光皮木瓜多酚类物质的提取纯化及抗氧化活性研究
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摘要
我国木瓜资源丰富,利用其生产具有生理活性的多酚物质具有广阔的市场前景。本研究以光皮木瓜(C.sinensis)为原料,通过溶剂热回流法,采用响应曲面分析确定了木瓜中多酚提取的最佳工艺条件;探索了大孔吸附树脂对木瓜多酚纯化的最佳条件;研究了木瓜多酚提取物的抗氧化活性。主要研究结果如下:
(1)采用试验设计软件Design Expert,首次通过中心旋转组合试验设计对木瓜多酚提取工艺参数进行优化,建立提取木瓜多酚的二次多项数学模型,得到水提最佳工艺条件为浸提温度86.5℃、固液比1:23.7g/mL,浸提时间1.5h,提取次数2次,以此条件进行试验,得到提取量平均值为94.46mg/g,与理论值92.98mg/g的相对误差为1.59%;醇提最佳工艺条件为浸提温度69.28℃,固液比1:31.6g/mL,乙醇浓度51.34%,浸提时间1.58h,提取次数2次,以此条件进行试验,得到提取量的平均值为127.53mg/g,与理论值125.73mg/g的相对误差仅为1.43%。对模型的方差分析得出试验所选用的二次多项模型具有高度的显著性。
(2)木瓜多酚纯化试验中选用了8种树脂,静态吸附、解吸试验得到NKA-9树脂对木瓜多酚具有较好的吸附和解析能力,静态吸附3h后基本达到吸附平衡,吸附速度较快。等温吸附试验结果表明,NKA-9树脂对木瓜多酚的吸附为吸热过程,属于物理化学相结合的吸附;吸附过程符合Langmuir等温吸附模型和Freundilich等温吸附模型。动态吸附试验结果表明,吸附曲线接近于理想的“S”型;控制流速1.0mL/min、上样浓度2.50mg/mL、pH5.0时,NKA-9树脂对木瓜多酚的吸附效果较理想。解吸最佳工艺条件为:乙醇浓度80%,洗脱流速为1mL/min。该方法简单可行,精制效果好,适合于工业化生产。
(3)木瓜多酚精制前后还原能力以及对O_2~(-·)、·OH和NO2-的清除效果进行了体外研究。结果表明,木瓜多酚提取物具有较强的还原能力和清除自由基能力,并优于对照Vc;经大孔吸附树脂纯化后提取物的抗氧化活性有一定的提高。
Chaenomeles sinensis is rich in our country, and it has a broad prospect to produce polyphenols with physiological activity using Chaenomeles sinensis.Taking Chaenomeles sinensis(Thouin) Koehne as material in this research, solvent extraction technology was used, and the optimal conditions of polyphenols extraction was determined by response surface methodology design for the first time.The optimum conditions for macroporous purification and antioxidant activities of polyphenols extraction from C.sinensis were discussed . The main conclusions of this research were as follows:
(1) Different extraction methods: water extraction and ethanol extraction of polyphenols were studied and effects of ethanol concentration, extracting time, liquid-to-solid ratio and extracting temperature on the extraction of polyphenols were investigated. On the basis of the previous results, the method of Response Surface Method was adopted according to the central composite experimental design principles of Design Expert. The results showed that the optimum conditions of polyphenols water extraction from Chaenomeles sinesis were as follows: the extraction temperature of 86.5℃,solid-liquid ratio of 1:23.7g/ml,extraction time of 1.5h and extraction of times 2.The relative error of predictive value (92.98mg/g) and measured value (94.46mg/g) was 1.59%.And the optimum conditions of polyphenols ethanol extraction from Chaenomeles sinesis were: the extraction temperature of 69.28℃, solid-liquid ratio of31.6 g/ml, ethanol concentration of 51.34% (v/v), extraction time of 1.58h and extraction of times 2. The relative error of predicted value (125.73mg/g) and measured value (127.53mg/g) was 1.43%. Variance analyses were very significant in the Quadratic equation models.
(2) Eight macroporous adsorption resin were used to purify polyphnoels from Chaenomeles sinesis through static adsorption and desorption experiment, with the evaluating indicator of absorption rate and desorption as rate. The result t indicated NKA-9 is best in the eight different resins and its adsopation equilibrium was achieved in 3 hours. The adsorbing process was an endothermic course, it belonged to physical absorption. The whole process accorded with Langmuir isothermal model and Freundlich isothermal model. The adsorption experiment showed the adsorption curve was close to type of“S”and NKA-9 resin had an effective adsorption on polyphenols with velocity of flow 1.0mL/min, polyphenols concentration of 2.50mg/mL and pH5.0. The optimal desorption parameters were eluting solvent of 71.05% ethanol, desorption velocity of 1mL/min .This method was simple and feasible with good effect of purification, which could meet the industrial requirements.
(3) By using reducing power, superoxide radical (O_2~(-·)) system, hydroxyl radical (·OH) system, and NO_2-system, the antioxidation activities of Chaenomeles sinensis polyphenols extraction were studied and compared with Vc , citric acid and etc. The results showed: Chaenomeles sinensis polyphenols extraction had better scavenging effect in free radical system, and the antioxidation activities of Chaenomeles sinensis polyphenols extraction could not be almost affected, and scavenging effect of some free radicalwas enhanced.
(1)采用试验设计软件Design Expert,首次通过中心旋转组合试验设计对木瓜多酚提取工艺参数进行优化,建立提取木瓜多酚的二次多项数学模型,得到水提最佳工艺条件为浸提温度86.5℃、固液比1:23.7g/mL,浸提时间1.5h,提取次数2次,以此条件进行试验,得到提取量平均值为94.46mg/g,与理论值92.98mg/g的相对误差为1.59%;醇提最佳工艺条件为浸提温度69.28℃,固液比1:31.6g/mL,乙醇浓度51.34%,浸提时间1.58h,提取次数2次,以此条件进行试验,得到提取量的平均值为127.53mg/g,与理论值125.73mg/g的相对误差仅为1.43%。对模型的方差分析得出试验所选用的二次多项模型具有高度的显著性。
(2)木瓜多酚纯化试验中选用了8种树脂,静态吸附、解吸试验得到NKA-9树脂对木瓜多酚具有较好的吸附和解析能力,静态吸附3h后基本达到吸附平衡,吸附速度较快。等温吸附试验结果表明,NKA-9树脂对木瓜多酚的吸附为吸热过程,属于物理化学相结合的吸附;吸附过程符合Langmuir等温吸附模型和Freundilich等温吸附模型。动态吸附试验结果表明,吸附曲线接近于理想的“S”型;控制流速1.0mL/min、上样浓度2.50mg/mL、pH5.0时,NKA-9树脂对木瓜多酚的吸附效果较理想。解吸最佳工艺条件为:乙醇浓度80%,洗脱流速为1mL/min。该方法简单可行,精制效果好,适合于工业化生产。
(3)木瓜多酚精制前后还原能力以及对O_2~(-·)、·OH和NO2-的清除效果进行了体外研究。结果表明,木瓜多酚提取物具有较强的还原能力和清除自由基能力,并优于对照Vc;经大孔吸附树脂纯化后提取物的抗氧化活性有一定的提高。
Chaenomeles sinensis is rich in our country, and it has a broad prospect to produce polyphenols with physiological activity using Chaenomeles sinensis.Taking Chaenomeles sinensis(Thouin) Koehne as material in this research, solvent extraction technology was used, and the optimal conditions of polyphenols extraction was determined by response surface methodology design for the first time.The optimum conditions for macroporous purification and antioxidant activities of polyphenols extraction from C.sinensis were discussed . The main conclusions of this research were as follows:
(1) Different extraction methods: water extraction and ethanol extraction of polyphenols were studied and effects of ethanol concentration, extracting time, liquid-to-solid ratio and extracting temperature on the extraction of polyphenols were investigated. On the basis of the previous results, the method of Response Surface Method was adopted according to the central composite experimental design principles of Design Expert. The results showed that the optimum conditions of polyphenols water extraction from Chaenomeles sinesis were as follows: the extraction temperature of 86.5℃,solid-liquid ratio of 1:23.7g/ml,extraction time of 1.5h and extraction of times 2.The relative error of predictive value (92.98mg/g) and measured value (94.46mg/g) was 1.59%.And the optimum conditions of polyphenols ethanol extraction from Chaenomeles sinesis were: the extraction temperature of 69.28℃, solid-liquid ratio of31.6 g/ml, ethanol concentration of 51.34% (v/v), extraction time of 1.58h and extraction of times 2. The relative error of predicted value (125.73mg/g) and measured value (127.53mg/g) was 1.43%. Variance analyses were very significant in the Quadratic equation models.
(2) Eight macroporous adsorption resin were used to purify polyphnoels from Chaenomeles sinesis through static adsorption and desorption experiment, with the evaluating indicator of absorption rate and desorption as rate. The result t indicated NKA-9 is best in the eight different resins and its adsopation equilibrium was achieved in 3 hours. The adsorbing process was an endothermic course, it belonged to physical absorption. The whole process accorded with Langmuir isothermal model and Freundlich isothermal model. The adsorption experiment showed the adsorption curve was close to type of“S”and NKA-9 resin had an effective adsorption on polyphenols with velocity of flow 1.0mL/min, polyphenols concentration of 2.50mg/mL and pH5.0. The optimal desorption parameters were eluting solvent of 71.05% ethanol, desorption velocity of 1mL/min .This method was simple and feasible with good effect of purification, which could meet the industrial requirements.
(3) By using reducing power, superoxide radical (O_2~(-·)) system, hydroxyl radical (·OH) system, and NO_2-system, the antioxidation activities of Chaenomeles sinensis polyphenols extraction were studied and compared with Vc , citric acid and etc. The results showed: Chaenomeles sinensis polyphenols extraction had better scavenging effect in free radical system, and the antioxidation activities of Chaenomeles sinensis polyphenols extraction could not be almost affected, and scavenging effect of some free radicalwas enhanced.
引文
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