不同浓度苹果多酚对壳聚糖复合膜液理化性质的影响

doi:10.3864/j.issn.0578-1752.2018.14.016

摘要/Abstract

摘要： 【目的】以5%（w/v）的壳聚糖（chitosan）溶液和苹果多酚（apple polyphenols，AP）为原料制备一种复合膜液，研究不同多酚添加量对复合膜液抗氧化活性、流变特性及稳定性的影响，以期制备性能良好的可食液体涂膜，为食品保鲜提供理论依据及技术参考。【方法】以浓度为5%的壳聚糖溶液为基质，通过添加苹果多酚，分别制备多酚含量为0.5%、1.0%、1.5%的复合膜液。同时以不添加多酚的膜液作对照。采用磁力搅拌将多酚均匀分散于膜液体系后，对膜液DPPH自由基清除能力、脂质氧化抑制能力、总还原力及OH自由基清除能力进行测定。采用AR-G2流变仪研究不同苹果多酚添加量对复合膜液剪切流变特性的影响。同时采用红外光谱（fourier transform infrared spectrum, FTIR）和X射线衍射（X-ray diffraction）对复合膜液体系中的分子间作用力和晶体结构进行表征。此外，采用Q600SDT热分析系统在50℃—400℃范围内对复合膜液样品进行热稳定性分析。【结果】苹果多酚可显著提高复合膜液的抗氧化活性（P＜0.01），且随苹果多酚添加量增加，复合膜液抗氧化活性也随之增加。当苹果多酚添加量为0.5%时，复合膜液的DPPH自由基清除率、脂质氧化抑制率和OH自由基清除率分别为41.33%、56.32%、35.44%；当苹果多酚添加量增至1.5%时，DPPH自由基清除率、脂质氧化抑制率和OH自由基清除率增加至94.3%、95.9%、98.4%。与同等浓度的BHT（2,6-二叔丁基-4-甲基苯酚）相比，复合膜液具有更高的抗氧化活性（P＜0.01）。此外，随着苹果多酚浓度的增加，复合膜液的总还原力也显著提高。流变学分析结果表明，复合膜液为非牛顿剪切变稀型，随剪切速率增加，复合膜液表观黏度逐渐降低，最终趋于平稳（5 Pa·s）。此外，随苹果多酚添加量增加，复合膜液的非牛顿假塑性流体特征逐渐明显。当苹果多酚添加量为1.5%时，复合膜液动态流变特性由黏性模量主导转变为弹性模量主导。红外光谱和X-RAD分析结果表明，苹果多酚中-OH和壳聚糖分子中的-OH以及-NH₂形成明显的分子间弱作用力，使复合膜液在3 400 cm^-1处的红外吸收峰出现红移，1 545 cm^-1、1 245 cm^-1处的红外吸收峰有轻微减弱，且这种分子间弱作用力降低了壳聚糖的结晶度。热分析结果表明，苹果多酚添加量增加显著提高了复合膜液的热稳定性。对照组的3个阶段质量损失温度为50.8℃、110.7℃、269.9℃，当添加量1.5%苹果多酚时，复合膜液的质量损失温度增至56.6℃、128.7℃、272.9℃。【结论】苹果多酚-壳聚糖复合膜液具有良好的抗氧化能力，且膜液的黏度和热稳定性也较好，可作为一种优良的可食性液体涂膜应用于食品保鲜方面。

关键词: 壳聚糖, 苹果多酚, 抗氧化性, 流变特性, 热稳定性

Abstract: 【Objective】The composite membrane liquids based on chitosan (5%, w/v) and varying apple polyphenols concentrations were developed in this work, and the composite membrane liquids with different polyphenol concentrations were fully investigated including their antioxidant activity, rheological properties and thermal stability. This result could provide theoretical basis for food preservation. 【Method】 The composite membrane liquids were prepared by adding different amounts of apple polyphenols (0.5%, 1.0% and 1.5%, respectively). Besides, effects of the different addition amounts of apple polyphenols on the antioxidant activity of the composite membrane fluids were measured. A controlled-strain rheometer was used to investigate static rheological properties of the composite membrane liquids, including the relationships between G′ and G″. The potential interactions between chitosan and apple polyphenols and the crystal structure of the composite membrane were characterized by Fourier transform infrared spectrum (FTIR) and X-ray diffraction, respectively. In addition, thermogravimetric (TG) and derivative thermogravimetric (DTG) analyses were conducted by using a thermal analysis equipment to characterize the thermal stability of the lyophilized composite membrane samples.【Result】The addition of apple polyphenols could significantly improve the antioxidant activities of the chitosan membrane liquid (P<0.01). The increase of apple polyphenols concentrations could lead to the increased antioxidant ability of the composite membrane liquids. When the apple polyphenols addition was 0.5%, the DPPH scavenging rate, inhibition capacity of lipid oxidation and OH radical scavenging rate were determined to be 41.33%, 56.32%, 35.44%, respectively. As the addition amount of apple polyphenols was increased to 1.5%, the antioxidant ability of the composite membrane liquids increased to 94.3%, 95.9%，98.4%, respectively, significantly higher than that of 0.5% polyphenol-incorporated composite membrane liquid (P<0.01). Compared to the BHT (1.5%), antioxidation properties of the composite membrane liquids with 1.5% apple polyphenols were higher (P<0.01). Moreover, the rheological analyses suggested that the composite membrane liquid was non-Newton pseudoplastic liquid (n<1，R2>0.99). With the increase of shear rate, the viscosity of the composite membrane liquids displayed an initially decrease but then a relatively stable trend (approximately 5 Pa·s). Meanwhile, the incorporation of apple polyphenols enhanced the viscoelastic property of the composite membrane liquids. Dynamic rheology of the composite membrane liquid transformed from G′G″. The results of FTIR and X-ray showed that the intermolecular interactions of apple polyphenols (-OH) and chitosan (-OH, -NH2) were formed, resulting in the slight change of absorption peak of the composite membrane at 3 400 cm-1, 1 545 cm-1 and 1 245 cm-1 and resulting in the reduced crystallinity of chitosan. According to the result of thermal analysis, thermal stability of the composite membrane liquids increased, probably due to the hydrogen bonds formed via the linkages between apple polyphenols and chitosan.【Conclusion】The composite membrane liquids prepared by adding apple polyphenols into the chitosan had higher antioxidant capacity, viscosity and thermal stability, thus could be used as a potential edible coating material for food preservation.

Key words: chitosan, apple polyphenols, antioxidant capacity, rheological properties, thermal stability

梁迪，杨曦，郭玉蓉. 不同浓度苹果多酚对壳聚糖复合膜液理化性质的影响[J]. 中国农业科学, 2018, 51(14): 2799-2813.

LIANG Di, YANG Xi, GUO YuRong. Effects of Different Concentrations of Apple Polyphenols on the Physicochemical Properties of Chitosan Membrane Fluids[J]. Scientia Agricultura Sinica, 2018, 51(14): 2799-2813.

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