核桃青皮的强抗氧化活性成分及其抗氧化稳定性

doi:10.3864/j.issn.0578-1752.2016.03.012

摘要/Abstract

摘要： 【目的】以大孔树脂纯化的核桃青皮抗氧化成分为对象，对其组分进行鉴定，并研究其抗氧化稳定性，为核桃青皮的开发和有效利用提供理论依据。【方法】以DPPH自由基清除能力为指标，采用D101型的大孔树脂纯化核桃青皮粗提取物，浓缩冷冻干燥后，采用超高压液相色谱-高分辨质谱联用仪（UPLC-MS）对具有较强抗氧化活性部分的核桃青皮纯化物进行成分分析，并通过分析pH、温度、光照、金属离子、氧化剂H2O2、还原剂Na2SO3和防腐剂山梨酸钾7种因素对核桃青皮抗氧化物质清除DPPH自由基的影响，研究其抗氧化性能的稳定性。【结果】UPLC-MS结果表明，核桃青皮中具有强抗氧化活性的主要成分为绿原酸、短叶苏木酚羧酸、花靛-葡萄糖/半乳糖、鞣花、槲皮素-阿拉伯糖、表儿茶素或儿茶素、槲皮素-3-O-葡萄糖苷等7种成分。抗氧化成分稳定性研究结果表明：随着pH的增大，核桃青皮抗氧化物质对DPPH自由基清除率逐渐减小，当pH为12时，抗氧化物质对DPPH自由基的消除率几乎为0；抗氧化物质对DPPH自由基清除率能力随着放置时间的延长而下降；在室内、光照和避光3种处理下，核桃青皮抗氧化物质溶液的DPPH自由基消除率在0-2 h内逐渐下降，且三者之间无显著性差异（P＞0.05）。在放置2-5 h内，光照处理的消除率均低于同期的室内和避光处理；在4、37、70和90℃ 4种处理下，核桃青皮抗氧化物质溶液对DPPH自由基的消除率总体呈下降的趋势，而在50℃处理下则呈先下降后上升再下降的趋势；Fe3+能使抗氧化物质维持较高的抗氧化活性，而Cu2+ 、Mg2+、K+、Al3+则使核桃青皮抗氧化物质的抗氧化能力降低。亚硫酸钠使核桃青皮抗氧化物质的抗氧化能力维持较低水平；浓度为0.10%和0.05%的H2O2能提高核桃青皮抗氧化物质的抗氧化能力，此后抗氧化能力随着其浓度的增加而下降；防腐剂山梨酸钾溶液能显著降低（P<0.05）核桃青皮抗氧化物质的抗氧化能力，二者呈负相关关系。【结论】核桃青皮提取物具有较强的抗氧化活性，其抗氧化组分主要为7种多酚类活性物质。环境因子对核桃青皮活性物质的抗氧化稳定性具有一定的影响。

关键词: 核桃青皮, 抗氧化活性成分, 鉴定, 抗氧化稳定性

Abstract: 【Objective】This research was conducted to study the analysis and antioxidation stability of antioxidative functional components from walnut green rind (AFCsWGR) which were purified by macroporous resin chromatography, which could provide a theoretical basis for the exploitation and effective utilization of walnut green rinds. 【Method】The crude extract was purified by D101 macroporous resin combined with DPPH free radical scavenging ability, and then concentrated and freeze-dried. Ultra high pressure liquid chromatography high resolution mass spectrometry (UPLC-MS) was used to analyze the AFCsWGR with strong antioxidative activity. The antioxidation stability of AFCsWGR was studied by analyzing the effect of pH, temperature, light, metal ions, oxygenant, reducer and preservative on antioxidation stability.【Result】The results showed that a total of seven antioxidative functional components in walnut green rinds were found, which included chlorogenic acid, brevifolin carboxylic acid, indigo flower- glucose/galactose, ellagic acid, quercetin arabinoside, epicatechin/catechin, quercetin -3-O- glucoside. The results of antioxidation stability of AFCsWGR showed that with the increase of pH value, the DPPH free radical scavenging rate of AFCsWGR decreased. The DPPH free radical scavenging rate was almost zero when the pH value was 12. The DPPH free radical scavenging rate of AFCsWGR could effectively be declined with the extension of storage time. The antioxidant capacity of AFCsWGR was gradually declined under indoor, light and avoiding light treatments, but there was no significant difference among them (P＞0.05). The DPPH free radical scavenging rate of light treatment was lower than the other treatments during 2-5 h. The DPPH free radical scavenging rate of AFCsWGR treated at 4, 37, 70 and 90℃ was presented as a decreasing trend, but with the change trend of increasing first and decreasing thereafter was observed in 50℃ treatment. Fe³⁺could maintain a higher antioxidant activity of AFCsWGR. However, Al³⁺, K⁺, Cu²⁺and Mg²⁺could effectively reduce the antioxidant activity of AFCsWGR. Sodium sulfite solution could reduce antioxidant ability of AFCsWGR. 0.10% and 0.05% H₂O₂could improve the antioxidant ability of AFCsWGR, thereafter, the antioxidant ability decreased with the increase of the concentration of H₂O_2. Potassium sorbate solution could significantly reduce the antioxidant capacity of AFCsWGR (P＜0.05), which exhibited a negative correlation between the antioxidant capacity of AFCsWGR and the contents of potassium sorbate solution.【Conclusion】The walnut green rind extract had a strong antioxidant activity. The main antioxidative functional components in the walnut green rinds were seven polyphenol active substances. Environmental factors could affect the antioxidation stability of AFCsWGR.:

Key words: walnut green rind, antioxidative functional components, identification, antioxidation stability

田平平，李仁宙，简永健，李健明，王杰. 核桃青皮的强抗氧化活性成分及其抗氧化稳定性[J]. 中国农业科学, 2016, 49(3): 543-553.

TIAN Ping-ping, LI Ren-zhou, JIAN Yong-jian, LI Jian-ming, WANG Jie. Analysis of Antioxidative Functional Components from Walnut Green Rind and Its Antioxidation Stability[J]. Scientia Agricultura Sinica, 2016, 49(3): 543-553.

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