采用超高效液相-三重四级杆质谱仪(UPLC-MS/MS)对紫薯花青苷进行定性分析,共检测出3类12种花青苷,其苷元分别为飞燕草素、矢车菊素和芍药素,其中芍药素-3-(咖啡酰-对-羟基苯甲酰-槐糖苷)-5-葡糖苷含量最高,分别采用AB-8大孔树脂、聚酰胺和葡聚糖凝胶层析柱对其进行分离纯化,纯化后纯度可达98%。并分别采用福林酚试剂法和测定清除DPPH自由基活性的方法,评价其抗氧化活性。可得出结论,芍药素-3-(咖啡酰-对-羟基苯甲酰-槐糖苷)-5-葡糖苷的抗氧化活性与其含量成正相关,相同苷元的酰基花青苷的活性高于非酰基花青苷,咖啡酸和对羟基苯甲酸可显著提高花青苷的抗氧化活性。该研究可为紫薯花青苷定性、分离纯化和活性研究奠定了基础。
Ultra performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS/MS) was used to identify and analyze chemical structures of anthocyanins in purple sweet potato. There were 12 types of anthocyanins detected and could be divided into three main categories: cyanidins, peonidins, and delphinidins. Peonidin-3-(caffeoyl-p-hydroxybenzoyl-sophoroside)-5-glucoside was the major component, which was then isolated and purified by AB-8 macroporous resin, polyamide and dextran gel column, and the purity was up to 98%. Moreover, the antioxidant activity of the purified peonidin-3-(caffeoyl-p-hydroxybenzoyl-sophoroside)-5-glucoside was determined by folin-phenol reagent method and its scavenging effect on DPPH free radicals. The results showed that its antioxidant activity was positively dose-dependent, and acyl anthocyanins had higher activity than non-acyl anthocyanins with the same aglycone, which may be due to the presence of caffeic acid and p-hydroxybenzoic acid in their structures. Overall, this research lays a foundation for qualitative analysis, isolation and studying antioxidant activities of anthocyanins in purple sweet potato.
[1] LI W L, YU H Y, ZHANG X J, et al. Purple sweet potato anthocyanin exerts antitumor effect in bladder cancer [J]. Curr Oncol Rep,2018, 40(1):73-82.
[2] LI J, SHI Z, MI Y. Purple sweet potato color attenuates high fat-induced neuroinflammation in mouse brain by inhibiting MAPK and NF-κ Bactivation [J]. Mol Med Rep,2018,17(3):4 823-4 831.
[3] CAI Z, SONG L, QIAN B, et al. Understanding the effect of anthocyanins extracted from purple sweet potatoes on alcohol-induced liver injury in mice [J]. Food Chem,2018,245: 263-470.
[4] ZHANG Z F, LU JUN, ZHENG Y L, et al. Purple sweet potato color attenuates hepatic insulin resistance via blocking oxidative stress and endoplasmic reticulum stress in high-fat-diet-treated mice[J].J Nutr Biochem, 2013, 24:1 008-1 018.
[5] ZHANG X, YANG Y, WU Z, et al. The modulatory effect of anthocyanins from purple sweet potato on human intestinal microbiota in vitro[J]. J Agr Food Chem,2016,64:2 582-2 590.
[6] HU J T, CHEN G P, ZHANG Y J, et al. Anthocyanin composition and expression analysis of anthocyanin biosynthetic genes in kidney bean pod[J]. Plant Physiol Biochem, 2015,97:304-312.
[7] KARAKAYA S, SIMSEK S, EKER A T, et al. Stability and bioaccessibility of anthocyanins in bakery products enriched with anthocyanins [J]. Food Funct, 2016, 7(8):34-37.
[8] KAHKONENN M P, HEINONEN M. Antioxidant activity of anthocyanins and their aglycons[J]. J Agr Food Chem, 2003,51(4):628-633.
[9] ALI H M, ALMAGRIBI W, ALRASHIDI M N, et al. Antiradical and reductant activities of anthocyanidins and anthocyanins, structureactivity relationship and synthesis[J]. Food Chem,2016,194:1 275-1 282.
[10] LEE M J, PARK J S, CHOI D S, et al. Characterization and quantitation of anthocyanins in purple-fleshed sweet potatoes cultivated in Korea by HPLC-DAD and HPLC-ESI-QTOF-MS/MS[J]. J Agr Food Chem,2013,61:3 148-3 158.
[11] HE W, ZENG M M, CHEN J, et al. Identification and quantitation of anthocyanins in purple-fleshed sweet potatoes cultivated in China by UPLC-PDA and UPLC-QTOF-MS/MS[J].Food Chem,2016,64:171-177.
[12] ZHAO J G, YAN Q Q, XUE R Y, et al. Isolation and identification of colourless caffeoyl compounds in purple sweet potato by HPLC-DAD-ESI/MS and their antioxidant activities[J].Food Chem,2014,161:22-26.
[13] JULIA M, ENRIQUE J, DAZ M, et al. Recovery of anthocyanins using membrane technologies: A review [J]. Cri Rev Anal Chem, 2018, 48(3):143-175.
[14] CRISTIN T, HORTON D, SAM A,et al. Analysis of anthocyanins in foods by liquid chromatography, liquid chromatography-mass spectrometry and capillary electrophoresis [J]. J Chromatogr A,2000,881: 403-410.
[15] ZHU Z Z, LIU Y, GUAN Q Y, et al. Purification of purple sweet potato extract by dead-end filtration and investigation of membrane fouling mechanism[J]. Food Bioprocess Technol,2015, 8:1 680-1 689.
[16] JARI H, HENGAMEH F, ANSSI V, et al. Extraction and purification of anthocyanins from purple-fleshed potato[J]. Food Bioprod Pr,2016,99:136-146.
[17] HU, Y J, DENG L Q, CHEN J W, et al. An analytical pipeline to compare and characterise the anthocyanin antioxidant activities of purple sweet potato cultivars [J]. Food Chem,2016,194:46-54.
[18] KANO M, TAKAYANAGI T, HARADA K, et al. Antioxidative activity of anthocyanins from purple sweet potato, Ipomoerabatatas cultivar Ayamurasaki[J].Biosc Biotech Biochem,2005,69(5): 979-988.
[19] REYES L F, MILLER J C, CISNEROS-ZEVALLOS L, et al. Antioxidant capacity, anthocyanins and total phenolics in purple-and red-fleshed potato(Solanum tuberosum L.) genotypes[J]. Food Chem, 2005, 82:271-277.
[20] PAULA A C, LUTFIYE E, RYAN C, et al. Pre-heating and polyphenol oxidase inhibition impact on extraction of purple sweet potato anthocyanins[J]. Food Chem,2015,180:227-234.
[21] 刘彩芬, 秦公伟,韩豪,等. UPLC-MS/MS分析不同品种蓝莓中的花青苷[J]. 中国实验方剂学杂志, 2018,24(21):62-68.
[22] ZHAO C L, CHEN Z J, BAI X S, et al. Structure-activity relationships of anthocyanidin glycosylation [J]. Mol Divers,2014,18(3):687-700.
[23] HUSSEIN M A, WAFAA A, MONA N A, et al. Antiradical and reductant activities of anthocyanidins and anthocyanins, structure-activity relationship and synthesis[J]. Food Chem, 2016, 194: 1 275-1 279.
[24] DA SILVA P F, PAULO L, BARBAFINA A, et al. Photoprotection and the photophysics of acylated anthocyanins[J]. Chem,2012,18(12),3 736-3 744.
[25] JUDIT R H, ANDREA N, ERIKA F, et al. Anthocyanin composition, antioxidant efficiency, and a-amylase inhibitor activity of different Hungarian sour cherry varieties (Prunus cerasus L.) [J]. Food Chem,2016,194,222-229.
[26] NOBUHIRO S, YUZO N, YOSHIHIRO O, et al. The role of acyl-glucose in anthocyanin modifications [J]. Molecules,2014,19(11):18 747-18 766.
