复合改性淀粉膜材料工艺优化与性能分析

本文研究了酶解脱支和醚化复合改性淀粉为基材制备了淀粉膜,在此基础上添加其他助剂逐渐提升淀粉膜材料的性能,利用现代分析仪器解析其结构特征并初步探讨相关机理。通过优化实验确定了淀粉膜材料工艺参数：复合改性淀粉材料浓度为3%,甘油含量为30%,料液温度为95 ℃,柠檬酸含量为10%时,制备的复合改性淀粉膜材料性能较好,此时淀粉膜的抗拉强度为4.11 MPa,断裂伸长率为38%,提高了45%,水蒸气透过系数为0.51 g?mm/(m2?h?kPa),降低了39%。结构分析结果表明淀粉膜体系具有较为开放的交联网络结构,淀粉链优先与柠檬酸与甘油形成的酯结合,此外柠檬酸的水解作用会导致体系网络结构减弱。因此,添加柠檬酸可有效改善复合改性淀粉膜材料的机械性能和阻隔性能,制备出综合性能优良的复合膜,为淀粉基食品包装应用研究提供了理论依据。     

Effects of storage conditions and acid solvent types on structural,mechanical and physical properties of kudzu starch (Pueraria lobata)‐chitosan composite films

Effects of acid solvents (acetic, lactic and malic acid) on properties of kudzu starch‐chitosan composite films were evaluated at −20 or 25°C during storage of 60 days. The yellowness of films enhanced, whereas water content and water vapour permeability of films declined with increasing storage time. Tensile strength of films choosing acetic and lactic acid as solvents, and solubility of all the films increased within 30 days thereafter decreased. Storage temperature had no impact on X‐ray diffraction, water content and solubility. Under the same storage conditions, the film using acetic acid as solvent presented the strongest mechanical property, the smallest solubility and the lightest colour. The film made from lactic acid solution was the most flexible and the yellowiest. The film with malic acid solvent showed the highest ordering degree, the lowest water content and the best water barrier property.     

Physicochemical,Microstructural, and Antibacterial Properties of β‐Chitosan and Kudzu Starch Composite Films

Abstract: This study investigated physicochemical, microstructural, and antibacterial properties of β‐chitosan–kudzu starch composite films with addition of 0%, 20%, 60%, or 100% kudzu starch (w starch/w chitosan) in 1% chitosan solution. Molecular interactions between chitosan and kudzu starch and the crystal structure of the films were also determined. Adding 60% kudzu starch reduced water vapor permeability and solubility of pure β‐chitosan film by about 15% and 20%, respectively, whereas mechanical strength and flexibility of the film were increased about 50% and 25%, respectively. Micrograph showed that β‐chitosan film was totally amorphous, and the composite films generally became rougher with more starch added. Fourier transform infrared and X‐ray diffraction spectra showed that the 2 film‐forming components were compatible with each other. Pure β‐chitosan film resulted in 9.5 and 11.5 log CFU/mL reduction in Escherichia coli and Listeria innocua based on plate count method, respectively. Addition of kudzu starch reduced the antibacterial activity of film, but still achieved 8.3 and 10.3 log CFU/mL reduction in E. coli and L. innocua, respectively when kudzu starch to chitosan weight ratio was 1:1. Reduced antibacterial activity might attribute to the interaction of amino groups in β‐chitosan with the hydroxyl groups in kudzu starch. This study demonstrated that kudzu starch effectively improved water barrier of β‐chitosan film, and the composite films retained strong antibacterial ability. Practical Application: One percent of β‐chitosan containing 60% kudzu starch (w/w chitosan) composite films possessed better mechanical and water barrier properties than pure β‐chitosan films, and showed strong antibacterial activity against both Gram‐positive and Gram‐negative bacteria. The films may be used as wraps or coatings to prolong the shelf life of different foods or other similar applications.     

Effect of surfactants on water barrier and physical properties of tapioca starch/decolorized hsian-tsao leaf gum films

The objective of this research is to enhance the water barrier properties of tapioca starch/dHG edible films by incorporating sucrose ester surfactants with different HLB values. The moisture sorption isotherms, mechanical properties, microstructure and optical character of the resulting films were examined as well. It was found that the water barrier property of starch/dHG films is promoted significantly by surfactants, alongside a decreasing tendency in tensile strength and tensile strain at break. Scanning electron micrographs of the starch/dHG/surfactant composite films revealed the folded (multi-layer) microstructure in contrast to the homogeneous matrix of the control films. Starch/dHG/surfactant composite films show low opacity values. With increasing HLB value of the surfactant, the water vapor permeability and tensile strength of starch/dHG/surfactant composite films decrease. Moreover, the water vapor permeability, tensile strength, strain at break, and equilibrium moisture content of starch/dHG/surfactant composite films decrease when the surfactant content is increased, accompanied by an increasing tendency in opacity value. On the other hand, starch/dHG composite film with an emulsion of surfactant and beeswax shows a lower mechanical strength and significantly higher opacity value with less improvement in water vapor permeability.     

茶多酚/还原石墨烯纳米复合物增强羧甲基壳聚糖薄膜性能的研究

目的 探究茶多酚还原氧化石墨烯(grapheneoxide,GO)的能力,进一步利用茶多酚/还原氧化石墨烯(reduced graphene oxide,RGO)改善羧甲基壳聚糖薄膜的综合性能。方法 首先利用茶多酚的还原性制备出茶多酚/RGO,通过X射线衍射仪(X-ray diffractometry,XRD)和傅里叶变换红外光谱仪(Fourier transform infrared spectrometer,FT-IR)表征验证。进一步以羧甲基壳聚糖为基材,甘油为塑化剂,通过流延法制备出一系列不同茶多酚/RGO含量的复合薄膜,测试其力学性能、阻隔性能、光学性能及热稳定性等,分析不同配比对复合薄膜性能的影响。结果 茶多酚和GO的质量比为2:1时,GO被还原的效果较好;与纯羧甲基壳聚糖膜相比,当茶多酚/RGO含量为2.0%时,复合膜的拉伸强度提高了96.9%;当茶多酚/RGO含量为1.0%时,水蒸气透过率最低,为7.0×10-13 [g·cm/(cm2·s·Pa)];随着茶多酚/RGO的添加,复合薄膜能够阻挡50%以上的310 nm以下的紫外光透过,表现出具有良好的抗紫外性。结论 茶多...     

Properties of low methoxyl pectin‐carboxymethyl cellulose based on montmorillonite nanocomposite films

In this study, the low methoxyl pectin‐carboxymethyl cellulose‐based montmorillonite (LMP‐CMC‐MMT, LCM) nanocomposite films with nine ratios of LMP:CMC (from 10:0 to 0:10) and different MMT contents (1–8 wt%) were prepared. The mechanical properties, colour, opacity and water vapour permeability (WVP) of composite films were investigated. The maximum of tensile strength (TS) of composite films was 39.85 ± 2.51 MPa at LMP:CMC ratio of 4:6 and 4 wt% MMT (LCM47), which indicated the formation of hydrogen bonds between MMT and LMP‐CMC. The reduction of WVP of the LCM47 composite film was 333% of that of the CMC film due to the tortuous path caused by MMT incorporation. LCM composite films had the higher b*‐ and ΔE*‐values and lower L*‐values in comparison with LMP‐CMC (LC) composite films. The LCM composite films showed a decrease in transparency as MMT content increased.     

Emulsion stabilized by starch nanocrystals

The starch nanocrystals made use of in this study were prepared by sulfuric acid hydrolysis of wx maize starch. The stable oil‐in‐water emulsions of 50 vol% paraffin liquid were prepared by using starch nanocrystals as emulsifier when the weight percentage concentration of starch nanocrystal relative to water was above 0.02 wt%. The size of the droplets decreased with the raising of the concentration of starch nanocrystal. These emulsions were very stable to coalescence over months and the creaming of emulsions decreased with the increasing of starch nanocrystal concentration. The surface tension of starch nanocrystal dispersions was found decreased from 71.7 to 45.8 mN/m when the nanocrystal concentration grew from 0.05 to 3.0 wt%. This indicates that starch nanocrystals are surface active particles. Further tests on the emulsifying ability of supernatant of centrifuged starch nanocrystal dispersions and the emulsion stability at the melting temperature of starch nanocrystals confirmed that the emulsions were indeed stabilized by starch nanocrystals.     

Simultaneous Extraction of Carboxylated Cellulose Nanocrystals and Nanofibrils via Citric Acid Hydrolysis—Sustainable Route

In this study, cellulose nanocrystals (CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils (CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose (CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.     

Simultaneous Extraction of Carboxylated Celulose Nanocrystals and Nanofibrils via Citric Acid Hydrolysis——A Sustainable Route

In this study, cellulose nanocrystals(CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils(CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose(CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.     

Physical and Antimicrobial Properties of Compression-Molded Cassava Starch-Chitosan Films for Meat Preservation

Cassava starch-chitosan films were obtained by melt bending and compression molding, using glycerol and polyethylene glycol as plasticizers. Both the starch/chitosan and the polymer/plasticizer ratios were varied in order to analyze their effect on the physical properties of the films. Additionally, the antimicrobial activity of 70:30 polymer:plasticizer films was tested in cold-stored pork meat slices as affected by chitosan content. All film components were thermally stable up to 200 °C, which guaranteed their thermostability during film processing. Starch and chitosan had limited miscibility by melt blending, which resulted in heterogeneous film microstructure. Polyethylene glycol partially crystallized in the films, to a greater extent as the chitosan ratio increased, which limited its plasticizing effect. The films with the highest plasticizer ratio were more permeable to water vapor, less rigid, and less resistant to break. The variation in the chitosan content did not have a significant effect on water vapor permeability. As the chitosan proportion increased, the films became less stretchable, more rigid, and more resistant to break, with a more saturated yellowish color. The incorporation of the highest amount of chitosan in the films led to the reduction in coliforms and total aerobic counts of cold-stored pork meat slices, thus extending their shelf-life.     

基于玫瑰茄花青素的猪肉新鲜度智能指示膜研究

本研究以玫瑰茄花青素提取物制备可检测肉类新鲜度的智能指示膜,分别以淀粉、壳聚糖和聚乙烯醇两两混合作为成膜基底材料,比较分析了不同基底材料复合膜在机械性能、水溶性、微观结构以及颜色稳定性等方面的差异。结果表明:壳聚糖/聚乙烯醇/玫瑰茄花青素复合膜的抗拉强度最大,为98.28 MPa;聚乙烯醇/淀粉/玫瑰茄花青素复合膜的断裂伸长率最大,为88.16%,含水率最低且稳定性最高;扫描电子显微镜结果表明不同基底材料复合膜的微观结构差异较大。将聚乙烯醇/淀粉/玫瑰茄花青素复合膜用于猪肉新鲜度的检测,结果表明:在25℃贮藏环境下,随着时间延长,猪肉的挥发性盐基氮的含量不断上升,36 h后,猪肉的挥发性盐基氮值大于15 mg/100 g,表明猪肉已经腐败,同时复合膜的颜色变成淡紫色,60 h后变为褐色。研究结果可为猪肉新鲜度智能指示膜的研究开发提供参考。     

Physicochemical,Water Vapor Barrier and Mechanical Properties of Corn Starch and Chitosan Composite Films

Biodegradable flexible films were developed from corn starch (CS) and chitosan (CH); their microstructure, mechanical and barrier properties were evaluated. Chitosan and starch blend filmogenic suspensions showed a pseudoplastic behavior, similar to that of chitosan solutions. Smooth surfaces, homogeneous and compact film structures were observed from microstructure studies using scanning electron microscopy (SEM). The addition of glycerol reduced film opacity and increased film solubility of both CS and composite CS‐CH films. Water vapor permeability values of composite CS‐CH films plasticized with glycerol ranged between 3.76 and 4.54× 10⁻¹¹ g s⁻¹ m⁻¹ Pa⁻¹, lower than those of the single component films. CS‐CH films were resistant and their flexibility increased with glycerol addition. Tensile strength values of CS‐CH films were comparable to those of low‐density and high‐density polyethylenes but lower than that obtained for cellophane, however, composite biodegradable films showed lower elongation at break values than the synthetic commercial ones. In conclusion, CS‐CH films can be described as biofilms with a homogeneous matrix, stable structure and interesting water barrier and mechanical properties, with great possibilities of utilization, and with the advantage of biodegradability.     

柚皮纳米微晶纤维素的制备及其用于改进羧甲基淀粉膜性能的研究

以柚皮纤维素为原料,采用硫酸酸解法制备柚皮纳米微晶纤维素,对纳米微晶纤维素的形貌、结晶结构进行表征分析,以复合膜表面形貌、力学性能、水蒸气透过率和透光率为指标,研究不同添加量柚皮纳米微晶纤维素对羧甲基淀粉膜性能的影响。研究发现：柚皮纳米微晶纤维素为长度为60~180 nm,直径为3~15 nm的棒状晶体;X-射线衍射表明其仍为纤维素I型结构;复合膜电镜图光滑平整;纳米微晶纤维素添加量为5%时,复合膜的拉伸强度较原膜提高最大（52.22%）;而随着纳米微晶纤维素的添加,复合膜的断裂伸长率呈下降趋势;当添加量为7%时,复合膜水蒸气透过率降低最大（23%）;纳米微晶纤维素的添加量大于3%时显著降低复合膜的透光率,但未改变原膜在不同波长下的透光率。因此,添加柚皮纳米微晶纤维素能有效改善复合膜的性能,制备出综合性能优良的羧甲基淀粉复合膜。     

不同基材复配紫薯花青素制备智能指示膜及其应用

以马铃薯淀粉（starch,S）、羧甲基纤维素钠（carboxymethyl-cellulose sodium,CMC）以及魔芋葡甘露聚糖（konjac glucomannan,KMG）两两互配为成膜基材,紫薯花青素（P）作为新鲜度指示剂,制备智能指示膜,比较KMG/S/P（KSP）、S/CMC/P（SCP）、KMG/CMC/P（KCP）3 种智能指示膜的力学性能、水分质量分数、水溶性、微观结构、相容性及稳定性等的差异,并运用鱼肉进行初步应用评价。结果表明：SCP膜的抗拉伸强度最高（（15.39±1.15）MPa）、水溶性最低（（24.17±1.21）%）,且颜色稳定性好;而KCP膜断裂伸长率最大（（44.79±1.43）%）;扫描电子显微镜观察结果表明不同智能指示膜微观结构差异明显,其中SCP膜横切面光滑紧密。利用SCP检测鱼肉新鲜度,25 ℃下鱼肉贮藏24 h后挥发性盐基氮含量达15.2 mg/100 g,已经开始腐败,此时智能指示膜显示出浅红色,48 h后变为浅蓝色。因此,SCP膜适合新鲜度检测,且运用紫薯花青素开发稳定的指示膜有良好的应用前景。     

Effect of Molecular Weight,Acid, and Plasticizer on the Physicochemical and Antibacterial Properties of β‐Chitosan Based Films

Abstract: Effects of chitosan molecular weight (1815 and 366 kDa), type of acid (1% acetic, formic, and propionic acid, or 0.5% lactic acid) and plasticizer (0, 25% glycerol or sorbital w/w chitosan) on the mechanical, water barrier, and antibacterial properties of β‐chitosan films were investigated. Tensile strength (TS) of high molecular weight (Hw) films was 53% higher than that of low molecular weight (Lw) ones, acetate, and propionate films had the highest TS (43 and 40 MPa) among tested acids, and plasticizer‐reduced film TS 34%. Film elongation at break (EL) was higher in Hw films than in Lw ones, in which formate and acetate films were the highest (9% and 8%, respectively), and plasticizer increased the film EL 128%. Molecular weight of chitosan did not influence water vapor permeability (WVP) of the films. Acetate and propionate films had lower WVP than other acid types of films, and plasticizer increased film WVP about 35%. No difference was found between glycerol and sorbitol films in terms of film mechanical and water barrier properties. Lw β‐chitosan films showed significant antibacterial activity against E. coli and L. innocua. This study demonstrated that β‐chitosan films are compatible to α‐chitosan films in physicochemical properties and antibacterial activity, yet with simple sample preparation. Practical Application: β‐chitosan based edible films at molecular weight of about 300 kDa showed great antibacterial activity against Gram‐positive and Gram‐negative bacteria. The films have similar mechanical and water barrier properties to α‐chitosan based films at the similar molecular weight, but simple sample preparation procedures and more attractive color. The release of active chitosan fragment from the film matrix acts as an antibacterial agent, making β‐chitosan films suitable as intelligent food wraps or coatings for a wide range of food products to control moisture loss and prevent surface bacterial growth.     

高直链玉米淀粉-壳聚糖复合膜透气透水性能研究

本文以高直链玉米淀粉(HACS)和壳聚糖(CS)为基本材料,甘油为增塑剂,甲基纤维素(MC)为增强剂制备可食性复合膜,研究了高直链玉米淀粉与壳聚糖的配比、甘油的添加量以及甲基纤维素的添加量对复合膜的透气透水性能的影响.结果表明,HACS:CS为2:1时,膜的CO2透过量和O2透过量最低,水蒸气透过量(WVT)也处于较低...     

Preparation and properties of rice starch–chitosan blend biodegradable film

Biodegradable blend films from rice starch–chitosan were developed by casting film-solution on leveled trays. The influence of the ratio of starch and chitosan (2:1, 1.5:1, 1:1, and 0.5:1) on the mechanical properties, water barrier properties, and miscibility of biodegradable blend films was investigated. The biodegradable blend film from rice starch–chitosan showed an increase in tensile strength (TS), water vapor permeability (WVP), lighter color and yellowness and a decreasing elongation at the break (E), and film solubility (FS) after incorporation of chitosan. The introduction of chitosan increased the crystalline peak structure of starch film; however, too high chitosan concentration yielded phase separation between starch and chitosan. The amino group band of the chitosan molecule in the FTIR spectrum shifted from 1541.15 cm⁻¹ in the chitosan film to 1621.96 cm⁻¹ in the biodegradable blend films. These results pointed out that there was a molecular miscibility between these two components. The properties of rice starch–chitosan biodegradable blend film and selected biopolymer and synthetic polymer films were compared; the results demonstrated that rice starch–chitosan biodegradable blend film had mechanical properties similar to the other chitosan films. However, the water vapor permeability of rice starch–chitosan biodegradable blend film was characterized by relatively lower water vapor permeability than chitosan films but higher than polyolefin.     

Paste viscosity of rice starches of different amylose content and carboxymethylcellulose formed by dry heating and the physical properties of their films

Starch modified by combination with sodium carboxymethylcellulose (CMC) has been reported to have improved film properties. In this study, rice starches with different amylose content were heat-treated in a dry state after being impregnated with low or medium-viscosity CMC. Noticeable change was found in pasting properties of the starches after dry heat treatment with CMC. It indicated that crosslinkage occurred between the starch and CMC. The waxy starch showed significant change in viscosity throughout pasting after dry heating with CMC, suggesting that the ester bonds were mostly formed between the hydroxyl groups in amylopectin branches of rice starch and carboxylate acid groups of CMC. Particle size also increased after heat treatment with CMC. The modified starch-based films showed improvement in the tensile strength. Both water vapor and oxygen permeability reduced for the modified starch-based films. Dynamic mechanical analysis (DMA) study showed that the values of G′ of modified starch-based film were higher than those of native starch-based film over the temperature range −40 to 60 °C. The heating process with CMC could be used as a modification method for starch and provide desirable properties of starch-based films.     

不同淀粉的壳聚糖/淀粉复合薄膜结构性能比较

为改善功能因子的生物利用率,本文采用流延法,分别将壳聚糖(分子量150000g/mol)与玉米淀粉、马铃薯淀粉和木薯淀粉制备复合薄膜及其包衣片剂,并通过红外光谱、扫描电镜、拉伸仪、模拟消化实验等手段对壳聚糖/淀粉复合薄膜结构性能进行分析。借助壳聚糖上的-NH3+与淀粉的-OH间的氢键作用,可形成壳聚糖/淀粉复合结构,受淀粉结构差异的影响,复合薄膜中壳聚糖/淀粉复合结构的有序性存在差异,进而影响复合薄膜的机械力学性能、耐酸性及其薄膜包衣片剂的控释性能。其中,复合薄膜CTS/Potato、CTS/Tapioca中壳聚糖/淀粉复合结构的有序性优于复合薄膜CTS/Corn,其耐酸性能良好,在模拟胃液中运转2h,薄膜的损失率分别在18.71%～26.15%、16.14%～19.64%之间。同时,这两种复合薄膜包衣片剂的控释性能亦表现良好,约有60%的模型功能因子可顺利递送至小肠、结肠部位,具有作为药物、活性功能因子小肠、结肠定向释放载体材料的可能。     

Properties of wheat starch film-forming dispersions and films as affected by chitosan addition

In order to evaluate the impact of chitosan on the physical properties of wheat starch–glycerol films, part of the wheat starch was replaced by chitosan, and the effect of composition on the properties of both the films and the film-forming dispersions was studied. The latter became more stable and viscous as the chitosan proportion was increased in the mixture. Both polymers appeared to integrate homogeneously in the film matrix. The combined effect of the glycerol and chitosan proportions affected the mechanical and barrier properties of the films. The tensile strength and elastic modulus of the films were improved as chitosan ratio increased. The oxygen and water vapor permeability slightly increased in line with the amount of chitosan in the blend although the induced differences were very small. Chitosan ratio directly affected the antimicrobial properties of the films, which showed a significant bactericide activity when the chitosan–starch ratio in the film was 50%. Nevertheless, at a starch:chitosan ratio of 80:20, counts of coliforms did not exceed the initial value in the meat after 7 storage days.