TY  - JOUR
A1  - Vijayakrishnan, Balakumar
A1  - Issaree, Arisara
A1  - Corilo, Yuri E.
A1  - Ferreira, Christina Ramires
A1  - Eberlin, Marcos N.
A1  - Peter, Martin G.
T1  - MSn of the six isomers of (GlcN)(2)(GlcNAc)(2) aminoglucan tetrasaccharides (diacetylchitotetraoses) rules of fragmentation for the sodiated molecules and application to sequence analysis of hetero-chitooligosaccharides
JF  - Carbohydrate polymers : an international journal devoted to scientific and technological aspects of industrially important polysaccharides
N2  - The six possible isomers of di-N-acetylchitotetraoses [AADD, ADDA, ADAD, DADA, DAAD, and DDAA, where D stands for 2-amino-2-deoxy-3-D-glucose (GlcN) and A for 2-acetamido-2-deoxy-beta-D-glucose (GlcNAc)] were analyzed by ESI(+)-MSn. Collision induced dissociation via MSn experiments were performed for the sodiated molecules of m/z 769 [M+Na](+) for each isomer, and fragments were generated mainly by glycosidic bond and cross-ring cleavages. Rules of fragmentation were then established. A reducing end D residue yields the (O.2)A(4) cross-ring [M-59+Na](+) fragment of m/z 710 as the most abundant, whereas isomers containing a reducing end A prefer to lose water to form the [M-18+Na](+) ion of m/z 751, as well as abundant (O.2)A(4) cross-ring [M-101+Na](+) fragments of m/z 668 and B-3 [M-221+Na](+) ions of m/z 548. MS3 of C- and Y-type ions shows analogous fragmentation behaviour that allows identification of the reducing end next-neighbour residue. Due to gas-phase anchimeric assistance, B-type cleavage between the glycosidic oxygen and the anomeric carbon atom is favoured when the glycon is an A residue. Relative ion abundances are generally in the order B >> C > Y, but may vary depending on the next neighbour towards the non-reducing end. These fragmentation rules were used for partial sequence analysis of hetero-chitooligosaccharides of the composition D(2)A(3), D(3)A(3), D(2)A(4), D(4)A(3), and D(3)A(4).
KW  - Chitosan
KW  - Fragmentation
KW  - Oligosaccharides
KW  - Sequence analysis
KW  - Tandem mass spectrometry
Y1  - 2011
U6  - https://doi.org/10.1016/j.carbpol.2010.04.041
SN  - 0144-8617
VL  - 84
IS  - 2
SP  - 713
EP  - 726
PB  - Elsevier
CY  - Oxford
ER  -