基于电喷雾-四极杆-飞行时间质谱的高聚合度人乳寡糖异构体结构解析
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摘要
人乳寡糖是一类存在于人乳中的天然益生元,在促进婴儿肠道菌群生长、完善免疫系统功能和抵抗病原体侵染过程中发挥着不可替代的作用。人乳寡糖的功能与其结构密切相关,但其结构组成复杂、连接方式多样,存在大量的同分异构体,且随着寡糖聚合度的升高,同分异构体的数目和复杂性都急剧增加。因此,高聚合度的寡糖异构体的结构解析是人乳寡糖研究的难点之一,对寡糖的生物功能研究具有重要意义。本研究采用电喷雾-四极杆-飞行时间质谱(ESI-Q/TOF-MS),在负离子模式下对分离获得的18个高聚合度人乳寡糖(其中3个为首次报道)进行了结构解析,探讨了同组异构体之间碎片离子的差异,并详细总结了寡糖异构体的裂解规律,为复杂的高聚合度人乳寡糖异构体的结构解析及新型糖结构的发现提供了科学依据。
Human milk oligosaccharides are a kind of natural prebiotics that exist in human milk. They play an irreplaceable role in the growth of infantile intestinal flora, the improvement of immune system and the resistance to pathogen infection. The function of human milk oligosaccharides is closely related to their structures which are complex with various linkages. Besides, the oligosaccharides have a large number of isomers, the number and complexity of which increase dramatically with the degrees of their polymerization. Therefore, the structural analysis of oligosaccharide isomers with a high degree of polymerization is one of the difficulties in the study of human milk oligosaccharides, and is of great significance for the study of the biological function of oligosaccharides. In this study, electrospray ionization-quadrupole-time of flight mass spectrometry(ESI-Q/TOF-MS) was used to analyze the structures of eighteen high-degree polymerized human milk oligosaccharides in a negative ion mode, and three of them were firstly reported. Differences of fragment ions between the isomers were discussed, and the cleavage rules of oligosaccharide isomers were summarized. This study provided a scientific basis for the structural analysis of the complex isomers of highly polymerized human milk oligosaccharides and the discovery of novel sugar structures.
Human milk oligosaccharides are a kind of natural prebiotics that exist in human milk. They play an irreplaceable role in the growth of infantile intestinal flora, the improvement of immune system and the resistance to pathogen infection. The function of human milk oligosaccharides is closely related to their structures which are complex with various linkages. Besides, the oligosaccharides have a large number of isomers, the number and complexity of which increase dramatically with the degrees of their polymerization. Therefore, the structural analysis of oligosaccharide isomers with a high degree of polymerization is one of the difficulties in the study of human milk oligosaccharides, and is of great significance for the study of the biological function of oligosaccharides. In this study, electrospray ionization-quadrupole-time of flight mass spectrometry(ESI-Q/TOF-MS) was used to analyze the structures of eighteen high-degree polymerized human milk oligosaccharides in a negative ion mode, and three of them were firstly reported. Differences of fragment ions between the isomers were discussed, and the cleavage rules of oligosaccharide isomers were summarized. This study provided a scientific basis for the structural analysis of the complex isomers of highly polymerized human milk oligosaccharides and the discovery of novel sugar structures.
引文
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27 Yan J Y,Ding J J,Jin G W,Yu D P,Yu L,Long Z,Guo Z M,Chai W G,Liang X M.Anal.Chem.,2018,90(5):3174-3182
28 Taufik E,Fukuda K,Senda A,Saito T,Williams C,Tilden C,Eisert R,Oftedal O,Urashima T.Glycoconjugate J.,2012,29(2-3):119-134
2 Wu S,Tao N N,German J B,Grimm R,Lebrilla C B.J.Proteome Res.,2010,9(8):4138-4151
3 Thurl S,Munzert M,Boehm G,Matthews C,Stahl B.Nutr.Rev.,2017,75(11):920-933
4 Tao N N,Wu S,Kim J,An H J,Hinde K,Power M L,Gagneux P,German J B,Lebrilla C B.J.Proteome Res.,2011,10(4):1548-1557
5 Ballard O,Morrow A L.Pediatr.Clin.North Am.,2013,60(1):49-74
6 Thurl S,Munzert M,Henker J,Boehm G,Muller-Werner B,Jelinek J,Stahl B.Br.J.Nutr.,2010,104(9):1261-1271
7 Barile D,Rastall R A.Curr.Opin.Biotechnol.,2013,24(2):214-219
8 Peterson R,Cheah W Y,Grinyer J,Packer N.Glycobiology,2013,23(12):1425-1438
9 Newburg D S.Biochemistry(Mosc),2013,78(7):771-785
10 Bode L.Glycobiology,2012,22(9):1147-1162
11 Tudehope D I.J.Pediatr.,2013,162(3 Suppl):S17-25
12 Plaza-Diaz J,Fontana L,Gil A.Nutrients,2018,10(8):1038
13 Kobata A.Prebiotics and Probiotics in Human Milk.Mcguire M K,McGuire M A,Bode L(Editors).USA.Academic Press,2017:17-44
14 Kobata A.Proc.Jpn.Acad.B,2010,86(7):731-747
15 Ninonuevo M R,Park Y,Yin H F,Zhang J H,Ward R E,Clowers B H,German J B,Freeman S L,Killeen K,Grimm R,Lebrilla C B.J.Agric.Food Chem.,2006,54(20):7471-7480
16 Wu S,Grimm R,German J B,Lebrilla C B.J.Proteome Res.,2011,10(2):856-868
17 Remoroza C A,Mak T D,De Leoz M L A,Mirokhin Y A,Stein S E.Anal.Chem.,2018,90(15):8977-8988
18 Yan J Y,Ding J J,Liang X M.Anal.Methods,2017,9(7):1071-1077
19 Georgi G,Bartke N,Wiens F,Stahl B.Am.J.Clin.Nutr.,2013,98(2):578S-585S
20 Zhang H T,Zhang S,Tao G J,Zhang Y B,Mulloy B,Zhan X B,Chai W G.Anal.Chem.,2013,85(12):5940-5949
21 Gao C,Zhang Y B,Liu Y,Feizi T,Chai W G.Anal.Chem.,2015,87(23):11871-11878
22 Chai W G,Piskarev V,Lawson A M.Anal.Chem.,2001,73(3):651-657
23 Chai W G,Piskarev V,Lawson A M.J.Am.Soc.Mass Spectrom.,2002,13(6):670-679
24 LIU Shi-Long,LANG Yin-Zhi,ZHU He,YAN Li-Na,LV You-Jing,ZHAO Xiao-Liang,CAI Chao,YU Guang-Li.Chem.J.Chinese Universities,2015,36(6):1087-1093刘世龙,郎银芝,祝贺,闫立娜,吕友晶,赵小亮,蔡超,于广利.高等学校化学学报,2015,36(6):1087-1093
25 HANYao,LV Zhi-Hua,JIANG Ting-Fu,WANG Yuan-Hong.Chinese J.Anal.Chem.,2006,34(9):1213-1218韩瑶,吕志华,姜廷福,王远红.分析化学,2006,34(9):1213-1218
26 Totten S M,Wu L D,Parker E A,Davis J C C,Hua S,Stroble C,Ruhaak L R,Smilowitz J T,German J B,Lebrilla CB.Anal.Bioanal.Chem.,2014,406(30):7925-7935
27 Yan J Y,Ding J J,Jin G W,Yu D P,Yu L,Long Z,Guo Z M,Chai W G,Liang X M.Anal.Chem.,2018,90(5):3174-3182
28 Taufik E,Fukuda K,Senda A,Saito T,Williams C,Tilden C,Eisert R,Oftedal O,Urashima T.Glycoconjugate J.,2012,29(2-3):119-134