Study on Ultrasound-assisted Optimization of Chitooligosaccharide-Pectin Stabilized Pickering Emulsion and Its Stability
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摘要: 为探究超声辅助制备壳寡糖稳定的Pickering乳液的最佳工艺及其稳定性，本文以壳寡糖、果胶为Pickering颗粒原料，以葵花籽油为油相，选取乳化活性指数（EAI）和乳化稳定性指数（ESI）为指标，通过单因素实验和响应面优化超声辅助制备壳寡糖-果胶稳定的Pickering乳液的工艺条件，并考察优化条件下乳液的稳定性。结果表明，壳寡糖-果胶稳定的Pickering乳液的最佳制备工艺为：壳寡糖与果胶质量比为0.05，溶液pH为5.22，油相体积分数为32%，超声功率为350 W，该优化条件下制备的乳液EAI为（5.129±0.003）m2/g，ESI为（796.68±4.43）min；稳定性实验及乳液内部显微结构观察表明，乳液在25～50 ℃和0～100 mmol/L盐离子（NaCl）条件下具有良好的乳化稳定性。因此，结合超声技术辅助优化获得的新型Pickering乳液，改善了乳液的乳化特性，为壳寡糖Pickering颗粒制备及其应用提供了参考。
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关键词:
- 壳寡糖 /
- 果胶 /
- 超声乳化法 /
- Pickering乳液 /
- 稳定性
Abstract: To investigate the optimal process of ultrasound-assisted preparation of chitooligosaccharide-stabilized Pickering emulsion and its stability performance, chitooligosaccharide and pectin were used as Pickering particle raw materials and sunflower oil as the oil phase, and emulsification activity index (EAI) and emulsion stability index (ESI) were selected as the indexes, the process conditions of ultrasound-assisted preparation of chitooligosaccharide-pectin stabilized Pickering emulsions were optimized by single factor experiment and response surfaces methodology, and the stability of the emulsions prepared under optimization was investigated. The results showed that the optimum conditions for chitooligosaccharide-pectin stabilized Pickering emulsion were as follow: Mass ratio of chitosan and pectin was 0.05, solution pH was 5.22, oil phase volume fraction was 32%, and ultrasonic power was 350 W. The EAI and ESI of emulsions reached (5.129±0.003) m2/g and (796.68±4.43) min respectively at the optimal condition. The stability experiments and the observation of the internal microstructure of the emulsions showed that the emulsions had excellent emulsification stability at 25~50 ℃ and 0~100 mmol/L salt ion (NaCl). Therefore, the novel Pickering emulsion optimized by ultrasound tech-nology improved the emulsification characteristics of the emulsion, which provided a reference for the preparation of chitooligosaccharide Pickering particles and their applications.-
Key words:
- chitooligosaccharide /
- pectin /
- phacoemulsification /
- Pickering emulsion /
- stability
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图 2 不同质量比Pickering乳液的显微结构（40×）、黏度和EAI、ESI
Figure 2. Microstructure (40×), viscosity and EAI, ESI of Pickering emulsion under different mass ratio
注：A：0.00；B：0.05；C：0.10；D：0.40；E：0.70；F：1.00；不同小写字母表示不同质量比下制备的乳液黏度、EAI之间具有显著性差异（P<0.05）；不同大写字母表示不同质量比下制备的乳液ESI具有显著性差异（P<0.05）。
图 3 不同pH下Pickering乳液的外观分层和乳析指数
Figure 3. Appearance delamination and creaming index of Pickering emulsions at different pH
图 4 不同pH下Pickering乳液的显微结构（40×）、黏度、EAI和ESI
Figure 4. Microstructure (40×), viscosity and EAI, ESI of Pickering emulsion under different pH
注：A：2.5；B：3.5；C：4.5；D：5.5；E：6.5；不同小写字母表示不同pH下制备的乳液黏度、EAI之间具有显著性差异（P<0.05）；不同大写字母表示不同pH下制备的乳液ESI具有显著性差异（P<0.05）。
图 5 不同油相体积分数下Pickering乳液的外观分层和乳析指数
Figure 5. Appearance delamination and creaming index of Pickering emulsion at different oil phase volume fraction
图 6 不同油相体积分数下Pickering乳液的显微结构（40×）、黏度和EAI、ESI
Figure 6. Microstructure (40×), viscosity and EAI, ESI of Pickering emulsion under different oil phase volume fraction
注：A：10%；B：20%；C：30%；D：40%；E：50%；不同小写字母表示不同油相体积分数下制备的乳液黏度、EAI之间具有显著性差异（P<0.05）；不同大写字母表示不同油相体积分数下制备的乳液ESI具有显著性差异（P<0.05）。
图 7 不同超声功率下Pickering乳液的外观分层和乳析指数
Figure 7. Appearance delamination and creaming index of Pickering emulsion at different ultrasonic power
图 8 不同超声功率下Pickering乳液的显微结构（40×）、黏度和EAI、ESI
Figure 8. Microstructure (40×), viscosity and EAI, ESI of Pickering emulsion under different ultrasonic power
注：A：0 W；B：150 W；C：250 W；D：350 W；E：450 W；不同小写字母表示不同超声功率下制备的乳液黏度、EAI之间具有显著性差异（P<0.05）；不同大写字母表示不同超声功率下制备的乳液ESI具有显著性差异（P<0.05）。
9 不同变量对Pickering乳液EAI交互作用的3D曲面图和二维等高线
9. 3D Surface diagram and two-dimensional contour line of interaction between different variables on Pickering emulsion EAI
图 10 不同变量对Pickering乳液ESI交互作用的3D曲面图和二维等高线
Figure 10. 3D Surface diagram and two-dimensional contour line of interaction between different variables on Pickering emulsion ESI
图 11 Pickering乳液在不同温度处理下的显微结构（40×）、EAI、ESI和乳析指数
Figure 11. Microstructure (40×), EAI, ESI and emulsification index of Pickering emulsion at different temperature
注：A：25 ℃；B：50 ℃；C：75 ℃。
图 12 Pickering乳液在不同盐离子处理下的显微结构（40×）、EAI、ESI和乳析指数
Figure 12. Microstructure (40×), EAI, ESI and emulsification index of Pickering emulsion treated with different salt ion
注：A：0 mmol/L；B：100 mmol/L；C：300 mmol/L。
表 1 响应面试验的因素水平设计
Table 1. Factors and levels of response surface methodology
水平 A 壳寡糖-果胶质量比 B 溶液pH C 油相体积分数
（%）D 超声功率
（W）−1 0.05 5.0 30 150 0 0.10 5.5 40 250 1 0.15 6.0 50 350 
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表 2 响应面试验方案及结果
Table 2. Experiment scheme and results of response surface methodology
试验号 A B C D EAI
（m2/g）ESI
（min）试验号 A B C D EAI
（ m2/g）ESI
（min）1 −1 0 1 0 2.298 554.4 16 1 0 1 0 0.848 304.4 2 0 1 −1 0 2.157 381.3 17 −1 0 0 −1 3.650 372.9 3 0 0 0 0 6.696 854.3 18 1 0 0 −1 0.754 378.6 4 1 0 −1 0 1.100 315.0 19 −1 −1 0 0 3.662 772.0 5 1 0 0 1 0.975 362.9 20 0 1 0 1 1.894 411.3 6 −1 0 0 1 4.848 701.5 21 0 0 −1 1 3.098 795.9 7 0 −1 0 1 1.511 525.0 22 1 −1 0 0 1.206 261.5 8 0 0 1 1 1.759 636.7 23 0 0 0 0 7.534 915.3 9 0 0 0 0 6.834 833.9 24 0 −1 −1 0 6.088 458.7 10 0 0 −1 −1 1.520 520.0 25 0 1 1 0 2.213 567.8 11 0 −1 0 −1 1.621 294.1 26 0 1 0 −1 1.834 455.0 12 −1 0 −1 0 6.556 754.0 27 0 −1 1 0 1.186 515.0 13 0 0 0 0 6.659 994.4 28 0 0 0 0 6.379 961.8 14 1 1 0 0 0.963 358.6 29 0 0 1 −1 1.122 442.7 15 −1 1 0 0 4.456 407.4
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表 3 EAI的回归模型方差分析
Table 3. Variance analysis of regression model of EAI
项目 平方和 自由度 均方 F P 显著性 模型 141.23 14 10.09 22.00 < 0.0001 ** A 32.09 1 32.09 69.98 < 0.0001 ** B 0.26 1 0.26 0.56 0.4663 C 10.25 1 10.25 22.36 0.0003 ** D 1.07 1 1.07 2.33 0.1488 AB 0.27 1 0.27 0.59 0.4566 AC 4.01 1 4.01 8.75 0.0104 * AD 0.24 1 0.24 0.52 0.4826 BC 6.15 1 6.15 13.40 0.0026 ** BD 7.225E-003 1 7.225E-003 0.016 0.9019 CD 0.22 1 0.22 0.48 0.4986 A2 23.76 1 23.76 51.81 < 0.0001 ** B2 32.25 1 32.25 70.31 < 0.0001 ** C2 28.21 1 28.21 61.51 < 0.0001 ** D2 49.24 1 49.24 107.37 < 0.0001 ** 残差 6.42 14 0.46 失拟项 5.70 10 0.57 3.16 0.1392 纯误差 0.72 4 0.18 总离差 147.65 28 注：**P<0.01为极显著；*P<0.05为显著；表4同。
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表 4 ESI的回归模型方差分析
Table 4. Variance analysis of regression model of ESI
项目 平方和 自由度 均方 F P 显著性 模型 1.228E+006 14 87739.20 10.58 < 0.0001 ** A 2.137E+005 1 2.137E+005 25.77 0.0002 ** B 4998.00 1 4998.00 0.60 0.4504 C 3464.60 1 3464.60 0.42 0.5285 D 75208.33 1 75208.33 9.07 0.0093 ** AB 53291.72 1 53291.72 6.43 0.0238 * AC 8930.25 1 8930.25 1.08 0.3170 AD 26292.62 1 26292.62 3.17 0.0967 BC 4238.01 1 4238.01 0.51 0.4864 BD 18851.29 1 18851.29 2.27 0.1538 CD 1676.90 1 1676.90 0.20 0.6598 A2 3.815E+005 1 3.815E+005 46.01 < 0.0001 ** B2 4.451E+005 1 4.451E+005 53.68 < 0.0001 ** C2 1.602E+005 1 1.602E+005 19.33 0.0006 ** D2 2.552E+005 1 2.552E+005 30.78 < 0.0001 ** 残差 1.161E+005 14 8291.36 失拟项 97369.50 10 9736.95 2.08 0.2500 纯误差 18709.57 4 4677.39 总离差 1.344E+006 28
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表 5 响应面的验证实验结果与分析
Table 5. Verification test results and analysis of response surface methodology
序号 EAI（m2/g） ESI（min） 1 5.125 792.99 2 5.130 802.91 3 5.133 794.14 均值 5.129±0.003 796.68±4.43 相对平均偏差 0.06% 0.52% 回归方程预测值 5.13 799.435
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