壳聚糖基活性包装膜的性能及其在食品贮藏中应用的研究
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摘要
近年来，随着人们对食品安全和食品包装关注的不断提高，食品活性包装逐渐发展起来，以期保证食品的安全，维持食品的质量，延长食品的货架期。目前，活性包装的研究热点之一是以天然可再生、生物可降解的材料制备食品包装，并在其中添加抗氧化、抗菌和营养等功能性成分，赋予包装原本不具有的新功能。
壳聚糖是由甲壳类动物外壳中提取的甲壳素经过脱乙酰化得到的一种天然聚合物。由于壳聚糖具有生物可降解性、生物相容性、一定的抑菌性和无毒等特点，所以在食品活性包装领域有潜在的应用前景。但是，壳聚糖不具有抗氧化性，而且抑菌谱较窄，这些弱点限制了其在食品活性包装中的应用范围。
本论文以茶多酚和金银花提取物作为功能性添加剂，通过流延法制备了壳聚糖/茶多酚复合膜、壳聚糖/金银花提取物复合膜以及壳聚糖/茶多酚/金银花提取物三元复合膜，以期提高壳聚糖的抗氧化和抗菌等性能。对壳聚糖基复合膜与食品包装相关的性能进行了表征，并将壳聚糖基复合膜应用于大豆油和酱牛肉的储存，考察了壳聚糖基复合膜在实际使用中的保鲜效果，为研发基于壳聚糖的食品活性包装膜提供了基础数据和技术支撑。
将茶多酚加入到壳聚糖中制备了壳聚糖/茶多酚复合膜。研究结果表明，壳聚糖/茶多酚复合膜的抗氧化活性随茶多酚添加量的增加而显著提高，但是，随着时间的推移，因复合膜中酚类化合物的氧化，其抗氧化活性逐渐降低。添加茶多酚后，壳聚糖/茶多酚复合膜的阻湿性能显著提高。随着茶多酚添加量的增加，壳聚糖/茶多酚复合膜的抑菌能力和力学性能下降，溶胀度和溶解度上升，外观呈现出红褐色，透明度下降。
在壳聚糖中添加金银花提取物制备了壳聚糖/金银花提取物复合膜。研究结果表明，相比于壳聚糖膜，壳聚糖/金银花提取物复合膜抑制大肠杆菌的能力明显提高。此外，添加金银花提取物后，壳聚糖/金银花提取物复合膜的抗氧化性能和阻湿性能也显著增强。但是，其抗氧化性逊于壳聚糖/茶多酚复合膜。随着金银花提取物添加量的增加，壳聚糖/金银花提取物复合膜的力学性能和溶胀度明显下降，溶解度上升，外观呈现出灰褐色，透明度下降。
将茶多酚和金银花提取物分别以不同配比加入到壳聚糖中制备了壳聚糖/茶多酚/金银花提取物三元复合膜。研究结果表明，壳聚糖/茶多酚/金银花提取物三元复合膜的抗氧化活性随茶多酚比例的提高而提高，而其抗菌能力则随金银花提取物比例的提高而增强。当茶多酚和金银花提取物的配比为1:1时，壳聚糖/茶多酚/金银花提取物三元复合膜具有较高的拉伸强度、弹性模量和水蒸气透过系数以及较低的溶解度。随着茶多酚配比的减小和金银花提取物配比的增大，壳聚糖/茶多酚/金银花提取物三元复合膜的断裂伸长率、溶胀度和透明度显著下降。
将壳聚糖基复合膜用于大豆油的保存，考察了其抑制大豆油氧化的效果。结果表明，壳聚糖基复合膜可以有效抑制大豆油的氧化。各种壳聚糖基复合膜抑制大豆油氧化的效果为：壳聚糖/茶多酚/金银花提取物三元复合膜>壳聚糖/茶多酚复合膜>壳聚糖/金银花提取物复合膜>壳聚糖膜。茶多酚和金银花提取物在提高壳聚糖膜的抗氧化性方面有协同增效的作用。添加不同茶多酚和金银花提取物配比（TP:HFE）的壳聚糖/茶多酚/金银花提取物三元复合膜抑制大豆油氧化的效果为：5:1>3:1>1:1>1:3>1:5，其中茶多酚起主要作用。
将壳聚糖基复合保鲜膜用于肉制品的保鲜，考察了其对酱牛肉的保鲜效果。结果表明，壳聚糖基复合膜在保护酱牛肉的气味和色泽、减少粘液形成以及抑制细菌繁殖方面效果非常明显。各种壳聚糖基复合膜对酱牛肉的保鲜效果为：壳聚糖/茶多酚/金银花提取物三元复合膜>壳聚糖/金银花提取物复合膜>壳聚糖/茶多酚复合膜>壳聚糖膜。茶多酚和金银花提取物在维护酱牛肉的感官品质和抑制微生物生长方面有协同增效的作用。添加不同茶多酚和金银花提取物配比（TP:HFE）的壳聚糖/茶多酚/金银花提取物三元复合膜对酱牛肉的保鲜效果为：1:5>1:3>1:1>3:1>5:1，其中金银花提取物起主要作用。
With increasing concerns on food safety and food packagings, active food packagingshave been developed in recent years to ensure safety of foods, maintain food quality andextend shelf life of foods. Currently, one of the research hotpoints for active packagings is toprepare food packagings by using natural renewable and biodegradable materials and endowthe packagings new functions through adding functional additives, such as antioxidants,antibacterial agents and nutrition, etc.
Chitosan, a natural carbohydrate copolymer yielded from deacetylation of chitin, is abiodegradable, biocompatible, and non-toxic polysaccharide. Due to its antimicrobialactivity, chitosan has a great potential for applications in food packaging. Although chitosanis a promising biopolymer for active food packaging, it does not have significant antioxidantactivity and has narrow antibacterial spectrum. These weaknesses limit its applications.Improvements of antioxidant activity and antibacterial activity could expand applications ofchitosan in active food packagings.
In this thesis, tea polyphenols (TP) and honeysuckle flowers extract (HFE) were used asadditives, chitosan/TP films, chitosan/HFE films and chitosan/TP/HFE composite films wereprepared through casting method aiming at enhancing the antioxidant activity andantimicrobial activity of chitosan films. The properties related to food packaging of theprepared chitosan based films were characterized. The prepared chitosan based films wereapplied to storages of soybean oil and spiced beef to investigate their actual effectiveness.The results of this study could provide basic data and technical support for developingchitosan based active food packagings.
Chitosan films incorporated with different amounts of TP were prepared. The results showed that the antioxidant activity of the chitosan/TP films increased with increasing of TPconcentration, but the antioxidant activity of the chitosan/TP films declined with time due tooxidation of phenolic compounds in the films. After the addition of TP, moisture barrierperformance of the chitosan/TP films was significantly increased. With increasing of TPconcentration, the antimicrobial activity, mechanical properties and transparence of thechitosan/TP films decreased, while swelling ratio and solubility increased. Meanwhile, theincorporation of TP gave rise to the films red-brown appearance.
Chitosan films incorporated with different amounts of HFE were prepared. The resultsindicated that the ability to inhibit Escherichia coli of the chitosan/HFE films wassignificantly enhanced. After the addition of HFE, antioxidant activity and moisture barrierperformance of the chitosan/HFE films were significantly increased. But, the antioxidantactivity of the chitosan/HFE films was lower than that of the chitosan/TP films. Withincreasing of HFE concentration, mechanical properties, swelling ratio, and transparence ofthe chitosan/HFE film declined, while solubility increased. Meanwhile, the incorporation ofHFE gave rise to the films taupe appearance.
Chitosan films incorporated TP and HFE at different ratios were prepared. The resultsshowed that antioxidant activity of the chitosan/TP/HFE composite films increased withincreasing of TP proportion, while the antimicrobial activity of the chitosan/TP/HFEcomposite films increased with increasing of HFE proportion. When the ratio of TP to HFEwas1:1, the chitosan/TP/HFE composite films have higher tensile strength, elastic modulusand water vapor permeability as well as lower solubility. With decreasing of TP proportionand increasing of HFE proportion, elongation at break, swelling ratio, and transparence ofchitosan/TP/HFE composite films declined.
The chitosan based films were used for soybean oil storage to investigate effectivenessof preserving soybean oil from oxidation. The results showed that the chitosan based filmscan effectively inhibit oxidation of soybean oil. The effectiveness of inhibiting oxidation forthe chitosan based films follows the order: chitosan/TP/HFE composite films> chitosan/TPfilms> chitosan/HFE films> chitosan film. Incorporation TP and HFE into chitosan has synergetic effect in enhancing antioxidant activity of chitosan. For the chitosan/TP/HFEcomposite films with different ratios of TP:HFE the effectiveness of inhibiting oxidationfollows the order:5:1>3:1>1:1>1:3>1:5, in which TP plays important role.
The chitosan based films were used to preserve spiced beef. It was found that sampleswrapped with chitosan based composite films (chitosan/TP, chitosan/HFE, andchitosan/TP/HFE) showed lower changes in odor, discoloration, slime formation, overallacceptability and less microbial growth than those wrapped with chitosan film and controlone. The fresh-keeping effectiveness of chitosan based composite films follows the order:chitosan/TP/HFE composite films> chitosan/HFE film> chitosan/TP film> chitosan film.Incorporation TP and HFE into chitosan has synergetic effect in inhibiting microbial growthand extending the shelf life of the spiced beef. For the chitosan/TP/HFE composite filmswith different ratios of TP:HFE, the fresh-keeping effectiveness for spiced beef follows theorder:1:5>1:3>1:1>3:1>5:1, in which HFE plays important role.
壳聚糖是由甲壳类动物外壳中提取的甲壳素经过脱乙酰化得到的一种天然聚合物。由于壳聚糖具有生物可降解性、生物相容性、一定的抑菌性和无毒等特点，所以在食品活性包装领域有潜在的应用前景。但是，壳聚糖不具有抗氧化性，而且抑菌谱较窄，这些弱点限制了其在食品活性包装中的应用范围。
本论文以茶多酚和金银花提取物作为功能性添加剂，通过流延法制备了壳聚糖/茶多酚复合膜、壳聚糖/金银花提取物复合膜以及壳聚糖/茶多酚/金银花提取物三元复合膜，以期提高壳聚糖的抗氧化和抗菌等性能。对壳聚糖基复合膜与食品包装相关的性能进行了表征，并将壳聚糖基复合膜应用于大豆油和酱牛肉的储存，考察了壳聚糖基复合膜在实际使用中的保鲜效果，为研发基于壳聚糖的食品活性包装膜提供了基础数据和技术支撑。
将茶多酚加入到壳聚糖中制备了壳聚糖/茶多酚复合膜。研究结果表明，壳聚糖/茶多酚复合膜的抗氧化活性随茶多酚添加量的增加而显著提高，但是，随着时间的推移，因复合膜中酚类化合物的氧化，其抗氧化活性逐渐降低。添加茶多酚后，壳聚糖/茶多酚复合膜的阻湿性能显著提高。随着茶多酚添加量的增加，壳聚糖/茶多酚复合膜的抑菌能力和力学性能下降，溶胀度和溶解度上升，外观呈现出红褐色，透明度下降。
在壳聚糖中添加金银花提取物制备了壳聚糖/金银花提取物复合膜。研究结果表明，相比于壳聚糖膜，壳聚糖/金银花提取物复合膜抑制大肠杆菌的能力明显提高。此外，添加金银花提取物后，壳聚糖/金银花提取物复合膜的抗氧化性能和阻湿性能也显著增强。但是，其抗氧化性逊于壳聚糖/茶多酚复合膜。随着金银花提取物添加量的增加，壳聚糖/金银花提取物复合膜的力学性能和溶胀度明显下降，溶解度上升，外观呈现出灰褐色，透明度下降。
将茶多酚和金银花提取物分别以不同配比加入到壳聚糖中制备了壳聚糖/茶多酚/金银花提取物三元复合膜。研究结果表明，壳聚糖/茶多酚/金银花提取物三元复合膜的抗氧化活性随茶多酚比例的提高而提高，而其抗菌能力则随金银花提取物比例的提高而增强。当茶多酚和金银花提取物的配比为1:1时，壳聚糖/茶多酚/金银花提取物三元复合膜具有较高的拉伸强度、弹性模量和水蒸气透过系数以及较低的溶解度。随着茶多酚配比的减小和金银花提取物配比的增大，壳聚糖/茶多酚/金银花提取物三元复合膜的断裂伸长率、溶胀度和透明度显著下降。
将壳聚糖基复合膜用于大豆油的保存，考察了其抑制大豆油氧化的效果。结果表明，壳聚糖基复合膜可以有效抑制大豆油的氧化。各种壳聚糖基复合膜抑制大豆油氧化的效果为：壳聚糖/茶多酚/金银花提取物三元复合膜>壳聚糖/茶多酚复合膜>壳聚糖/金银花提取物复合膜>壳聚糖膜。茶多酚和金银花提取物在提高壳聚糖膜的抗氧化性方面有协同增效的作用。添加不同茶多酚和金银花提取物配比（TP:HFE）的壳聚糖/茶多酚/金银花提取物三元复合膜抑制大豆油氧化的效果为：5:1>3:1>1:1>1:3>1:5，其中茶多酚起主要作用。
将壳聚糖基复合保鲜膜用于肉制品的保鲜，考察了其对酱牛肉的保鲜效果。结果表明，壳聚糖基复合膜在保护酱牛肉的气味和色泽、减少粘液形成以及抑制细菌繁殖方面效果非常明显。各种壳聚糖基复合膜对酱牛肉的保鲜效果为：壳聚糖/茶多酚/金银花提取物三元复合膜>壳聚糖/金银花提取物复合膜>壳聚糖/茶多酚复合膜>壳聚糖膜。茶多酚和金银花提取物在维护酱牛肉的感官品质和抑制微生物生长方面有协同增效的作用。添加不同茶多酚和金银花提取物配比（TP:HFE）的壳聚糖/茶多酚/金银花提取物三元复合膜对酱牛肉的保鲜效果为：1:5>1:3>1:1>3:1>5:1，其中金银花提取物起主要作用。
With increasing concerns on food safety and food packagings, active food packagingshave been developed in recent years to ensure safety of foods, maintain food quality andextend shelf life of foods. Currently, one of the research hotpoints for active packagings is toprepare food packagings by using natural renewable and biodegradable materials and endowthe packagings new functions through adding functional additives, such as antioxidants,antibacterial agents and nutrition, etc.
Chitosan, a natural carbohydrate copolymer yielded from deacetylation of chitin, is abiodegradable, biocompatible, and non-toxic polysaccharide. Due to its antimicrobialactivity, chitosan has a great potential for applications in food packaging. Although chitosanis a promising biopolymer for active food packaging, it does not have significant antioxidantactivity and has narrow antibacterial spectrum. These weaknesses limit its applications.Improvements of antioxidant activity and antibacterial activity could expand applications ofchitosan in active food packagings.
In this thesis, tea polyphenols (TP) and honeysuckle flowers extract (HFE) were used asadditives, chitosan/TP films, chitosan/HFE films and chitosan/TP/HFE composite films wereprepared through casting method aiming at enhancing the antioxidant activity andantimicrobial activity of chitosan films. The properties related to food packaging of theprepared chitosan based films were characterized. The prepared chitosan based films wereapplied to storages of soybean oil and spiced beef to investigate their actual effectiveness.The results of this study could provide basic data and technical support for developingchitosan based active food packagings.
Chitosan films incorporated with different amounts of TP were prepared. The results showed that the antioxidant activity of the chitosan/TP films increased with increasing of TPconcentration, but the antioxidant activity of the chitosan/TP films declined with time due tooxidation of phenolic compounds in the films. After the addition of TP, moisture barrierperformance of the chitosan/TP films was significantly increased. With increasing of TPconcentration, the antimicrobial activity, mechanical properties and transparence of thechitosan/TP films decreased, while swelling ratio and solubility increased. Meanwhile, theincorporation of TP gave rise to the films red-brown appearance.
Chitosan films incorporated with different amounts of HFE were prepared. The resultsindicated that the ability to inhibit Escherichia coli of the chitosan/HFE films wassignificantly enhanced. After the addition of HFE, antioxidant activity and moisture barrierperformance of the chitosan/HFE films were significantly increased. But, the antioxidantactivity of the chitosan/HFE films was lower than that of the chitosan/TP films. Withincreasing of HFE concentration, mechanical properties, swelling ratio, and transparence ofthe chitosan/HFE film declined, while solubility increased. Meanwhile, the incorporation ofHFE gave rise to the films taupe appearance.
Chitosan films incorporated TP and HFE at different ratios were prepared. The resultsshowed that antioxidant activity of the chitosan/TP/HFE composite films increased withincreasing of TP proportion, while the antimicrobial activity of the chitosan/TP/HFEcomposite films increased with increasing of HFE proportion. When the ratio of TP to HFEwas1:1, the chitosan/TP/HFE composite films have higher tensile strength, elastic modulusand water vapor permeability as well as lower solubility. With decreasing of TP proportionand increasing of HFE proportion, elongation at break, swelling ratio, and transparence ofchitosan/TP/HFE composite films declined.
The chitosan based films were used for soybean oil storage to investigate effectivenessof preserving soybean oil from oxidation. The results showed that the chitosan based filmscan effectively inhibit oxidation of soybean oil. The effectiveness of inhibiting oxidation forthe chitosan based films follows the order: chitosan/TP/HFE composite films> chitosan/TPfilms> chitosan/HFE films> chitosan film. Incorporation TP and HFE into chitosan has synergetic effect in enhancing antioxidant activity of chitosan. For the chitosan/TP/HFEcomposite films with different ratios of TP:HFE the effectiveness of inhibiting oxidationfollows the order:5:1>3:1>1:1>1:3>1:5, in which TP plays important role.
The chitosan based films were used to preserve spiced beef. It was found that sampleswrapped with chitosan based composite films (chitosan/TP, chitosan/HFE, andchitosan/TP/HFE) showed lower changes in odor, discoloration, slime formation, overallacceptability and less microbial growth than those wrapped with chitosan film and controlone. The fresh-keeping effectiveness of chitosan based composite films follows the order:chitosan/TP/HFE composite films> chitosan/HFE film> chitosan/TP film> chitosan film.Incorporation TP and HFE into chitosan has synergetic effect in inhibiting microbial growthand extending the shelf life of the spiced beef. For the chitosan/TP/HFE composite filmswith different ratios of TP:HFE, the fresh-keeping effectiveness for spiced beef follows theorder:1:5>1:3>1:1>3:1>5:1, in which HFE plays important role.
引文
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