Characterization and pH-response release of chitosan-polyvinylpyrrolidone hydrogel films loaded with tea polyphenols
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摘要:
茶多酚具备优异的抗氧化和抗菌活性，但是茶多酚的稳定性较差，在一定程度上限制了其应用，开发具有控释功能的复合材料对茶多酚等活性物质的利用具有重要意义。智能水凝胶具有独特的三维网络结构，具有良好的力学性能和阻隔性能，能够因外部环境改变而发生响应，被广泛应用于医药和农业领域，用于特定药物的装载和释放以及土壤肥料的控释等方面。本文选取壳聚糖、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、凝胶含量以及抗氧化能力，进而通过测定不同pH值的水凝胶膜中茶多酚的释放速率探究其pH响应性，并且通过动力学模型拟合来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薄膜的理化性质，茶多酚水凝胶膜的水蒸气透过率为(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)%，而抗氧化活性相对于传统薄膜提高了近5倍；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对pH变化做出响应，有效实现茶多酚等活性物质的控制释放，有潜力应用于食品包装领域。 负载茶多酚的壳聚糖-聚乙烯吡咯烷酮水凝胶膜的微观结构及不同pH值下茶多酚的释放速率 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 showed that the interaction between the crosslinker and chitosan formed a stable hydrogel structure, while the addition of tea polyphenols further improved the crosslinking strength and more stable structure between the components. The addition of crosslinking agent and tea polyphenols improved the physical and chemical properties of the film as a whole, the water vapor transmittance of the hydrogel film was (0.159±0.010) g·mm/(m2·h·kPa), the tensile strength was (40.58±2.11) MPa, the elongation at break was (62.32±3.50)%, the swelling ratio at swelling equilibrium was (346.27±3.16)%, and the gel content was (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.-
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、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的SEM图像
Figure 2. SEM images of CS-PVP film, CS-PVP-GL film and CS-PVP-GL-TP film
图 3 CS-PVP薄膜、CS-PVP-GL薄膜、CS-PVP-GL-TP薄膜的傅里叶红外光谱图
Figure 3. Fourier infrared 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
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 films 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DPPH自由基清除率
Figure 8. 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 in CS-PVP-GL-TP film release kinetic curves 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 tea polyphenols 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\times \left(1-{\mathrm{e}}^{-0.17951 t}\right) $ 0.99338 4 $ {M}_{t}=75.18297\times \left(1-{\mathrm{e}}^{-0.16145 t}\right) $ 0.99619 5 $ {M}_{t}=58.97272\times \left(1-{\mathrm{e}}^{-0.12216 t}\right) $ 0.98828 6 $ {M}_{t}=51.00868\times \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 $ 0.9695 6 $ {M}_{t}=10.18583{t}^{1/2}- $1.66637 0.98314 Ritger-peppas equation 3 $ {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 
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