紫薯花青苷定性分析及其主要花青苷的制备与抗氧化活性研究
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摘要
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.
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.
引文
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[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.
[2] LI J,SHI Z,MI Y. Purple sweet potato color attenuates high fat-induced neuroinflammation in mouse brain by inhibiting MAPK and NF-κBactivation[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] LEEM 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 HPLCESI-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-QTOFMS/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.