海藻MGMG型甘油糖脂的研究
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摘要
目的鉴定中药海藻(羊栖菜Sargassum fusiforme)中的单半乳糖基单酰基甘油酯(monogalactosylmonoacylglycerol,MGMG),分析sn-1型和sn-2型位置异构体的化学特征。方法利用多种色谱手段分离得到MGMG,采用NMR、HR-ESI-MS等谱学方法鉴定结构,采用HPLC、HPLC-ESI-MS/MS分析位置异构体的互变及其色谱-质谱特征。结果分离到并鉴定5个MGMG,酰基分别为十八碳四烯酰基、十八碳三烯酰基、二十碳四烯酰基、十八碳二烯酰基和十八碳单烯酰基;sn-1型和sn-2型MGMG单体均不稳定,会相互迅速转变直至sn-1型为主(相对峰面积85∶15)的平衡状态。sn-2型在反相色谱柱上的保留时间较sn-1型小,先被洗脱;两者二级质谱碎片离子丰度有较大差异,以[M+Na-Gal]~+为基峰(100%),sn-2型的[M+Na-RCOOH]~+丰度>50%,sn-1型的[M+Na-RCOOH]~+丰度<20%。结论首次从褐藻门中分离鉴定上述5个MGMG,阐明了sn-1型和sn-2型MGMG之间的互变过程,首次报道这2种位置异构体的色谱-质谱特征,可用于MGMG类化合物酰基取代位置的鉴定。
Objective To indentify monogalactosylmonoacylglycerol(MGMG) and analyze the chemical characteristics of sn-1 and sn-2 type isomers in Marine TCM Sargassum fusiforme.Methods The MGMG compounds were isolated by multiple chromatography methods and their structures were determined by spectroscopic methods such as NMR and HRESI-MS.The interconversion and chromatography-mass spectrometry feature of MGMG positional isomers were analyzed through HPLC and HPLC-ESI-MS/MS.Results Five MGMGs were isolated from Sargassum fusiforme,and the fatty acyl compositions were stearidonoyl,linolenoyl,arachidoyl,linoleyl,and oleyl.The sn-1 and sn-2 type of MGMG were unstable.The interconversion tended to be sn-1 type rapidly,and kept balanced content at 85:15.The relative retention time of sn-2 type was less than sn-1 type on C_(18) reverse phase chromatography.The abundant fragment ions of MS/MS were significantly differences.The base peak was [M+Na-Gal]~+(100%),and the peak intensity of [M+Na-RCOOH]~+ was always more than 50% from sn-2 type while less than 20% from sn-1 type.Conclusion Five MGMGs were isolated from brown algae for the first time.This was the first report about the interconversion and chromatography-mass spectrometry feature of sn-1 and sn-2 type.It can use to determine the fatty acyl attachment in each MGMG.
Objective To indentify monogalactosylmonoacylglycerol(MGMG) and analyze the chemical characteristics of sn-1 and sn-2 type isomers in Marine TCM Sargassum fusiforme.Methods The MGMG compounds were isolated by multiple chromatography methods and their structures were determined by spectroscopic methods such as NMR and HRESI-MS.The interconversion and chromatography-mass spectrometry feature of MGMG positional isomers were analyzed through HPLC and HPLC-ESI-MS/MS.Results Five MGMGs were isolated from Sargassum fusiforme,and the fatty acyl compositions were stearidonoyl,linolenoyl,arachidoyl,linoleyl,and oleyl.The sn-1 and sn-2 type of MGMG were unstable.The interconversion tended to be sn-1 type rapidly,and kept balanced content at 85:15.The relative retention time of sn-2 type was less than sn-1 type on C_(18) reverse phase chromatography.The abundant fragment ions of MS/MS were significantly differences.The base peak was [M+Na-Gal]~+(100%),and the peak intensity of [M+Na-RCOOH]~+ was always more than 50% from sn-2 type while less than 20% from sn-1 type.Conclusion Five MGMGs were isolated from brown algae for the first time.This was the first report about the interconversion and chromatography-mass spectrometry feature of sn-1 and sn-2 type.It can use to determine the fatty acyl attachment in each MGMG.
引文
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[2]Pettit G R,Bond T J,Herald D L,et al.Isolation and structure of spongilipid from the republic of Singapore marine Porifera Spongia cf.Hispida[J].Canadian JChem,1997,75(6):920-925.
[3]Cateni F,Falsone G,Zilic J,et al.Glyceroglycolipids from Euphorbia nicaeensis All.with antiinflamatory activity[J].Arkivoc,2004,37(3):54-65.
[4]Rho M C,Matsunaga K,Yasuda K,et al.A novel monogalactosylacylglycerol with inhibitory effect on platelet aggregation from the cyanophyceae Oscillatoria rosea[J].J Nat Prod,1996,59(3):308-309.
[5]Luyen B T T,Thao N P,Tai B H,et al.Chemical constituents of Triticum aestivum and their effects on adipogenic differentiation of 3T3-L1 preadipocytes[J].Arch Pharm Res,2015,38(6):1011-1018.
[6]彭燕,刘永宏.黄海海燕的化学成分研究[J].中国药学杂志,2011,46(24):1883-1885.
[7]Fang Z,Yang J S,Ah J H,et al.Capsofulvesins A-C,cholinesterase inhibitors from Capsosiphon fulvescens[J].Chem Pharm Bull,2012,60(11):1351-1358.
[8]Hiraga Y,Shikano T,Widianti T,et al.Three new glycolipids with cytolytic activity from cultured marine dinoflagellate Heterocapsa circularisquama[J].Nat Prod Res,2008,22(8):649-657.
[9]王广树,王凌燕,杨晓虹,等.石蒜科植物朱顶红中非生物碱类成分的研究[J].中国药学杂志,2006,43(18):1374-1375.
[10]Al-Fadhli A,Wahidulla S,D’Souza L.Glycolipids from the red alga Chondria armata(Kütz.)Okamura[J].Glycobiology,2006,16(10):902-915.
[11]Murakami N,Morimoto T,Imamura H,et al.Enzymatic transformation of glyceroglycolipids into sn-1 and sn-2lysoglyceroglycolipids by use of Rhizopus arrhizus Lipase[J].Tetrahedron,1994,50(7):1993-2002.