纳米TiO2对魔芋葡甘聚糖/玉米醇溶蛋白复合膜结构和性能的影响

本文以魔芋葡甘聚糖、玉米醇溶蛋白为成膜基质,添加不同含量（1%、2%、3%）的纳米TiO₂,以流延方式制备纳米TiO₂/魔芋葡甘聚糖/玉米醇溶蛋白复合膜,并对复合膜的微观结构、热性能、力学性能、疏水性、水蒸气透过率和抑菌性能进行了分析。结果表明,纳米TiO₂与魔芋葡甘聚糖、玉米醇溶蛋白间发生相互作用,有良好的相容性;添加纳米TiO₂使复合膜表面粗糙度增加,复合膜热稳定性和疏水性增强,力学性能降低;纳米TiO₂添加量为1% wt时,复合膜的水蒸气透过率（5.7×10?13 g·cm/（cm2·s·Pa））和溶胀率（16.4%）最小,水接触角值（99.6 °）最大;复合膜对金黄色葡萄球菌和大肠杆菌有明显的抑制作用,对枯草芽孢杆菌的抑制作用不明显。本研究为纳米TiO₂/魔芋葡甘聚糖/玉米醇溶蛋白复合膜作为包装材料的开发与应用提供一定参考依据。     

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。     

Rye secalin characterisation and use to improve zein-based film performance

Rye prolamins (secalin) were extracted, characterised and used as biopolymer source to produce plasticised films, as well as composite films in the presence of corn zein. Secalin film showed lower contact angle values and higher moisture content, solubility and swelling index than zein film, whereas the water vapour permeability of the two films was not different. Also, secalin film exhibited lower tensile strength and Young’s modulus and higher elongation at break. The average functional properties of the secalin/zein blend were morphologically confirmed by SEM analysis of the composite film surface that showed a good miscibility and compatibility of the two different biopolymers. These results indicated that secalin films were less hydrophobic and more flexible than those previously prepared by using other prolamins, whereas a material with hydrophobic features similar to those of zein films and a flexibility comparable to that exhibited by secalin films was obtained by preparing a secalin/zein blend.     

玉米-小麦淀粉/玉米醇溶蛋白双层膜热学及微观特性

研究了玉米-小麦淀粉成膜液与玉米醇溶蛋白成膜液不同配比制作的5 种可食用复合膜理化特性的差异, 并分别通过扫描电子显微镜观察、热重分析、差示扫描量热分析、X射线衍射分析、傅里叶变换红外光谱分析对其 热学特性和微观结构进行研究。结果表明：添加一层玉米醇溶蛋白后,双层膜阻水性提高,机械性能得到改善,由 扫描电子显微镜观察结果可知双层膜间结合紧密,热重分析和差示扫描量热分析结果显示双层膜热稳定性得到提 高,X射线衍射结果表明生物大分子之间相容性较好,傅里叶变换红外光谱分析结果发现双层膜间产生了新的氢键 等作用力,为玉米-小麦淀粉/玉米醇溶蛋白双层膜在食品包装中的应用提供了重要的参考依据。     

介质极性对柔性玉米醇溶蛋白乳化性的影响

为了探究介质极性对柔性玉米醇溶蛋白乳化性的影响,本研究采用扫描电镜、动态光散射仪、圆二色谱仪等技术研究了不同介质环境下（60%、70%、80%、90%、92%（v/v）乙醇水溶液）玉米醇溶蛋白的聚集状态、粒径分布、表面疏水性、结构性质和不同聚合物乳化液的性质。结果显示介质极性影响了柔性玉米醇溶蛋白的聚集形态,聚合物颗粒大小与介质极性成反比。介质极性越高,形成聚合物的乳化活性越高,但乳化稳定性越低。当乙醇浓度从60%增加至92%时,乳化稳定性从67.97%增加至86.47%,液滴从355.60 nm降至251.00 nm,乳化液的电位从?40 mV降至?42.85 mV。此外,介质极性越低,玉米醇溶蛋白α-螺旋结构和表面疏水性越大,进而诱导其形成不同形态聚合物,从而表现出不同的乳化特性。本研究结果为拓宽玉米醇溶蛋白的应用范围提供理论基础。     

Barrier properties of corn zein nanocomposite coated polypropylene films for food packaging applications

The feasibility of corn zein nanocomposite (CZNC) coatings as an alternative to synthetic polymer barrier layer on polypropylene (PP) films was examined. The effect of layered silicate content in the CZNC layers on the barrier and surface hydrophobicity of the CZNC-PP films were investigated. Incorporation of organomodified montmorillonite (OMMT) by solution intercalation into zein matrix significantly improved oxygen and water vapor barrier of coated PP films. The barrier properties were also investigated theoretically by using various phenomenological permeability models. Tortuous permeation path formed by the fine delamination of nanoclays was found to be responsible for the barrier improvements in zein layers. In conclusion, durable CZNC-PP laminates were developed. CZNC coating of PP films has reduced the oxygen permeability nearly four times, while water vapor permeability reduced by 30% with 5 wt.% OMMT content in 5.9 μm corn zein coating.     

Thermal Behavior of Zein‐based Biodegradable Films

In previous work, zein was plasticized with oleic acid to obtain flexible films. However, it was observed that film properties were affected by the preparation method employed. Our objective was to investigate the effect of processing methods on thermal behavior of zein films by differential scanning calorimetry (DSC). Films containing 41% oleic acid were prepared by casting ethanol solutions of its components on flat surfaces or by extrusion of zein resins prepared by cold water precipitation of ethanol solutions of zein and oleic acid. Extrusion was carried out in single‐screw or twin‐screw extruders. Zein films were finished by hot rolling or heated in a Carver press. DSC thermograms showed large oleic acid melting peaks for cast films, smaller peaks for resin films, and no apparent peaks for heat‐treated samples. It was suggested that the resin formation process enhanced zein‐oleic acid interactions and promoted plasticization. All samples showed glass transitions at low temperatures.     

乳酸对玉米醇溶蛋白基面团品质提升的作用

以玉米醇溶蛋白、玉米淀粉、沙蒿胶为原料制备玉米醇溶蛋白基无麸质面团（简称Z面团）,以玉米淀粉和沙蒿胶所制面团（简称NZ面团）为对照。通过调控面团中乳酸含量（L）和原料粉含量（F）的比例（简写为L/F,mL/g）,比较乳酸含量对Z面团与NZ面团粉质性能的影响规律,表明玉米醇溶蛋白是影响Z面团粉质性能的关键组分。面团中L/F为2∶50的Z面团（Z2）稳定时间最长,弱化度最低,粉质质量指数最高,加工品质良好。探究在乳酸调节下,Z面团中玉米醇溶蛋白的理化性质与结构变化,发现乳酸会引起玉米醇溶蛋白的脱酰胺反应和蛋白质水解,促进α-玉米醇溶蛋白二倍体向单倍体转变,改变玉米醇溶蛋白的表面疏水性和二级结构组成。基于以上研究,将Z面团制为面条,考察乳酸含量对玉米醇溶蛋白基面条蒸煮品质的影响,其中Z2面条不易断条,蒸煮损失最少,质地良好。综上,适量的乳酸可改善玉米醇溶蛋白基无麸质面团粉质性能,提高玉米醇溶蛋白的表面疏水性,增加β-折叠占比,优化玉米醇溶蛋白基面条蒸煮品质。     

揉混时间对酸化面团中玉米醇溶蛋白的影响

以玉米醇溶蛋白（zein）、玉米淀粉、沙蒿胶为原料,制备了zein基无麸质模拟面团（Z面团）。基于粉质检测,比较了不同乳酸含量的zein模拟面团在揉混成型时（扭矩达1.1Nm;设为ZS面团）与揉混12 min时（设为ZL面团）面团的揉混扭矩、水分组成情况,以及蛋白分布状态;研究耐揉混面团的最佳乳酸添加量,通过一定时长揉混作用下,不同乳酸含量的面团中zein理化性质,讨论了经长时间揉混面团逐渐弱化的原因,为zein模拟面团的加工、相关谷物制品的制备提供参考。结果表明,添加少量乳酸能促使zein在面团中构建起蛋白质网络,但长时间的揉混会导致酸化面团强度下降,破坏面团中zein网络连贯性,降低zein对淀粉颗粒包裹水平,面团中弱结合水占比下降、游离水占比增加,zein发生脱酰胺反应、表面疏水性上升、相对分子质量下降。面团经长时间的揉混逐渐弱化,是因为揉混作用会扩大乳酸对面团中zein的作用效果,促使蛋白质表面疏水性增加、蛋白质碎片化,进而导致zein网络连贯性下降。     

Effect of plasticizing sugars on rheological and thermal properties of zein resins and mechanical properties of zein films

Zein is the most important protein in corn. Zein has good film forming properties. One of the film forming methods is production of zein resin and then thermomolding by hot press. Pure zein film is very brittle. Plasticizers can improve mechanical and film making properties of zein. In this research, sugars (fructose, galactose and glucose) were used as plasticizers and rheological properties of zein resin were studied by dynamic oscillatory tests for determination of plasticization effectiveness. Effect of plasticizers on thermal properties of resins was investigated by DSC at −100 to 150 °C. No crystallization and melting peaks related to zein and plasticizers were observed. As well as there was not significant difference at glass transition temperature between zein resins containing various sugars. Zein films were prepared from zein resins by rolling and hot press and then mechanical properties of films were measured. Films containing galactose had better tensile properties than other films and showed higher tensile strength, strain at break, and Young modulus than films containing fructose and glucose.     

抗菌性玉米醇溶蛋白/壳聚糖复合膜的制备与性质

采用分步法,先配制壳聚糖/醋酸/乙醇溶液体系,再向其中加入玉米醇溶蛋白,最后利用流延法制成玉米醇溶蛋白/壳聚糖(zein/chitosan,Z/C)复合膜,探讨壳聚糖质量分数对Z/C复合膜理化性质与抗菌特性的影响。结果表明:在壳聚糖质量分数为2%~8%范围内,混合溶液的黏度和电导率随壳聚糖质量分数变化成阶梯状变化,且壳聚糖的添加对复合膜性质有显著影响,Z/C复合膜的断后伸长率从1.00%提高到6.67%,接触角从65.97°减小到53.61°,水蒸气透过率从5.23 g·m/(m2·h·Pa)提高到9.16 g·m/(m2·h·Pa);扫描电子显微镜观察,复合后薄膜保持光滑、均一;大肠杆菌抑菌实验表明添加壳聚糖使复合膜具有较强的抗菌特性。     

Effect of moderate electric fields in the permeation properties of chitosan coatings

Edible films and coatings can provide additional protection for food, while being a fully biodegradable, environmentally friendly packaging system. Preliminary works have shown that the presence of a moderate electric field during the preparation of chitosan coating solutions may influence e.g. their transport properties. If such effect is confirmed, moderate electric fields could be used to tailor edible films and coatings for specific applications. The aim of this work was to determine the effect of field strength on functional properties of chitosan coatings (obtained from lobster from the Cuban coasts). Four different field strengths were tested (50, 100, 150, 200 V cm⁻¹) and, for each electric field treatment, the water vapor, oxygen and carbon dioxide permeabilities of the films formed were determined, together with their color, opacity and solubility in water. The surface microstructure of the films was analyzed using atomic force microscopy (AFM).The results showed that ohmic heating had statistically significant effects on film's physical properties and structure. In general, the most pronounced effect of the field strength was observed for treatments made at 100 V cm⁻¹ or higher, a positive correlation being found between the water vapor, oxygen and carbon dioxide permeability coefficients and field strength. The AFM results show that the surface of chitosan films is much more uniform when an electric field is applied, which may be related with a more uniform gel structure leading to the differences observed in terms of transport properties.     

不同类型电场辅助冰温贮藏对生鲜猪肉保水性的影响

为研究不同类型电场辅助冰温贮藏对生鲜猪肉保水性的影响,以猪背最长肌为研究对象,对比分析在交变电场辅助冰温、静电场辅助冰温及普通冰温（对照组）贮藏条件下生鲜猪肉水分含量、贮藏损失、蒸煮损失、横向弛豫时间T2、肌原纤维蛋白表面疏水性及结构的变化。结果表明：交变电场和静电场处理组生鲜猪肉水分含量和不易流动水弛豫峰面积比例P21显著高于对照组（P＜0.05）,贮藏损失、蒸煮损失、肌原纤维蛋白表面疏水性及自由水弛豫峰面积比例P22显著低于对照组（P＜0.05）,但交变电场处理组和静电场处理组各指标之间无显著差异。综上,输出电压为3 300～4 000 V所产生的交变电场和输出电压为3 800 V所产生的静电场辅助冰温贮藏均可延缓肌原纤维蛋白降解及不易流动水向自由水转化,从而提高生鲜猪肉的保水性,降低贮藏过程中的汁液损失。     

干法糖基化改性玉米醇溶蛋白产物的物化特性及在胶囊壳中的应用

利用菊粉对玉米醇溶蛋白进行干法糖基化改性,通过SDS-PAGE凝胶电泳、热分析(DSC)、傅里叶红外和扫描电子显微镜等手段考察改性前后蛋白的变化。结果表明:SDSPAGE电泳谱图可确认玉米醇溶蛋白与菊粉进行了有效的接合;傅里叶红外分析也确认糖基化改性后,玉米醇溶蛋白以共价键的形式接入了菊粉糖分子;DSC分析所得玉米醇溶蛋白膜及其改性产物膜的变性温度分别为188.47,194.02℃;扫描电子显微镜发现改性后膜的表面更加平整,无孔洞。参照《中华人民共和国药典(2015版)》中关于明胶胶囊壳的相关检测指标,对菊粉改性的玉米醇溶蛋白产物制成胶囊壳进行测定,该产品各项指标均达到要求。     

Simple and complex coacervation methods for the nanoencapsulation of Rosa damascena mill L. anthocyanin in zein/potato starch: A new approach to enhance antioxidant and thermal properties

The structure and antioxidant properties of zein and potato starches as well as the stability of anthocyanins strongly depend on the pH. However, due to the stability of anthocyanins in at acidic medium, their encapsulation has been limited to low pHs. In the present work, an encapsulation of anthocyanins extracted from Rosa damascena mill L. (as a model) into zein, starch, and their binary mixtures by simple and complex coacervation methods over a wide range of pH (especially higher pHs), and different encapsulating agent doses and different initial volumes of anthocyanin were studied in order to obtain new conditions for the preservation of anthocyanins and to improve the antioxidant activities of zein and potato starches. High levels of antioxidant activity and encapsulation efficiency for zein/starch/anthocyanin nanocapsules and maximum antioxidant activity for zein/starch nanocapsules (without anthocyanin) were obtained at pHs 8 and 2, respectively. Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray powder diffraction, and thermal gravimetric analysis techniques were used to analyze simple and complex coacervates biopolymer interactions, morphology, and thermal stability. The size of zein nanocapsules (283–366 nm) decreased in the range of 50–175 nm after the encapsulation of anthocyanin (pH 8), which makes them suitable for drug delivery processes. The prepared nanocapsules showed a high scavenging ability.     

Water vapor and oxygen-barrier performance of corn–zein coated polypropylene films

A novel corn–zein coating structure on polypropylene (PP) films was developed to examine its feasibility as an alternative water vapor and oxygen-barrier for flexible packaging industry. The barrier properties of the resulting films were evaluated as affected by coating formulation (solvent, corn–zein, plasticizer concentration and plasticizer type). Corn–zein with different amounts (5% and 15%) was dissolved in 70% and 95% aqueous ethanol solution at 50 °C, respectively. Solutions of corn–zein plasticized by polyethylene glycol (PEG) and glycerol (GLY) with various levels (20% and 50%) were applied on corona-discharged-treated PP by using solvent-casting method. The significant improvements in water vapor and oxygen-barrier properties of uncoated PP films were obtained with corn–zein coating. Water vapor permeability (WVP) of the coated films decreased significantly with increasing corn–zein concentration. The application of plasticized corn–zein coating on PP films showed nearly more than three order of reduction in oxygen permeability (OP). The high water vapor and oxygen-barriers were obtained for films coated with coating formulation consisting of higher amounts of corn–zein plasticized by GLY. The statistical analysis defined the key parameters of coating formulation that had major effect on the final properties of coated PP films as corn–zein, plasticizer concentration, and plasticizer type.     

Wettability, surface microstructure and mechanical properties of films based on phosphorus oxychloride-treated zein

BACKGROUND: Zein, the predominant protein in corn, has been extensively studied as an alternative packaging material in edible and biodegradable films. However, films made from 100% zein are brittle under normal conditions. The aim of this investigation was to improve the film‐forming properties of zein by chemical phosphorylation. The surface hydrophobicity, surface microstructure and mechanical properties of films based on untreated and phosphorus oxychloride (POCl₃)‐treated zein were evaluated and compared. The effect of POCl₃ treatment on the rheological properties of zein solutions was also studied. RESULTS: POCl₃ treatment, especially at pH 7 and 9, led to an increase in the apparent viscosity of zein solutions. Atomic force microscopy (AFM) analysis showed that the film based on POCl₃‐treated zein at pH 7 had a stone‐like surface microstructure with a higher roughness (R_q) than the untreated zein film. The AFM data may partially account for the phenomenon that this film exhibited high surface hydrophobicity (H₀). POCl₃ treatment diminished the tensile strength (TS) of zein films from 4.83–6.67 to 1.3–2.29 MPa. However, the elongation at break (EAB) of the films at pH 7 and 9 increased from 3.0–4.5% (control film) to 150.1–122.7% (POCl₃‐treated film), indicating the potential application of zein films in wrapping foods or in non‐food industries such as sugar, fruit or troche that need good extension packing materials. CONCLUSION: The data presented suggest that the properties of zein films could be modulated by chemical phosphorylation treatment with POCl₃ at an appropriate pH value. Copyright © 2011 Society of Chemical Industry     

Physical performance of biodegradable films intended for antimicrobial food packaging

Antimicrobial films were prepared by including enterocins to alginate, polyvinyl alcohol (PVOH), and zein films. The physical performance of the films was assessed by measuring color, microstructure (SEM), water vapor permeability (WVP), and tensile properties. All studied biopolymers showed poor WVP and limited tensile properties. PVOH showed the best performance exhibiting the lowest WVP values, higher tensile properties, and flexibility among studied biopolymers. SEM of antimicrobial films showed increased presence of voids and pores as a consequence of enterocin addition. However, changes in microstructure did not disturb WVP of films. Moreover, enterocin-containing films showed slight improvement compared to control films. Addition of enterocins to PVOH films had a plasticizing effect, by reducing its tensile strength and increasing the strain at break. The presence of enterocins had an important effect on tensile properties of zein films by significantly reducing its brittleness. Addition of enterocins, thus, proved not to disturb the physical performance of studied biopolymers. Development of new antimicrobial biodegradable packaging materials may contribute to improving food safety while reducing environmental impact derived from packaging waste. Practical Application: Development of new antimicrobial biodegradable packaging materials may contribute to improving food safety while reducing environmental impact derived from packaging waste.     

Use of Electrospinning to Develop Antimicrobial Biodegradable Multilayer Systems: Encapsulation of Cinnamaldehyde and Their Physicochemical Characterization

In this work, three active bio-based multilayer structures, using a polyhydroxybutyrate-co-valerate film with a valerate content of 8 % (PHBV8) as support, were developed. To this end, a zein interlayer with or without cinnamaldehyde (CNMA) was directly electrospun onto one side of the PHBV8 film and the following systems were developed: (1) without an outer layer; (2) using a PHBV8 film as outer layer; and (3) using an alginate-based film as outer layer. These multilayer structures were characterized in terms of water vapour and oxygen permeabilities, transparency, intermolecular arrangement and thermal properties. The antimicrobial activity of the active bio-based multilayer systems and the release of CNMA in a food simulant were also evaluated. Results showed that the presence of different outer layers reduced the transport properties and transparency of the multilayer films. The active bio-based multilayer systems showed antibacterial activity against Listeria monocytogenes being the multilayer structure prepared with CNMA and PHBV outer layers (PHBV + zein/CNMA + PHBV) the one that showed the greater antibacterial activity. The release of CNMA depended on the multilayer structures, where both Fick’s and Case II transport—polymer relaxation explained the release of CNMA from the multilayer systems.Overall, the deposition of electrospun CNMA-loaded zein fibres on a PHBV8 layer is a promising methodology for the development of active bio-based multilayer systems, with a great potential for food packaging applications.     

Electric field effects on β-lactoglobulin thermal unfolding as a function of pH – Impact on protein functionality

The presence of moderate electric fields (MEF) during ohmic heating (OH) treatment of whey protein systems have demonstrated potential to change physicochemical and functional properties, like aggregation rate and extension or viscoelastic behaviour. However, the specific action of MEF upon the molecular structure of proteins, particularly during thermal processing has yet to be clarified. The effects of MEF in pure fractions of β-lactoglobulin (β-lg) under non-aggregating conditions (low concentration and ionic strength), were investigated in this work. Protein samples were identically heat-treated through conventional and OH methods and at different pH values. β-lg's structural features were characterized by evaluation of secondary structure distribution and local conformational changes using techniques such as circular dichroism, intrinsic and extrinsic fluorescence and free thiol groups reactivity. It was confirmed that MEF affects β-lg upon thermal unfolding, resulting in distinctive structural features, surface hydrophobicity and SH reactivity. The mechanism of action is probably related with the molecular motion induced by the oscillating electric field and is more pronounced at neutral pH, where β-lg is more susceptible to thermal structural changes. These results contribute to a better understanding of OH processing and its effects in food matrices reinforce the possibility of using MEF as a toll to change protein functionality.Industrial relevanceOhmic heating is an emerging technology and is being established as reference method for processing protein-rich food such as dairy and egg products. Non-thermal effects of the applied electric fields during ohmic heating have been addressed but few works deal with their real impact in structural and molecular properties of food proteins with high biological value.In this work demonstrated that the presence of an electric field during ohmic heating processing influences structural aspects of beta-lactoglobulin. This knowledge plays an important role on process design (i.e. pasteurization binomials and fouling control) and product quality because these proteins play an essential role in food's nutritional and organoleptic properties, as well as on functionality, allergenicity and stability aspects.