桂花多酚类化合物电喷雾萃取电离质谱分析
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摘要
为建立桂花中多酚类化合物的电喷雾萃取电离质谱(extractive electrospray ionization-mass spectrometry,EESI-MS)分析法,以四季桂花为材料,采用高效液相色谱(high performance liquid chromatography,HPLC)法和EESI-MS测定了其醇提液中主要的多酚类化合物组成。结果表明:四季桂花中总酚和总黄酮含量分别为(133.38±0.12)mg/g和(72.49±0.09)mg/g。采用HPLC法从其醇提液中检测到了15种多酚类化合物,其中杨梅素、桑黄素、芦丁、柚皮素和(+)-儿茶素含量较为丰富。EESI-MS在负离子模式下从四季桂花醇提液中检测出了原儿茶酸、p-香豆酸、咖啡酸、表儿茶素和绿原酸5种化合物;正离子模式下检测出了肉桂酸、桑黄素和杨梅素等3种化合物。EESI-MS具有样品用量少、不需复杂分离预处理、分析速度快等优点,可用于食品中多酚类化合物的分析。
This study aimed to establish a method for the determination of polyphenols in Osmanthus fragrans flowers by extractive electrospray ionization-mass spectrometry(EESI-MS). The main polyphenolic compounds in the methanol extract of O. fragrans var. semperflorens flowers were determined by high performance liquid chromatography(HPLC) and EESI-MS. The results showed that the contents of total phenols and total flavonoids in the methanol extract were(133.38 ± 0.12) and(72.49 ± 0.09) mg/g, respectively. Fifteen polyphenolic compounds were detected by HPLC, with myricetin, morin, rutin, naringenin and(+)-catechin being abundant. p-Protocatechuic acid, coumaric acid, caffeic acid, and epicatechin were detected by EESI-MS in the negative ion mode while cinnamic acid, morin and myricetin were detected in the positive ion mode. The EESI-MS method in this study had the advantages of low sample consumption, no complex pretreatment and short analysis time and could be used for the analysis of polyphenols in food samples.
This study aimed to establish a method for the determination of polyphenols in Osmanthus fragrans flowers by extractive electrospray ionization-mass spectrometry(EESI-MS). The main polyphenolic compounds in the methanol extract of O. fragrans var. semperflorens flowers were determined by high performance liquid chromatography(HPLC) and EESI-MS. The results showed that the contents of total phenols and total flavonoids in the methanol extract were(133.38 ± 0.12) and(72.49 ± 0.09) mg/g, respectively. Fifteen polyphenolic compounds were detected by HPLC, with myricetin, morin, rutin, naringenin and(+)-catechin being abundant. p-Protocatechuic acid, coumaric acid, caffeic acid, and epicatechin were detected by EESI-MS in the negative ion mode while cinnamic acid, morin and myricetin were detected in the positive ion mode. The EESI-MS method in this study had the advantages of low sample consumption, no complex pretreatment and short analysis time and could be used for the analysis of polyphenols in food samples.
引文
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[15]于腾辉,刘星星,邓敏,等.中性解吸电喷雾萃取电离质谱法直接检测蜂蜜中的敌敌畏[J].分析化学,2016,44(9):1432-1436.DOI:10.11895/j.issn.0253-3820.150968.
[16]方菲菲,杜尚广,戴喜末,等.电喷雾萃取电离质谱法分析莲子中的生物碱[J].高等学校化学学报,2014,35(4):730-735.DOI:10.7503/cjcu20131121.
[17]卢海艳,张华,周鹏,等.内部萃取电喷雾电离质谱直接分析脐橙[J].高等学校化学学报,2015,36(10):1912-1918.DOI:10.7503/cjcu20150233.
[18]TSAI T H,TSAI T H,CHIEN Y C,et al.In vitro antimicrobial activities against cariogenic streptococci and their antioxidant capacities:a comparative study of green tea versus different herbs[J].Food Chemistry,2008,110(4):859-864.DOI:10.1016/j.foodchem.2008.02.085.
[19]刘清,李玉,姚惠源.Folin-Ciocalteu比色法测定大麦提取液中总多酚的含量[J].食品科技,2007,32(4):175-177.DOI:10.3969/j.issn.1005-9989.2007.04.052.
[20]王浩,刘德秀,杨巍.吸光光度法检测保健食品蜂胶中总黄酮[J].公共卫生与预防医学,2006,17(2):67-67.DOI:10.3969/j.issn.1006-2483.2006.02.030.
[21]曹艳萍,代宏哲,曹炜,等.Folin-Ciocaileu比色法测定红枣总酚[J].安徽农业科学,2008,36(4):1299-1302.DOI:10.3969/j.issn.0517-6611.2008.04.010.
[22]TIAN Y,LLIMATAINEN J,ALANNE A L,et al.Phenolic compounds extracted by acidic aqueous ethanol from berries and leaves of different berry plants[J].Food Chemistry,2017,220:266-281.DOI:10.1016/j.foodchem.2016.09.145.
[23]邓敏,方小伟,郭夏丽,等.基于中性解吸-电喷雾萃取电离质谱直接检测蜂蜜中的四环素[J].高等学校化学学报,2016,37(8):1430-1434.DOI:10.7503/cjcu20160127.
[24]CHEN G L,CHEN S G,XIE Y Q,et al.Total phenolic,flavonoid and antioxidant activity of 23 edible flowers subjected to in vitrodigestion[J].Journal of Functional Foods,2015,17:243-259.DOI:10.1016/j.jff.2015.05.028.
[25]邓荣华,郭宇星,李晓明,等.芦蒿秸秆总黄酮富集纯化及产物鉴定[J].食品科学,2013,34(9):85-89.DOI:10.7506/spkx1002-6630-201309019.
[26]马悦,赵乐凤,吕子燕,等.高效液相色谱-四极杆-静电场轨道阱高分辨质谱分析桑葚中黄酮类和多酚类物质[J].质谱学报,2017,38(1):45-51.DOI:10.7538/zpxb.2017.38.01.0045.
[27]李磊,谢冰,寇晓虹.高效液相色谱-串联质谱测定黄冠梨果皮中主要酚类物质[J].食品工业,2012(5):132-135.
[28]SHI J,SUN J,WEI X,et al.Identification of(-)-epicatechin as the direct substrate for polyphenol oxidase from longan fruit pericarp[J].LWT-Food Science and Technology,2009,41(10):1742-1747.DOI:10.1016/j.lwt.2008.02.003.
[29]尹智慧,孙长海,方洪壮.槲皮素与桑色素ESI-MS裂解行为的比较分析[J].分析测试学报,2017,36(2):205-211.DOI:10.3969/j.issn.1004-4957.2017.02.009.
[30]李想.黄酮醇类化合物ESI-ITMSn质谱裂解规律的量子化学研究[D].佳木斯:佳木斯大学,2015:14-18.
[2]任全进,朱洪武,于金平.桂花资源的利用价值[J].中国野生植物资源,1999(4):32-33.
[3]檀华蓉,曹德菊,夏静.桂花营养价值分析研究[J].安徽农业科学,1997(1):49-50.DOI:10.13989/j.cnki.0517-6611.1997.01.018.
[4]阳文琼,邓振平.微波消解-ICP-AES法测定代用茶桂花产品中的铁锌铜锰[J].食品科学,2009,30(10):228-230.DOI:10.3321/j.issn:1002-6630.2009.10.053.
[5]DENG C,SONG G,HU Y.Application of HS-SPME and GC-MS to characterization of volatile compounds emitted from Osmanthusflowers[J].Annali Di Chimica,2004,94(12):921.DOI:10.1002/adic.200490114.
[6]XIN H P,WU B H,ZHANG H H,et al.Characterization of volatile compounds in flowers from four groups of sweet osmanthus(Osmanthus fragrans)cultivars[J].Canadian Journal of Plant Science,2012,93(5):923-931.DOI:10.4141/cjps2012-333.
[7]YANG X Y,ZHAO B G,LIU X H,et al.Analysis of volatile compounds from the fresh flowers of Osmanthus fragrans var.thunbergii and O.fragrans var.latifolius by SPME and GC-MS[J].Journal of Nanjing Forestry University,2008(4):86-90.DOI:10.3969/j.issn.1000-2006.2008.04.019.
[8]尹伟,宋祖荣,刘金旗,等.桂花的化学成分研究[J].中国中药杂志,2015,40(4):679-685.DOI:10.4268/cjcmm20150420.
[9]SUGIYAMA M,KIKUCHI M.Studies on the constituents of Osmanthus species.X.Structures of phenolic glucosides from the leaves of Osmanthus asiaticus NAKAI[J].Chemical&Pharmaceutical Bulletin,2008,38(11):2953-2955.DOI:10.1248/cpb.40.325.
[10]LEE D G,CHOI J S,YEON S W,et al.Secoiridoid glycoside from the flowers of Osmanthus fragrans var.aurantiacus,makino inhibited the activity ofβ-secretase[J].Applied Biological Chemistry,2010,53(3):371-374.DOI:10.3839/jksabc.2010.057.
[11]LU B Y,LI M Q,ZHOU F,et al.The Osmanthus fragrans flower phenylethanoid glycoside-rich extract:acute and subchronic toxicity studies[J].Journal of Ethnopharmacology,2016,187:205-212.DOI:10.1016/j.jep.2016.04.049.
[12]LEE D G,LEE S M,BANG M H,et al.Lignans from the flowers of Osmanthus fragrans var.aurantiacus and their inhibition effect on NO production[J].Archives of Pharmacal Research,2011,34(12):2029-2035.DOI:10.1007/s12272-011-1204-y.
[13]JIANG Y,MAO S,HUANG W,et al.Phenylethanoid glycoside profiles and antioxidant activities of Osmanthus fragrans Lour.flowers by UPLC/PDA/MS and simulated digestion model[J].Journal of Agricultural&Food Chemistry,2016,64(12):2459.DOI:10.1021/acs.jafc.5b03474.
[14]贾滨,张兴磊,丁健桦,等.电喷雾萃取电离质谱技术及其应用进展[J].科学通报,2012(20):1918-1927.DOI:10.1360/972012-598.
[15]于腾辉,刘星星,邓敏,等.中性解吸电喷雾萃取电离质谱法直接检测蜂蜜中的敌敌畏[J].分析化学,2016,44(9):1432-1436.DOI:10.11895/j.issn.0253-3820.150968.
[16]方菲菲,杜尚广,戴喜末,等.电喷雾萃取电离质谱法分析莲子中的生物碱[J].高等学校化学学报,2014,35(4):730-735.DOI:10.7503/cjcu20131121.
[17]卢海艳,张华,周鹏,等.内部萃取电喷雾电离质谱直接分析脐橙[J].高等学校化学学报,2015,36(10):1912-1918.DOI:10.7503/cjcu20150233.
[18]TSAI T H,TSAI T H,CHIEN Y C,et al.In vitro antimicrobial activities against cariogenic streptococci and their antioxidant capacities:a comparative study of green tea versus different herbs[J].Food Chemistry,2008,110(4):859-864.DOI:10.1016/j.foodchem.2008.02.085.
[19]刘清,李玉,姚惠源.Folin-Ciocalteu比色法测定大麦提取液中总多酚的含量[J].食品科技,2007,32(4):175-177.DOI:10.3969/j.issn.1005-9989.2007.04.052.
[20]王浩,刘德秀,杨巍.吸光光度法检测保健食品蜂胶中总黄酮[J].公共卫生与预防医学,2006,17(2):67-67.DOI:10.3969/j.issn.1006-2483.2006.02.030.
[21]曹艳萍,代宏哲,曹炜,等.Folin-Ciocaileu比色法测定红枣总酚[J].安徽农业科学,2008,36(4):1299-1302.DOI:10.3969/j.issn.0517-6611.2008.04.010.
[22]TIAN Y,LLIMATAINEN J,ALANNE A L,et al.Phenolic compounds extracted by acidic aqueous ethanol from berries and leaves of different berry plants[J].Food Chemistry,2017,220:266-281.DOI:10.1016/j.foodchem.2016.09.145.
[23]邓敏,方小伟,郭夏丽,等.基于中性解吸-电喷雾萃取电离质谱直接检测蜂蜜中的四环素[J].高等学校化学学报,2016,37(8):1430-1434.DOI:10.7503/cjcu20160127.
[24]CHEN G L,CHEN S G,XIE Y Q,et al.Total phenolic,flavonoid and antioxidant activity of 23 edible flowers subjected to in vitrodigestion[J].Journal of Functional Foods,2015,17:243-259.DOI:10.1016/j.jff.2015.05.028.
[25]邓荣华,郭宇星,李晓明,等.芦蒿秸秆总黄酮富集纯化及产物鉴定[J].食品科学,2013,34(9):85-89.DOI:10.7506/spkx1002-6630-201309019.
[26]马悦,赵乐凤,吕子燕,等.高效液相色谱-四极杆-静电场轨道阱高分辨质谱分析桑葚中黄酮类和多酚类物质[J].质谱学报,2017,38(1):45-51.DOI:10.7538/zpxb.2017.38.01.0045.
[27]李磊,谢冰,寇晓虹.高效液相色谱-串联质谱测定黄冠梨果皮中主要酚类物质[J].食品工业,2012(5):132-135.
[28]SHI J,SUN J,WEI X,et al.Identification of(-)-epicatechin as the direct substrate for polyphenol oxidase from longan fruit pericarp[J].LWT-Food Science and Technology,2009,41(10):1742-1747.DOI:10.1016/j.lwt.2008.02.003.
[29]尹智慧,孙长海,方洪壮.槲皮素与桑色素ESI-MS裂解行为的比较分析[J].分析测试学报,2017,36(2):205-211.DOI:10.3969/j.issn.1004-4957.2017.02.009.
[30]李想.黄酮醇类化合物ESI-ITMSn质谱裂解规律的量子化学研究[D].佳木斯:佳木斯大学,2015:14-18.