Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films

doi:10.11949/0438-1157.20230383

Abstract

Abstract:

Transition metal ions in food can catalyze the oxidation of lipids and lead to food quality degradation, so it has great significance to carry out antioxidant packaging research. In this study, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) films covered with poly(acrylic acid) (PAA) graft layer as the substrate, chitosan (CS) and sodium alginate (SA) as polyelectrolytes were used to produce PHBV-g-PAA/(CS/SA) _n non-release antioxidant packaging films with metal chelating ability by layer self-assembly method. The effects of polyelectrolyte solution concentration and pH on the chemical properties, microscopic morphology, active group content and $C u (Ⅱ)$ ion chelating ability of the active membranes were investigated. The results show that the active films were characterized by Fourier transform infrared spectroscopy with acid orange 7 staining, demonstrating that CS and SA polyelectrolytes have been successfully assembled alternately onto the surface of PHBV-g-PAA films. It was found that the thickness of the assembled layer increased with the growth of the polyelectrolyte solution concentration and pH by SEM. When the concentration of CS and SA polyelectrolyte solutions was 1.0 mg/ml and the pH was 5.0 and 7.0 respectively, the polyelectrolyte assembly layer was more uniform and flat. At this time, the surface amino density of the active film was 136.38 nmol/cm² and the amount of Cu(Ⅱ) ions chelated was 124.93 nmol/cm². The active film has a certain antioxidant capacity and was higher than PHBV and PHBV-g-PAA films, which has a broad application prospect in the field of food packaging.

Key words: poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polymer, layer self-assembly, adsorption (action), metal ion chelation, antioxidant active packaging, composite materials

摘要：

食品中的过渡金属离子能够催化氧化脂质导致食品质量下降，因此开展抗氧化包装研究具有重要意义。本研究以覆盖聚丙烯酸（PAA）接枝层的聚（3-羟基丁酸酯-co-3-羟基戊酸酯）（PHBV）薄膜为基材，壳聚糖（CS）和海藻酸钠（SA）为聚电解质，通过层层自组装法制得具备金属螯合能力的PHBV-g-PAA/(CS/SA) _n 非释放型抗氧化包装膜，研究聚电解质溶液浓度和pH对活性膜化学性质、微观形貌、活性基团含量以及Cu(Ⅱ)离子螯合能力的影响。结果表明：通过傅里叶变换红外光谱仪与酸性橙7染色法对活性膜进行表征，证明CS和SA聚电解质已成功交替组装到PHBV-g-PAA薄膜表面；通过SEM观察活性膜形貌结构发现，随着聚电解质溶液浓度和pH增大，组装层厚度不断增加，当CS和SA聚电解质溶液浓度为1.0 mg/ml、pH分别为5.0和7.0时，聚电解质组装层较为均匀平整；此时，活性膜表面氨基密度为136.38 nmol/cm²，Cu(Ⅱ) 离子螯合量为124.93 nmol/cm²。该活性膜具备一定的抗氧化能力且高于PHBV及PHBV-g-PAA薄膜，在食品包装领域具有广阔的应用前景。

关键词: 聚（3-羟基丁酸酯-co-3-羟基戊酸酯）, 聚合物, 层层自组装, 吸附（作用）, 金属离子螯合, 抗氧化活性包装, 复合材料

CLC Number:

TS 206.4

Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films[J]. CIESC Journal, 2023, 74(7): 3068-3078.

王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.

Figures/Tables 12

References 40

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样品编号	CS浓度/(mg/ml)	溶剂
0.5-3.0	0.5	稀乙酸（pH=2.8）
0.5-5.0	0.5	乙酸盐缓冲液（pH=4.8）
1.0-3.0	1.0	稀乙酸（pH=2.8）
1.0-5.0	1.0	乙酸盐缓冲液（pH=4.8）
3.0-3.5	3.0	稀乙酸（pH=2.8）
5.0-3.5	5.0	稀乙酸（pH=2.8）
5.0-4.5	5.0	乙酸盐缓冲液（pH=3.8）
5.0-5.5	5.0	乙酸盐缓冲液（pH=4.8）

样品编号	CS浓度/(mg/ml)	溶剂
0.5-3.0	0.5	稀乙酸（pH=2.8）
0.5-5.0	0.5	乙酸盐缓冲液（pH=4.8）
1.0-3.0	1.0	稀乙酸（pH=2.8）
1.0-5.0	1.0	乙酸盐缓冲液（pH=4.8）
3.0-3.5	3.0	稀乙酸（pH=2.8）
5.0-3.5	5.0	稀乙酸（pH=2.8）
5.0-4.5	5.0	乙酸盐缓冲液（pH=3.8）
5.0-5.5	5.0	乙酸盐缓冲液（pH=4.8）

样品编号	CS溶液pH	SA溶液pH
0.5-3.0	3.10 ± 0.03	7.03 ± 0.03
0.5-5.0	4.82 ± 0.02	7.03 ± 0.03
1.0-3.0	3.20± 0.02	6.90 ± 0.04
1.0-5.0	4.95 ± 0.02	6.90 ± 0.04
3.0-3.5	3.61 ± 0.03	6.49 ± 0.03
5.0-3.5	3.81 ± 0.01	6.33 ± 0.02
5.0-4.5	4.47 ± 0.02
5.0-5.5	5.71 ± 0.03

样品编号	CS溶液pH	SA溶液pH
0.5-3.0	3.10 ± 0.03	7.03 ± 0.03
0.5-5.0	4.82 ± 0.02	7.03 ± 0.03
1.0-3.0	3.20± 0.02	6.90 ± 0.04
1.0-5.0	4.95 ± 0.02	6.90 ± 0.04
3.0-3.5	3.61 ± 0.03	6.49 ± 0.03
5.0-3.5	3.81 ± 0.01	6.33 ± 0.02
5.0-4.5	4.47 ± 0.02
5.0-5.5	5.71 ± 0.03

样品编号	CS溶液透光率/%	SA溶液透光率/%
0.5-3.0	99.60 ± 0.20	99.50 ± 0.30
0.5-5.0	99.60 ± 0.10	99.50 ± 0.30
1.0-3.0	99.50 ± 0.05	99.50 ± 0.10
1.0-5.0	99.50 ± 0.10	99.50 ± 0.10
3.0-3.5	98.80 ± 0.10	98.40 ± 0.30
5.0-3.5	97.90 ± 0.10	97.30 ± 0.20
5.0-4.5	97.60 ± 0.50
5.0-5.5	48.60 ± 0.50