title: Differentiation of the stereochemistry and anomeric configuration for 1-3 linked disaccharides via tandem mass spectrometry and 18O-labeling.
abstract: Collision-induced dissociation (CID) of deprotonated hexose-containing disaccharides (m/z 341) with 1-2, 1-4, and 1-6 linkages yields product ions at m/z 221, which have been identified as glycosyl-glycolaldehyde anions. From disaccharides with these linkages, CID of m/z 221 ions produces distinct fragmentation patterns that enable the stereochemistries and anomeric configurations of the non-reducing sugar units to be determined. However, only trace quantities of m/z 221 ions can be generated for 1-3 linkages in Paul or linear ion traps, preventing further CID analysis. Here we demonstrate that high intensities of m/z 221 ions can be built up in the linear ion trap (Q3) from beam-type CID of a series of 1-3 linked disaccharides conducted on a triple quadrupole/linear ion trap mass spectrometer. (18)O-labeling at the carbonyl position of the reducing sugar allowed mass-discrimination of the "sidedness" of dissociation events to either side of the glycosidic linkage. Under relatively low energy beam-type CID and ion trap CID, an m/z 223 product ion containing (18)O predominated. It was a structural isomer that fragmented quite differently than the glycosyl-glycolaldehydes and did not provide structural information about the non-reducing sugar. Under higher collision energy beam-type CID conditions, the formation of m/z 221 ions, which have the glycosyl-glycolaldehyde structures, were favored. Characteristic fragmentation patterns were observed for each m/z 221 ion from higher energy beam-type CID of 1-3 linked disaccharides and the stereochemistry of the non-reducing sugar, together with the anomeric configuration, were successfully identified both with and without (18)O-labeling of the reducing sugar carbonyl group.
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, IN 47907-1393, USA.
authors.forename: Chiharu
authors.initials: C
authors.lastname: Konda
authors.forename: Brad
authors.initials: B
authors.lastname: Bendiak
authors.forename: Yu
authors.initials: Y
authors.lastname: Xia
mesh_terms: D004187:Disaccharides / Q000737:chemistry*; D010103:Oxygen Isotopes / Q000737:chemistry; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D004187:Disaccharides; D010103:Oxygen Isotopes
references.citation: Anal Chem. 1998 Jul 15;70(14):3009-14
references.pmid: 9684549
references.citation: J Am Soc Mass Spectrom. 2005 Jan;16(1):60-70
references.pmid: 15653364
references.citation: Anal Chem. 1999 May 15;71(10):1997-2002
references.pmid: 10361499
references.citation: Methods Enzymol. 2005;402:148-85
references.pmid: 16401509
references.citation: Biomed Environ Mass Spectrom. 1988 Apr 15;15(8):441-6
references.pmid: 3382798
references.citation: Anal Chem. 1993 Jun 1;65(11):1582-7
references.pmid: 8328673
references.citation: Anal Chem. 2005 Aug 1;77(15):4719-25
references.pmid: 16053281
references.citation: J Mass Spectrom. 2007 Aug;42(8):999-1011
references.pmid: 17567836
references.citation: J Am Chem Soc. 2007 Aug 8;129(31):9721-36
references.pmid: 17629269
references.citation: Annu Rev Biophys Biomol Struct. 1999;28:269-93
references.pmid: 10410803
references.citation: Carbohydr Res. 2011 Nov 8;346(15):2469-81
references.pmid: 21906727
references.citation: Biochemistry. 1988 Mar 8;27(5):1534-43
references.pmid: 3365408
references.citation: Anal Chem. 1995 Jun 1;67(11):1772-84
references.pmid: 9306731
references.citation: J Am Soc Mass Spectrom. 2008 Aug;19(8):1119-31
references.pmid: 18554925
references.citation: Rapid Commun Mass Spectrom. 2008 May;22(10):1579-86
references.pmid: 18433086
references.citation: Anal Chem. 2007 Aug 1;79(15):5896-905
references.pmid: 17585836
references.citation: Nat Methods. 2008 Oct;5(10):873-5
references.pmid: 18806791
references.citation: Anal Chem. 2006 Aug 15;78(16):5678-84
references.pmid: 16906711
references.citation: Science. 1989 Oct 6;246(4926):64-71
references.pmid: 2675315
references.citation: Anal Chem. 2006 Feb 1;78(3):670-9
references.pmid: 16448038
references.citation: Carbohydr Res. 2010 Nov 2;345(16):2390-400
references.pmid: 20887979
references.citation: Rapid Commun Mass Spectrom. 1993 Jul;7(7):614-9
references.pmid: 8347867
references.citation: Proteomics. 2007 Mar;7(5):655-67
references.pmid: 17295354
references.citation: Biol Mass Spectrom. 1991 Apr;20(4):215-31
references.pmid: 2054395
references.citation: J Am Soc Mass Spectrom. 2003 Jan;14(1):63-78
references.pmid: 12504335
references.citation: J Am Soc Mass Spectrom. 1994 Sep;5(9):859-66
references.pmid: 24222034
references.citation: Carbohydr Res. 2007 Feb 5;342(2):217-35
references.pmid: 17184755
references.citation: J Magn Reson. 2005 Mar;173(1):160-8
references.pmid: 15705524
references.citation: Mass Spectrom Rev. 2004 May-Jun;23(3):161-227
references.pmid: 14966796
references.citation: Anal Chem. 2004 Jul 15;76(14):3908-22
references.pmid: 15253624