas elongation at break values of both composite and bi-layer films were similar (2.2–5.7%).