Linkage and Sequence Analysis of Neutral Oligosaccharides by Negative-Ion MALDI Tandem Mass Spectrometry With Laser-Induced Dissociation

Chuncui Huang, Jingyu Yan, Lingpeng Zhan, Min Zhao, Jinyu Zhou, Huanyu Gao, Wenchun Xie, Yan Li, Wengang Chai

Anal Chim Acta. 2019 Sep 13;1071:25-35.

PMID: 31128752

Abstract:

Mass spectrometry (MS) has become the primary method for high-sensitivity structural determination of oligosaccharides. Fragmentation in the negative-ion MS can provide a wealth of structural information and these can be used for sequence determination. However, although negative-ion MS of neutral oligosaccharide using the deprotonated molecule [M-H]- as the precursor has been very successful for electrospray ionization (ESI), it has only limited success for matrix-assisted laser desorption/ionization (MALDI). In the present study, the features of negative-ion MALDI primary spectra were investigated in detail and the product-ion spectra using [M-H]- and [M+Cl]- as the precursors were carefully compared. The formation of [M-H]- was the main difficulty for MALDI while [M+Cl]- was proved to be useful as alternative precursor anion for MALDI-MS/MS to produce similar fragmentation for sequencing of neutral oligosaccharides. N-(1-naphthyl)ethylenediamine dihydrochloride was then used as both the matrix and the Cl- dopant to evaluate the extent of structural information that can be obtained by negative-ion fragmentation from [M+Cl]- using laser-induced dissociation (LID)-MS/MS for linkage assignment of gluco-oligosaccharides and for typing of blood-group ABO(H) and Lewis antigens on either type 1 or type 2 backbone-chains.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
ALP896126037	ABO dihydrochloride		896126-03-7 (free base)	Price