魔芋葡甘聚糖/变性淀粉复配性质及应用研究
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摘要
本文旨在尝试利用魔芋葡甘聚糖(Konjac glucomannan,简称KGM)和羧甲基淀粉(Carboxymethyl starch,简称CMS)复配形成溶胶及凝胶。通过分子动力学模拟预测魔芋葡甘聚糖和羧甲基淀粉的复配可能性,利用分子动力学模拟结果指导复配研究;以粘度和透明度为指标探讨了配比、浓度、温度、搅拌时间、盐离子等因素对魔芋葡甘聚糖/羧甲基淀粉复配溶胶的影响;以凝胶硬度、凝胶弹性、凝胶强度和凝胶析水率为指标研究了配比、凝胶温度、pH值、浓度和常温放置时间对复配凝胶的影响;通过二次正交旋转组合试验和正交试验确定了复配溶胶和复配凝胶的最佳工艺,并将复配凝胶应用于仿生鲍鱼生产中,以期为魔芋葡甘聚糖的复配研究和魔芋葡甘聚糖/羧甲基淀粉复配凝胶应用提供参考。研究得出以下结果:
1魔芋葡甘聚糖/羧甲基淀粉复配分子动力学模拟
通过分子动力学模拟得出,魔芋葡甘聚糖和羧甲基淀粉共混后,分子间发生氢键对接作用,复配后体系势能大幅度降低,体系趋于稳定,魔芋葡甘聚糖与羧甲基淀粉之间形成大量的分子内和分子间氢键,在60℃时形成的氢键数最多,二者维持一定的稳定构象。
2魔芋葡甘聚糖/羧甲基淀粉复配溶胶性质
当魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2时,魔芋葡甘聚糖/羧甲基淀粉复配溶胶粘度最大,羧甲基淀所占比例越大,复配溶胶透明度越高;随着浓度的增加,复配溶胶粘度增大,透明度降低;当温度为60℃时,复配溶胶达到最大粘度值,但温度对复配溶胶透明度的影响不大;搅拌时间在0.75 h左右时,溶胶具有较高粘度,随着搅拌时间的延长,溶胶透明度升高;KCl会引起魔芋葡甘聚糖/羧甲基淀粉复配溶胶粘度和透光率的下降。
3魔芋葡甘聚糖/羧甲基淀粉复配凝胶性质
当魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2时凝胶的硬度、弹性、凝胶强度及持水性有最大值;随着浓度的增加,魔芋葡甘聚糖/羧甲基淀粉复配凝胶的硬度、凝胶强度和持水性升高,浓度在25.0 g/L时凝胶的弹性最好;随着温度升高,硬度、弹性、凝胶强度和持水性都升高,50～60℃是凝胶的特征温度范围;随着pH值升高,复配凝胶的的硬度、弹性、凝胶强度和持水性升高,当pH>11.0时,各指标则相对稳定;凝胶放置24 h以内可以提高凝胶的强度、弹性和硬度,而凝胶持水性则随着放置时间的延长而降低。
4最佳溶胶和凝胶制备条件
通过二次正交旋转组合和验证试验得出浓度为10.0 g/L的魔芋葡甘聚糖/羧甲基淀粉复配溶胶的最佳制备条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为7.5︰2.5,温度60℃,搅拌时间0.875 h。通过正交试验和验证试验得出:魔芋葡甘聚糖/羧甲基淀粉复配凝胶的最佳制备条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2,浓度为32.5 g/L,凝胶温度为80℃,pH为11.0、放置时间为20 h。
5魔芋葡甘聚糖/羧甲基淀粉复配应用
将魔芋葡甘聚糖/羧甲基淀粉复配凝胶的最佳工艺应用于魔芋仿生鲍鱼生产,以产品凝胶强度和透明度为指标,经过试验验证得出最佳工艺条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2,浓度为32.5 g/L,凝胶温度90℃,pH为11.5。
以上结果表明,魔芋葡甘聚糖与羧甲基淀粉具有一定的复配交互作用,二者复配后在最佳条件下可形成性能较好的魔芋葡甘聚糖/羧甲基淀粉溶胶或魔芋葡甘聚糖/羧甲基淀粉凝胶,具有一定的实际生产应用价值。
This paper aims to improve the nature of the sol and the properties of the gel by using carboxymethyl starch (CMS) to mix with konjac glucomannan (KGM). The possibility of mixing of KGM and CMS was predicted by molecular dynamics simulation, and the result was used as instruction for mixing. The effects of ratio, concentration, temperature, stiring time, salt ions and other factors on the KGM/CMS complex sol were discussed in this paper. The effects of ratio, concentration, gel temperature, pH, and standing time on the complex gel were also studied. Then the best process could be ascertained through quadratic-rotation-orthogonal experiment and orthogonal experiment. In order to provide references for the complex study on the application of KGM and KGM/CMS, the complex gel was applied to biomimetic food such as abalone to test its practical application results.The results was as follows:
1 Molecular Dynamics Simulation of the Mixing of KGM/ CMS
The result of molecular dynamics simulation indicated that intermolecular hydrogen bond effect was generated after mixing of KGM/CMS, energy of position for system was decreased after mixing and was to being stable, intramolucular and intermoleculer hydrogen bond were formed between KGM/CMS, and the number of hydrogen bond was the highest when it was at 60℃, and the stable conformation was maintained.
2 Property of the KGM/CMS Complex Sol
The transparency of sol could be improved by increasing CMS, and when KGM/CMS application was 8︰2, the compounded sol had the best viscidity. With the increase of concentration, complex sol had higher viscidity and lower transparency. The best viscidity of sol got at 60℃, and the influence of temperature on transparency was not large. Constantly stirring could improve the transparency which is higher when stiring time was about 0.75 h. But the viscidity and luminousness of KGM/CMS complex sol would be dropped by KCl.
3 Property of the KGM/CMS Complex Gel
The mechanical properties such as hardness, flexibility, gel intensity and retentiveness, etc., were highest when KGM/CMS application was 8︰2. With the increase of concentration, the hardness, flexibility, gel intensity and retentiveness of KGM/CMS complex gel rose, and the flexibility of the gel was best at 25.0 g/L. The mechanical properties and retentiveness were improved as the temperature rising, and 50～60℃was the characteristic gel temperature range. The mechanical properties and retentiveness were also raised as the pH rising. While pH>11.0,they were relatively stable. The intensity, flexibility and hardness could be improved in 24 hours quiescence. However, the retentiveness of the gel debased as the setting time extending.
4 Best Conditions of the Sol and Gel
By quadratic-rotation-orthogonal experiment, it could be concluded as follows: The best conditions of the 10.0 g/L KGM/CMS complex sol were: KGM/CMS application 7.5︰2.5, temperature 60℃, stirring time 0.875 h. And the best conditions of the KGM/CMS complex gel by orthogonal experiments and validation were: KGM/CMS application 8︰2, concentration 32.5 g/L, gel temperature 80℃, pH value 11.0, and standing time 20 h.
5 Application of KGM/CMS
The best process conditions of KGM/CMS complex gel could be applied to the konjac biomimetic food, and experiments proved that the best technological conditions were KGM/CMS application 8︰2, concentration 32.5 g/L, gel temperature 90℃, and pH value 11.5 .
These results indicated that the sol and gel properties of KGM could be improved by CMS. After complex, KGM/CMS sol or KGM/CMS gel with better performance under certain conditions, and good practical application results were attained.
1魔芋葡甘聚糖/羧甲基淀粉复配分子动力学模拟
通过分子动力学模拟得出,魔芋葡甘聚糖和羧甲基淀粉共混后,分子间发生氢键对接作用,复配后体系势能大幅度降低,体系趋于稳定,魔芋葡甘聚糖与羧甲基淀粉之间形成大量的分子内和分子间氢键,在60℃时形成的氢键数最多,二者维持一定的稳定构象。
2魔芋葡甘聚糖/羧甲基淀粉复配溶胶性质
当魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2时,魔芋葡甘聚糖/羧甲基淀粉复配溶胶粘度最大,羧甲基淀所占比例越大,复配溶胶透明度越高;随着浓度的增加,复配溶胶粘度增大,透明度降低;当温度为60℃时,复配溶胶达到最大粘度值,但温度对复配溶胶透明度的影响不大;搅拌时间在0.75 h左右时,溶胶具有较高粘度,随着搅拌时间的延长,溶胶透明度升高;KCl会引起魔芋葡甘聚糖/羧甲基淀粉复配溶胶粘度和透光率的下降。
3魔芋葡甘聚糖/羧甲基淀粉复配凝胶性质
当魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2时凝胶的硬度、弹性、凝胶强度及持水性有最大值;随着浓度的增加,魔芋葡甘聚糖/羧甲基淀粉复配凝胶的硬度、凝胶强度和持水性升高,浓度在25.0 g/L时凝胶的弹性最好;随着温度升高,硬度、弹性、凝胶强度和持水性都升高,50～60℃是凝胶的特征温度范围;随着pH值升高,复配凝胶的的硬度、弹性、凝胶强度和持水性升高,当pH>11.0时,各指标则相对稳定;凝胶放置24 h以内可以提高凝胶的强度、弹性和硬度,而凝胶持水性则随着放置时间的延长而降低。
4最佳溶胶和凝胶制备条件
通过二次正交旋转组合和验证试验得出浓度为10.0 g/L的魔芋葡甘聚糖/羧甲基淀粉复配溶胶的最佳制备条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为7.5︰2.5,温度60℃,搅拌时间0.875 h。通过正交试验和验证试验得出:魔芋葡甘聚糖/羧甲基淀粉复配凝胶的最佳制备条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2,浓度为32.5 g/L,凝胶温度为80℃,pH为11.0、放置时间为20 h。
5魔芋葡甘聚糖/羧甲基淀粉复配应用
将魔芋葡甘聚糖/羧甲基淀粉复配凝胶的最佳工艺应用于魔芋仿生鲍鱼生产,以产品凝胶强度和透明度为指标,经过试验验证得出最佳工艺条件为:魔芋葡甘聚糖与羧甲基淀粉的配比为8︰2,浓度为32.5 g/L,凝胶温度90℃,pH为11.5。
以上结果表明,魔芋葡甘聚糖与羧甲基淀粉具有一定的复配交互作用,二者复配后在最佳条件下可形成性能较好的魔芋葡甘聚糖/羧甲基淀粉溶胶或魔芋葡甘聚糖/羧甲基淀粉凝胶,具有一定的实际生产应用价值。
This paper aims to improve the nature of the sol and the properties of the gel by using carboxymethyl starch (CMS) to mix with konjac glucomannan (KGM). The possibility of mixing of KGM and CMS was predicted by molecular dynamics simulation, and the result was used as instruction for mixing. The effects of ratio, concentration, temperature, stiring time, salt ions and other factors on the KGM/CMS complex sol were discussed in this paper. The effects of ratio, concentration, gel temperature, pH, and standing time on the complex gel were also studied. Then the best process could be ascertained through quadratic-rotation-orthogonal experiment and orthogonal experiment. In order to provide references for the complex study on the application of KGM and KGM/CMS, the complex gel was applied to biomimetic food such as abalone to test its practical application results.The results was as follows:
1 Molecular Dynamics Simulation of the Mixing of KGM/ CMS
The result of molecular dynamics simulation indicated that intermolecular hydrogen bond effect was generated after mixing of KGM/CMS, energy of position for system was decreased after mixing and was to being stable, intramolucular and intermoleculer hydrogen bond were formed between KGM/CMS, and the number of hydrogen bond was the highest when it was at 60℃, and the stable conformation was maintained.
2 Property of the KGM/CMS Complex Sol
The transparency of sol could be improved by increasing CMS, and when KGM/CMS application was 8︰2, the compounded sol had the best viscidity. With the increase of concentration, complex sol had higher viscidity and lower transparency. The best viscidity of sol got at 60℃, and the influence of temperature on transparency was not large. Constantly stirring could improve the transparency which is higher when stiring time was about 0.75 h. But the viscidity and luminousness of KGM/CMS complex sol would be dropped by KCl.
3 Property of the KGM/CMS Complex Gel
The mechanical properties such as hardness, flexibility, gel intensity and retentiveness, etc., were highest when KGM/CMS application was 8︰2. With the increase of concentration, the hardness, flexibility, gel intensity and retentiveness of KGM/CMS complex gel rose, and the flexibility of the gel was best at 25.0 g/L. The mechanical properties and retentiveness were improved as the temperature rising, and 50～60℃was the characteristic gel temperature range. The mechanical properties and retentiveness were also raised as the pH rising. While pH>11.0,they were relatively stable. The intensity, flexibility and hardness could be improved in 24 hours quiescence. However, the retentiveness of the gel debased as the setting time extending.
4 Best Conditions of the Sol and Gel
By quadratic-rotation-orthogonal experiment, it could be concluded as follows: The best conditions of the 10.0 g/L KGM/CMS complex sol were: KGM/CMS application 7.5︰2.5, temperature 60℃, stirring time 0.875 h. And the best conditions of the KGM/CMS complex gel by orthogonal experiments and validation were: KGM/CMS application 8︰2, concentration 32.5 g/L, gel temperature 80℃, pH value 11.0, and standing time 20 h.
5 Application of KGM/CMS
The best process conditions of KGM/CMS complex gel could be applied to the konjac biomimetic food, and experiments proved that the best technological conditions were KGM/CMS application 8︰2, concentration 32.5 g/L, gel temperature 90℃, and pH value 11.5 .
These results indicated that the sol and gel properties of KGM could be improved by CMS. After complex, KGM/CMS sol or KGM/CMS gel with better performance under certain conditions, and good practical application results were attained.
引文
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