Characterization and pH-response release of chitosan-polyvinylpyrrolidone hydrogel films loaded with tea polyphenols
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摘要: 为提高活性物质的利用率，选取壳聚糖、聚乙烯吡咯烷酮作为基材，以甘油为增塑剂、戊二醛为交联剂、茶多酚为抗氧化剂制备了具有pH响应的负载茶多酚的壳聚糖-聚乙烯吡咯烷酮水凝胶膜。通过SEM、FTIR表征薄膜的微观结构，测试了薄膜的水蒸气透过率、力学性能、溶胀度、凝胶含量及抗氧化能力，进而通过测定不同pH值环境下水凝胶膜中茶多酚的释放速率，探究其pH响应性，构建动力学模型确定茶多酚的释放规律。结果表明：交联剂与壳聚糖之间的相互作用形成了稳定的水凝胶结构，而茶多酚的加入使各组分之间的交联强度进一步提高，结构更加稳定；交联剂和茶多酚的加入在整体上改善了薄膜的理化性质，水凝胶膜水蒸气透过率为(0.159±0.010) g·mm/(m2·h·kPa)、抗拉强度为(40.58±2.11) MPa、断裂伸长率为62.32%±3.50%、溶胀平衡时的溶胀度为346.27%±3.16%、凝胶含量为87.94%±0.50%，抗氧化活性相对于传统薄膜提高了近5倍；负载茶多酚的水凝胶膜能够对pH变化有效响应，当pH值越小，茶多酚的累积释放率越大，相对于Higuchi、Ritger-Peppas模型，茶多酚的释放规律与一级动力学模型相吻合。负载茶多酚的壳聚糖-聚乙烯吡咯烷酮水凝胶膜能够有效实现茶多酚等活性物质的pH响应释放，有潜力应用于食品包装领域。Abstract: In order to improve the utilization rate of active substances, chitosan-polyvinylpyrrolidone hydrogel film loaded with tea polyphenols with pH response was prepared by selecting chitosan, polyvinylpyrrolidone as the substrate, glycerin as plasticizer, glutaraldehyde as crosslinker and tea polyphenol as antioxidant. The microstructure of the film was characterized by SEM and FTIR, and the water vapor transmittance, mechanical properties, swelling, gel content and oxidation resistance of the film were tested, and then the release rate of tea polyphenols in hydrogel films under different pH values was determined, the pH responsiveness was explored, and the release law of tea polyphenols was determined by constructing a kinetic model. The results show that the interaction between the crosslinker and chitosan forms a stable hydrogel structure, while the addition of tea polyphenols further improves the crosslinking strength and more stable structure between the components. The addition of crosslinking agent and tea polyphenols improves the physical and chemical properties of the film as a whole, the water vapor transmittance of the hydrogel film is (0.159±0.010) g·mm/(m2·h·kPa), the tensile strength was (40.58±2.11) MPa, the elongation at break is 62.32%±3.50%, the swelling ratio at swelling equilibrium is 346.27%±3.16%, and the gel content is 87.94%±0.50%. Compared with traditional films, the antioxidant activity is nearly 5 times higher. The hydrogel film loaded with tea polyphenols can effectively respond to pH changes, when the pH value is smaller, the cumulative release rate of tea polyphenols is larger, compared with the Higuchi and Ritger-Peppas model, the release law of tea polyphenols is consistent with the first-order kinetic model. Chitosan-polyvinylpyrrolidone hydrogel film loaded with tea polyphenols can effectively realize the pH response release of tea polyphenols and other active substances, and has the potential to be used in the field of food packaging.
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Key words:
- hydrogel film /
- oxidation resistance /
- pH response /
- active substance /
- release the kinetic model
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图 1 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的制备流程
Figure 1. Preparation process of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
CS—Chitosan; PVP—Polyvinylpyrrolidone; GL—Glutaraldehyde; TP—Tea polyphenol; GC—Glycerinum
图 2 CS-PVP薄膜(a)、CS-PVP-GL薄膜(b)、CS-PVP-GL-TP薄膜(c)的SEM图像
Figure 2. SEM images of CS-PVP film (a), CS-PVP-GL film (b) and CS-PVP-GL-TP film (c)
图 3 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜FTIR图谱
Figure 3. FTIR spectra of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 4 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的水蒸气透过率
Figure 4. Water vapor permeability of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
a, b, c—Significant difference (p<0.05)
图 5 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的抗拉强度和断裂伸长率
Figure 5. Tensile strength and elongation at break of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 6 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的溶胀度
Figure 6. Swelling ratio of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 7 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的凝胶含量
Figure 7. Gel content of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 8 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的1, 1-二苯基-2-三硝基苯肼 (DPPH) 自由基清除率
Figure 8. 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 10 不同pH值条件下CS-PVP-GL-TP薄膜中TP的累积释放速率
Figure 10. Cumulative release rate of TP in CS-PVP-GL-TP film at different pH values
图 11 不同pH值条件下CS-PVP-GL-TP薄膜中TP的释放动力学曲线
Figure 11. TP release kinetic curves of CS-PVP-GL-TP film at different pH values
表 1 不同pH值条件下CS-PVP-GL-TP薄膜中TP的释放动力学拟合方程
Table 1. Release kinetic fitting equations of TP in CS-PVP-GL-TP film at different pH values
The fitted equation pH value The expression of the fit R2 First-order kinetic equation 3 $ {M}_{t}=82.78289\left(1-{\mathrm{e}}^{-0.17951 t}\right) $ 0.99338 4 $ {M}_{t}=75.18297\left(1-{\mathrm{e}}^{-0.16145 t}\right) $ 0.99619 5 $ {M}_{t}=58.97272\left(1-{\mathrm{e}}^{-0.12216 t}\right) $ 0.98828 6 $ {M}_{t}=51.00868\left(1-{\mathrm{e}}^{-0.09799 t}\right) $ 0.99636 Higuchi equation 3 $ {M}_{t}=17.06298{t}^{1/2}+7.7254 $ 0.94187 4 $ {M}_{t}=15.65142{t}^{1/2}+4.82808 $ 0.95413 5 $ {M}_{t}=12.11531{t}^{1/2}+0.47913 $ 0.96950 6 $ {M}_{t}=10.18583{t}^{1/2}- $1.66637 0.98314 Ritger-Peppas
equation3 $ {M}_{t}=27.76727{t}^{0.362} $ 0.96908 4 $ {M}_{t}=22.52151{t}^{0.39476} $ 0.96985 5 $ {M}_{t}=13.24582{t}^{0.47103} $ 0.97085 6 $ {M}_{t}=8.74408{t}^{0.53971} $ 0.98314 Notes: Mt—Cumulative release rate of t; t—Release time; R2—Coefficient of determination. 
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