Wu Li, Zhou Kangxi, Chen Feng, Chen Guimei, Yu Ying, Lv Xucong, Zhang Wen, Rao Pingfan, Ni Li
College of Chemistry, Fuzhou University, Fuzhou, China.
Institute of Food Science and Technology, College of Biological Science and Engineering, Fuzhou University, Fuzhou, China.
Front Microbiol. 2021 Aug 2;12:715295. doi: 10.3389/fmicb.2021.715295. eCollection 2021.
This study is the first to investigate the difference in the composition of azaphilone pigments (MonAzPs) between functional Qu (FQ) and coloring Qu (CQ) and analyze their relationships with antioxidant activity. The composition of key active components and antioxidant activity of the ethanol extracts of FQ and CQ were analyzed by Uv-vis, HPLC, and chemical antioxidant tests. The composition of MonAzPs of the ethanol extracts was further analyzed by HPLC-MS. Seven yellow pigments (MYPs) with high abundance were successfully purified for the antioxidation evaluation and in the cell. Correlation analysis between the metabolites and the antioxidant activity of indicated that MonAzPs might play an essential role in the antioxidant activity ( > 0.80). By contrast, the monacolin K (MK), polysaccharide, ergosterol, and γ-aminobutyric acid (GABA) were not significantly correlated with the antioxidant activity. Orthogonal partial least squares discriminant analysis (OPLS-DA) based on the composition of MonAzPs revealed that the abundance of MYPs is significantly different between FQ and CQ ( < 0.05 and > 1.0). Seven MYPs (monasfluore A, monaphilone B, monascuspilion, monascin, monaphilone A, ankaflavin, and new yellow pigment) with high abundance were successfully purified for the antioxidation evaluation. Chemical antioxidant tests revealed that the antioxidant activities of monaphilone A, ankaflavin, and new yellow pigment only from CQ were significantly more potent than monasfluore A and monascuspilion only separated from FQ. The cellular antioxidant assay (CAA) showed that the new yellow pigment had the best antioxidant activity (quercetin equivalent 7.23 μM), followed by monasfluore A and monaphilone B, all of which were significantly better than monascin and ankaflavin, the two most frequently reported MYPs. Research on the structure-activity relationship demonstrated that alterations of the hydroxyl that occurred on C-3' or C-11 obviously affected the antioxidant activities of MYPs. Our findings provide evidence that MYPs may be the key active components for CQ to have a more potent antioxidant capacity than FQ. The alterations of the hydroxyl that occurred on C-3' or C-11 obviously affected the antioxidant activities of MYPs.
本研究首次探究了功能性红曲(FQ)和着色红曲(CQ)中氮杂环戊酮类色素(MonAzPs)组成的差异,并分析了它们与抗氧化活性的关系。采用紫外可见光谱法、高效液相色谱法和化学抗氧化试验,分析了FQ和CQ乙醇提取物中关键活性成分的组成及抗氧化活性。通过高效液相色谱-质谱联用仪进一步分析乙醇提取物中MonAzPs的组成。成功纯化出7种高丰度黄色色素(MYPs)用于抗氧化评价及细胞实验。代谢产物与抗氧化活性之间的相关性分析表明,MonAzPs可能在抗氧化活性中起关键作用(>0.80)。相比之下,莫纳可林K(MK)、多糖、麦角甾醇和γ-氨基丁酸(GABA)与抗氧化活性无显著相关性。基于MonAzPs组成的正交偏最小二乘判别分析(OPLS-DA)表明,FQ和CQ之间MYPs的丰度存在显著差异(<0.05且>1.0)。成功纯化出7种高丰度MYPs(莫纳荧光素A、莫纳菲酮B、红曲菌红素、红曲素、莫纳菲酮A、安卡黄素和新黄色色素)用于抗氧化评价。化学抗氧化试验表明,仅来自CQ的莫纳菲酮A、安卡黄素和新黄色色素的抗氧化活性明显强于仅从FQ中分离出的莫纳荧光素A和红曲菌红素。细胞抗氧化试验(CAA)表明,新黄色色素具有最佳的抗氧化活性(槲皮素当量为7.23 μM),其次是莫纳荧光素A和莫纳菲酮B,它们均显著优于最常报道的两种MYPs红曲素和安卡黄素。结构-活性关系研究表明,C-3'或C-11位上羟基的改变明显影响MYPs的抗氧化活性。我们的研究结果证明,MYPs可能是CQ比FQ具有更强抗氧化能力的关键活性成分。C-3'或C-11位上羟基的改变明显影响MYPs的抗氧化活性。