Page 195 - 201904

第 36 卷第 4 期 精 细 化 工 Vol.36, No.4
201 9 年 4 月 FINE CHEMICALS Apr. 2019

食品与饲料用化学品
黑加仑花色苷的分离纯化及其热降解动力学

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薛宏坤 ，韩茜宇 ，谭佳琪 ，王 瑜 ，王 鑫 4,5*
（1. 东北农业大学 工程学院，黑龙江 哈尔滨 150030；2. 黑龙江国际旅行卫生保健中心，黑龙江 哈尔
滨 150090；3. 东北农业大学 农学院，黑龙江 哈尔滨 150030；4. 东北农业大学 食品学院， 黑龙江 哈
尔滨 150030；5. 哈尔滨海关，黑龙江 哈尔滨 150028）

摘要：以黑加仑为原料，采用 AB-8 大孔树脂-Sephadex LH-20 凝胶柱层析联用方法和液相色谱-质谱联用技术对
黑加仑花色苷进行分离纯化和组分鉴定；分析了不同纯度花色苷在不同 pH 和温度下的降解动力学；通过 1,1-
二苯基-2-三硝基苯肼（DPPH）和 2,2-联氮基-双-(3-乙基苯并噻唑啉-6-磺酸)二铵盐（ABTS）自由基的清除评价
了不同纯度花色苷的抗氧化能力。结果表明：黑加仑中包含飞燕草素-3-葡萄糖苷、矢车菊素-3-芸香糖苷、牵牛
花素-3-葡萄糖苷、芍药素-3,5-二己糖苷和锦葵素-3-半乳糖苷 5 种组分。经分离纯化后最终获得 2 种花色苷，分
别为飞燕草素-3-葡萄糖苷（A 3 ）和矢车菊素-3-芸香糖苷（A 4 ）。pH 3.0 和温度 50 ℃时，花色苷的热稳定性最强。
不同纯度花色苷组分热降解均符合一级动力学模型。经大孔树脂纯化后的花色苷（A 1 ）、乙酸乙酯萃取后的花色
苷（A 2 ）、A 3 和 A 4 对 DPPH 自由基清除率的半数抑制浓度（IC 50 ）分别为 9.45、8.17、5.95 和 7.62 mg/L，而对
ABTS 自由基清除率的 IC 50 分别为 99.38、97.21、78.19 和 85.54 mg/L。
关键词：黑加仑；花色苷；纯化；降解动力学；抗氧化活性；食品与饲料用化学品
中图分类号：TS255.42 文献标识码：A 文章编号：1003-5214 (2019) 04-0721-09

Purification and Thermal Degradation Kinetics of

Anthocyanins from Blackcurrant

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XUE Hong-kun , HAN Qian-yu , TAN Jia-qi , WANG Yu , WANG Xin 4,5*
（1. College of Engineering, Northeast Agricultural University, Harbin 150030, Heilongjiang, China; 2. Heilongjiang
International Travel Health Care Center, Harbin 150090, Heilongjiang, China; 3. College of Agricultural, Northeast
Agricultural University, Harbin 150030, Heilongjiang, China; 4. College of Food, Northeast Agricultural University,
Harbin 150030, Heilongjiang, China; 5. Harbin Customs, Harbin 150028, Heilongjiang, China）
Abstract: Anthocyanins of blackcurrant were isolated and purified by combination of AB-8 macroporous
resin and Sephadex LH-20, and components were identified by liquid chromatography-mass spectrometry.
Thermal degradation kinetics of anthocyanins with different purity was analyzed at different pH values and
temperatures. Besides, their antioxidant activities were assessed by measuring their scavenging capacities
toward 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical and 2,2-amino-di(3-ethyl-benzothiazoline
sulphonic acid-6) ammonium salt (ABTS) free radical. The results showed that anthocyanins obtained from
blackcurrant were mainly delphinidin-3-glucoside, cyanidin-3-rutinoside, petunidin-3-glucoside, paeoniflorin-
3,5-dihexoside and malvidin-3-galactoside. The two purified anthocyanins fractions were obtained, which
were identified as delphinidin-3-glucoside (A 3) and cyanidin-3-rutinoside (A 4), respectively. The thermal
stability of anthocyanins was the strongest at pH 3.0 and temperature of 50 ℃. The thermal degradation of
anthocyanins with different purity followed the first order reaction kinetics. The half maximal inhibitory
concentration (IC 50) of anthocyanins purified by macroporous resin (A 1), anthocyanins extracted by ethyl
acetate (A 2), A 3 and A 4 on DPPH free radical were 9.45, 8.17, 5.95 and 7.62 mg/L, respectively. While the

收稿日期：2018-07-30; 定用日期：2018-12-07; DOI: 10.13550/j.jxhg.20180565
基金项目：国家科技支撑计划（2017YFD0401204-5）
作者简介：薛宏坤（1988—），男，博士生，E-mail：xuehk0906@163.com。联系人：王 鑫（1984—），男，副教授，E-mail：
1657956529@qq.com。