Functional Components and In Vtro Antioxidant Activities of Different Types of Hongqu
-
摘要:
目的 分析功能曲(Functional Qu, FQ)、色曲(Coloring Qu,CQ)、乌衣红曲(Wuyi Qu,WQ)和古田红曲(Gutian Qu,GQ)4类红曲的主要功能活性成分和体外抗氧化活性,促进红曲抗氧化资源的开发利用。 方法 首先,通过紫外可见分光光度法、色差法和高效液相色谱法分析4类红曲的色素、莫拉可林K(MK)、γ-氨基丁酸(GABA)、麦角固醇、多糖等主要功能活性成分。其次,通过铁离子还原抗氧化能力(Ferric ion reducing antioxidant power,FRAP)、DPPH (1,1-Diphenyl-2-picrylhydrazyl radical)自由基清除试验、ABTS(2,2'-Azinobis-(3-ethylbenzthiazoline-6-sulphonate)自由基清除试验分别测定4类红曲的铁离子还原力、DPPH自由基清除能力和ABTS自由基清除能力等体外抗氧化活性。最后,采用SIMCA和SPSS软件分析主要功能活性成分和抗氧化活性的相关性。 结果 4类红曲的主要功能活性成分结果显示:CQ的橙色价、黄色价和红色价显著高于FQ、GQ和WQ,GQ的橙色价、黄色价和红色价显著高于FQ和WQ,FQ的橙色价显著高于WQ。FQ的MK含量显著高于CQ、GQ和WQ。WQ的GABA含量显著高于CQ、FQ和GQ。WQ和FQ的麦角固醇含量显著高于CQ和GQ。FQ的多糖含量最高,其次是CQ。4类红曲的体外抗氧化活性测定结果显示:CQ的铁离子还原力、清除DPPH自由基和ABTS自由基清除能力均显著强于FQ、WQ和GQ,FQ的铁离子还原力强于WQ和GQ。4类红曲的主要功能活性成分和抗氧化活性的相关性分析显示,铁离子还原能力与色价之间极显著正相关(0.733 ≥ r ≥ 0.703),DPPH IC50和ABTS IC50与色价之间极显著负相关(−0.896 ≤ r ≤ −0.880和−0.773 ≤ r ≤ −0.758),说明在4类红曲主要功能活性成分中,色素是抗氧化活性的主要功效成分,MK、GABA、麦角固醇和多糖等功能活性成分与抗氧化活性无明显相关性。 结论 CQ的色素含量和抗氧化活性明显强于FQ、GQ、和WQ,抗氧化活性与色素极显著正相关,说明红曲中色素是抗氧化活性的主要功效成分。研究结果为红曲抗氧化资源的开发和应用提供了理论基础。 Abstract:Objective Key functional components and in vitro antioxidant activities of 4 types of Hongqu (Monascus-rice fermentation paste) were determined for product development. Method Color value, monacolin K (MK), γ-aminobutyric acid (GABA), ergosterol, and polysaccharide of Functional Qu (FQ), Coloring Qu (CQ), Wuyi Qu (WQ), and Gutian Qu (GQ) were measured by means of UV-Vis, colorimeter, and HPLC. Antioxidant activity of the Hongqu was determined by in vitro chemical assays including the ferric ion reducing antioxidant power (FRAP) and 1,1-Diphenyl-2-picrylhydrazyl (DPPH) and 2,2'-Azinobis-(3-ethylbenzthiazoline-6-sulphonate (ABTS) radical scavenging capacities. Correlation between the functional components and the antioxidant activities of Hongqu was analyzed using SIMCA and SPSS software. Result The Hongqu specimens varied in the following aspects. CQ was measured significantly higher on orange, yellow, and red color value than FQ, GQ, and WQ, while GQ on orange, yellow, and red color value than FQ and WQ, and FQ on orange color value than WQ. FQ contained significantly more MK than CQ, GQ, and WQ, whereas WQ significantly more GABA than CQ, FQ, and GQ, but WQ and FQ significantly more ergosterol than CQ and GQ, and FQ had the highest content of polysaccharides, which was followed by CQ. The FRAP and DPPH and ABTS scavenging abilities of CQ were significantly higher than those of FQ, WQ, and GQ, and FQ was stronger in FRAP than WQ or GQ. The color value of Hongqu positively correlated with FRAP (0.733 ≥ r ≥ 0.703) and negatively with the scavenging 50% DPPH (−0.896 ≤ r ≤ −0.880) and ABTS (−0.773 ≤ r ≤ −0.758). It appeared that pigment was the critical antioxidant components in the Hongqu. On the other hand, neither MK, GABA, ergosterol, nor polysaccharides significant correlated with the in vitro antioxidant activity of the 4 Hongqu. Conclusion An extremely significant correlation between the pigment and antioxidant activity were demonstrated in CQ more than the other 3 Hongqu. In the development of natural antioxidant products, Monascus pigment could be a viable potential candidate. -
表 1 不同红曲的橙色价(E465)、黄色价(E390)和红色价(E510)
Table 1. Orange, yellow, and red color value of various Hongqu
样品 Sample 橙色价 E465 黄色价 E390 红色价 E510 总色价 E 功能曲 FQ 98.80±47.02 c 128.51±50.11 c 121.72±54.38 c 349.02±150.98 c 色曲 CQ 1045.98±416.39 a 1426.66±499.59 a 1438.60±484.91 a 3911.23±1395.19 a 乌衣红曲WQ 73.26±19.40 d 112.36±38.07 c 101.81±34.26 c 287.43±91.12 d 古田红曲 GQ 187.15±23.73 b 274.72±43.72 b 292.63±36.64 b 754.50±97.13 b 同一列数据后不同小写字母表示差异显著(P < 0.05),表2、3同。
Different letters on the same column mean significant difference(P<0.05). The same for Table 2,3.表 2 不同红曲的色差
Table 2. Chromatism of various Hongqu
样品编号
Sample白/黑差
△L*红/绿差
△a*黄/蓝差
△b*总色差
△EFQ −51.81±1.02 b 11.54±2.52 a 5.80±0.60 ab 53.45±0.55 b CQ −53.97±0.76 c 11.78±1.12 a 8.15±2.06 a 55.88±0.31 a WQ −44.80±1.79 a 10.60±2.88 a 6.43±1.42 ab 46.55±2.40 c GQ −54.53±0.24 c 10.94±0.68 a 4.75±0.76 b 55.83±0.28 a 表 3 不同红曲的莫纳克林K(MK)
Table 3. MK contents in various Hongqu
样品编号
Sample
No.内酯式莫纳克林K
Lactone forms of
MK/(mg·g−1)酸式莫纳克林K
Acid forms of
MK/(mg·g−1)莫纳克林K
MK/
(mg·g−1)平均莫纳克林K
MK/
(mg·g−1)FQ1 29.13±0.02 4.60±0.01 33.73±0.00 16.13±11.08 a FQ2 17.66±0.08 2.61±0.02 20.27±0.11 FQ3 7.38±0.04 1.64±0.03 9.02±0.07 FQ4 7.78±0.04 2.88±0.01 10.66±0.05 FQ5 5.11±0.01 1.88±0.02 6.98±0.03 CQ1 — 0.10±0.04 0.10±0.04 0.26±0.13 b CQ2 — 0.41±0.01 0.41±0.01 CQ3 — 0.26±0.01 0.26±0.01 CQ4 — 0.38±0.00 0.38±0.00 CQ5 — 0.17±0.02 0.17±0.02 WQ1 — 0.03±0.00 0.03±0.00 0.03±0.01 c WQ2 — 0.03±0.00 0.03±0.00 WQ3 — 0.03±0.00 0.03±0.00 WQ4 — 0.04±0.00 0.04±0.00 WQ5 — 0.04±0.00 0.04±0.00 GQ1 — 0.02±0.00 0.02±0.00 0.02±0.01 c GQ2 — 0.02±0.00 0.02±0.00 GQ3 — 0.02±0.00 0.02±0.00 GQ4 — 0.03±0.00 0.03±0.00 GQ5 — 0.03±0.00 0.03±0.00 “—”表示未检出。
“—” means no detected.表 4 不同红曲主要功能活性成分、抗氧化等指标的相关系数
Table 4. Correlation coefficients on key functional components and antioxidant indices of various Hongqu
指标
Index红色价
E510黄色价
E390橙色价
E465总色差
△E麦角固醇
Ergosterol莫纳克林
K
MKγ-氨基丁酸
GABA多糖
Polysaccharide铁离子
还原力
FRAP清除50%
DPPH
的浓度
DPPH IC50清除50%
ABTS
的浓度
ABTS
IC50红色价 E510 1 0.983** 0.985** 0.810** −0.477* −0.135 −0.536* −0.053 0.703** −0.880** −0.759** 黄色价 E390 1 0.980** 0.778** −0.477* −0.138 −0.505* −0.057 0.733** −0.886** −0.758** 橙色价 E465 1 0.825** −0.493* −0.097 −0.556* 0.005 0.704** −0.896** −0.773** 总色差 △E 1 −0.627** −0.112 −0.798** −0.042 0.427 −0.805** −0.569** 麦角固醇 Ergosterol 1 0.386 0.773** 0.362 −0.448* 0.412 0.211 莫纳克林K MK 1 −0.061 0.657** −0.259 −0.187 −0.180 γ-氨基丁酸 GABA 1 0.001 −0.236 0.596** 0.319 多糖Polysaccharide 1 −0.323 −0.179 −0.140 铁离子还原力FRAP 1 −0.585** −0.635** 清除50%DPPH的浓度 DPPH IC50 1 0.788** 清除50%ABTS的浓度 ABTS IC50 1 “ **”表示极显著(P<0.01),“*”表示显著(P<0.05)。
“**” means extremely significant difference (P <0.01), “*” means significant difference(P <0.05). -
[1] 李钟庆, 郭芳. 红曲菌的形态与分类学[M]. 北京: 中国轻工业出版社, 2003. [2] BARBOSA R N, LEONG S L, VINNERE-PETTERSSON O, et al. Phylogenetic analysis of Monascus and new species from honey, pollen and nests of stingless bees [J]. Studies in Mycology, 2017, 86: 29−51. doi: 10.1016/j.simyco.2017.04.001 [3] 姚青. 以麦麸为基质的红曲霉的固态发酵及抗氧化活性研究[D]. 杭州: 浙江工业大学, 2015.YAO Q. Study on Monascus solid-state fermentation and antioxidant activity of matrix in wheat bran[D]. Hangzhou: Zhejiang University of Technology, 2015. (in Chinese) [4] CHEN W P, FENG Y L, MOLNÁR I, et al. Nature and nurture: Confluence of pathway determinism with metabolic and chemical serendipity diversifies Monascus azaphilone pigments [J]. Natural Product Reports, 2019, 36(4): 561−572. doi: 10.1039/C8NP00060C [5] 屈炯, 王斌, 吴佳佳, 等. 红曲色素组份分离及其抗氧化活性研究 [J]. 现代食品科技, 2008, 24(6):527−531. doi: 10.13982/j.mfst.1673-9078.2008.06.028QU J, WANG B, WU J J, et al. Study on separation of Monascus pigment and their antioxidative properties [J]. Modern Food Science and Technology, 2008, 24(6): 527−531.(in Chinese) doi: 10.13982/j.mfst.1673-9078.2008.06.028 [6] ENDO A. Monacolin K, a new hypocholesterolemic agent that specifically inhibits 3-hydroxy-3-methylglutaryl coenzyme A reductase [J]. The Journal of Antibiotics, 1980, 33(3): 334−336. doi: 10.7164/antibiotics.33.334 [7] 周香珍, 林书发, 何书华. 红曲药学评价研究进展 [J]. 中国现代中药, 2016, 18(7):936−941. doi: 10.13313/j.issn.1673-4890.2016.7.028ZHOU X Z, LIN S F, HE S H. Research progress in pharmacodynamics evaluation red yeast rice [J]. Modern Chinese Medicine, 2016, 18(7): 936−941.(in Chinese) doi: 10.13313/j.issn.1673-4890.2016.7.028 [8] 温学伟, 马新, 周立平, 等. 红曲抗氧化的研究进展 [J]. 食品工业科技, 2011, 32(2):376−378. doi: 10.13386/j.issn1002-0306.2011.02.115WEN X W, MA X, ZHOU L P, et al. Research advances of antioxidant action in Monascus [J]. Science and Technology of Food Industry, 2011, 32(2): 376−378.(in Chinese) doi: 10.13386/j.issn1002-0306.2011.02.115 [9] 谢振兴. GABA改善氧化应激和甲状腺功能及其机制研究[D]. 无锡: 江南大学, 2014.XIE Z X. Effects of GABA on oxidative stress and thyroid function and its mechanism[D]. Wuxi: Jiangnan University, 2014. (in Chinese) [10] HSIAO W Y, GU K L, WENG Y M. Antioxidant activity and contents of total phenolic, monacolin K, GABA and citrinin of Monascus-fermented soy sauce [J]. Advanced Materials Research, 2013, 807/808/809: 2066−2070. [11] 李月婵, 张子祎, 魏学源, 等. 红曲霉产胞外多糖的条件优化及功效活性的初步检测 [J]. 天津农学院学报, 2020, 27(2):79−83. doi: 10.19640/j.cnki.jtau.2020.02.017LI Y C, ZHANG Z Y, WEI X Y, et al. Optimization of conditions for the production of exopolysaccharides by Monascus and preliminary detection of efficacy activity [J]. Journal of Tianjin Agricultural University, 2020, 27(2): 79−83.(in Chinese) doi: 10.19640/j.cnki.jtau.2020.02.017 [12] 汪帅, 孙宇, 李春梅, 等. 豆甾醇的研究进展概述 [J]. 中国药业, 2019, 28(23):96−98. doi: 10.3969/j.issn.1006-4931.2019.23.031WANG S, SUN Y, LI C M, et al. Research progress of stigmasterol [J]. China Pharmaceuticals, 2019, 28(23): 96−98.(in Chinese) doi: 10.3969/j.issn.1006-4931.2019.23.031 [13] 张红林, 李桂玲, 苏国成, 等. 古田红曲米抗氧化活性物质的分离纯化 [J]. 现代食品科技, 2018, 34(5):136−142,75. doi: 10.13982/j.mfst.1673-9078.2018.05.020ZHANG H L, LI G L, SU G C, et al. Separation and purification of the antioxidant compounds from Gutian red yeast rice [J]. Modern Food Science and Technology, 2018, 34(5): 136−142,75.(in Chinese) doi: 10.13982/j.mfst.1673-9078.2018.05.020 [14] 王智耀, 卞丹, 何理琴, 等. 红曲黄酒酿造用曲真菌菌群分析 [J]. 中国食品学报, 2019, 19(1):200−206.WANG Z Y, BIAN D, HE L Q, et al. Studies on the fungal community of the traditional fermentation starter of Hong qu glutinous rice wine [J]. Journal of Chinese Institute of Food Science and Technology, 2019, 19(1): 200−206.(in Chinese) [15] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准 食品添加剂 红曲米: GB 1886.19—2015[S]. 北京: 中国标准出版社, 2016. [16] 中华人民共和国国家发展和改革委员会. 功能性红曲米: QB/T 2847—2007[S]. 北京: 中国标准出版社, 2007. [17] 福建省卫生和计划生育委员会. 食品安全地方标准 酿造用红曲: DBS35/ 002—2017[S]. 北京: 中国标准出版社, 2017. [18] 中华人民共和国工业和信息化部. γ-氨基丁酸: QB/T 4587—2013[S]. 北京: 中国轻工业出版社, 2014. [19] 汤葆莎, 吴俐, 陈君琛, 等. LED光源在促进秀珍菇菌丝降解代谢麦麸中的作用 [J]. 福建农业学报, 2016, 31(4):371−376. doi: 10.19303/j.issn.1008-0384.2016.04.008TANG B S, WU L, CHEN J C, et al. Effect of LED on wheat bran digestion by Pleurotus geesteranus mycelia [J]. Fujian Journal of Agricultural Sciences, 2016, 31(4): 371−376.(in Chinese) doi: 10.19303/j.issn.1008-0384.2016.04.008 [20] 吴俐, 沈恒胜, 汤葆莎, 等. 油茶枝液体培养茶薪菇菌丝的营养基质动态分析 [J]. 福建农业学报, 2013, 28(9):906−909. doi: 10.3969/j.issn.1008-0384.2013.09.015WU L, SHEN H S, TANG B S, et al. Dynamic changes in nutrition of culture medium for Agrocybe chaxingu Huang with Camellia oleifera Abel extracts [J]. Fujian Journal of Agricultural Sciences, 2013, 28(9): 906−909.(in Chinese) doi: 10.3969/j.issn.1008-0384.2013.09.015 [21] WU L, ZHOU K X, CHEN F, et al. Comparative study on the antioxidant activity of Monascus yellow pigments from two different types of Hongqu-functional qu and coloring qu [J]. Frontiers in Microbiology, 2021, 12: 715295. doi: 10.3389/fmicb.2021.715295 [22] 胡均亮, 陆方菊, 陈功, 等. 不同来源红曲米多酚类化合物和抗氧化活性的聚类分析 [J]. 中国酿造, 2017, 36(3):39−43. doi: 10.11882/j.issn.0254-5071.2017.03.009HU J L, LU F J, CHEN G, et al. Cluster analysis of polyphenol compounds and antioxidant activity of red kojic rice from different producing areas [J]. China Brewing, 2017, 36(3): 39−43.(in Chinese) doi: 10.11882/j.issn.0254-5071.2017.03.009 [23] ZHOU K X, WU L, CHEN G M, et al. Development of a novel restrictive medium for Monascus enrichment from Hongqu based on the synergistic stress of lactic acid and ethanol [J]. Frontiers in Microbiology, 2021, 12: 702951. doi: 10.3389/fmicb.2021.702951 [24] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准 食品添加剂 红曲黄色素: GB 1886.66—2015[S]. 北京: 中国标准出版社, 2016. [25] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准 食品添加剂 红曲红: GB 1886.181—2016[S]. 北京: 中国标准出版社, 2017. [26] 衣珊珊, 沈昌, 韩永斌, 等. 红曲色素形成机理及提高其色价的途径 [J]. 食品科学, 2005, 26(7):256−261. doi: 10.3321/j.issn:1002-6630.2005.07.063YI S S, SHEN C, HAN Y B, et al. Synthetic mechanism and approach to enhance the color value of Monascus pigments [J]. Food Science, 2005, 26(7): 256−261.(in Chinese) doi: 10.3321/j.issn:1002-6630.2005.07.063 [27] LU Q Y, LEE R P, HUANG J J, et al. Quantification of bioactive constituents and antioxidant activity of Chinese yellow wine [J]. Journal of Food Composition and Analysis, 2015, 44: 86−92. doi: 10.1016/j.jfca.2015.07.005 [28] 刘婷婷. 高产γ-氨基丁酸乳酸菌菌株选育及其转化条件优化[D]. 无锡: 江南大学, 2010.LIU T T. Screening of lacotbacillus high-efficiency producing γ-aminobutyric acid from L-glutamate acid and optimization of biotransformation conditions[D]. Wuxi: Jiangnan University, 2010. (in Chinese) [29] 郑鸿雁, 赵炜彤, 昌妍希, 等. GABA高产菌株的筛选、鉴定及诱变选育 [J]. 食品研究与开发, 2016, 37(2):177−182. doi: 10.3969/j.issn.1005-6521.2016.02.045ZHENG H Y, ZHAO W T, CHANG Y X, et al. Sceening and indentifiacation and mutagenesis of high-yielding strains for producing GABA [J]. Food Research and Development, 2016, 37(2): 177−182.(in Chinese) doi: 10.3969/j.issn.1005-6521.2016.02.045 [30] LIANG J X, ZHANG Q Q, HUANG Y F, et al. Comprehensive chemical profiling of monascus-fermented rice product and screening of lipid-lowering compounds other than monacolins [J]. Journal of Ethnopharmacology, 2019, 238: 111879. doi: 10.1016/j.jep.2019.111879 [31] LV X C, WENG X, ZHANG W, et al. Microbial diversity of traditional fermentation starters for Hong Qu glutinous rice wine as determined by PCR-mediated DGGE [J]. Food Control, 2012, 28(2): 426−434. doi: 10.1016/j.foodcont.2012.05.025 [32] 伍健萍. 红曲霉发酵多糖条件及抗氧化活性的初步研究[D]. 天津: 天津科技大学, 2011.WU J P. Preliminary study on the conditions and antioxidant activity of Monascus fermented polysaccharides [D]. Tianjin: Tianjin University of Science and Technology, 2011. (in Chinese) [33] 严敏嘉, 李小芳, 赵甜甜, 等. 红曲固态发酵过程中糖类物质的动态变化分析 [J]. 食品研究与开发, 2018, 39(3):79−83. doi: 10.3969/j.issn.1005-6521.2018.03.015YAN M J, LI X F, ZHAO T T, et al. Analysis of dynamic changes of sugars in the solid fermentation of Monascus [J]. Food Research and Development, 2018, 39(3): 79−83.(in Chinese) doi: 10.3969/j.issn.1005-6521.2018.03.015