Fragmentation of neutral oligosaccharides using the MALDI LTQ Orbitrap

Rohmer, Marion; Baeumlisberger, Dominic; Stahl, Bernd; Bahr, U.; Karas, Michael

doi:10.1016/j.ijms.2010.11.008

Cited by 15 publications

(19 citation statements)

References 47 publications

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“…We confirmed the polar head groups of GSLs in these three strains of microalgae were disaccharide and trisaccharide and determined their conceivable structures by use of MS analysis. The conceivable saccharide structures can be identified similarly with mass spectrometry in many previous studies . However, the exact structures of the two kinds of polar head group should be confirmed by stable isotope labeling or by the combination of multiple complimentary techniques such as nuclear magnetic resonance (NMR) after separation and purification.…”

Section: Discussionmentioning

confidence: 99%

Structural elucidation of two types of novel glycosphingolipids in three strains of Skeletonema by liquid chromatography coupled with mass spectrometry

Zhao

Chen

et al. 2013

Rapid Comm Mass Spectrometry

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Section: Discussionmentioning

confidence: 99%

Structural elucidation of two types of novel glycosphingolipids in three strains of Skeletonema by liquid chromatography coupled with mass spectrometry

Zhao

Chen

et al. 2013

Rapid Comm Mass Spectrometry

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“…41 For underivatized neutral oligosaccharides, fragment ions obtained from positive and negative mode may complement each other, enhancing structural assignment. 42,43 …”

Section: Ion Activationmentioning

confidence: 99%

Oligosaccharide Analysis by Mass Spectrometry: A Review of Recent Developments

Kailemia¹,

et al. 2013

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“…However, the spectral information delivered from underivatized oligosaccharides, such as linkage position and substituent pattern information, is generally considered less informative than in negative‐ion mode or by alkali metal cationization . The main advantage of negative‐ion mode is in the production of C‐type glycosidic cleavage ions series which deliver sequence information and which is associated with related A‐type cross‐ring cleavage ions series carrying linkage information . The main glycosidic and cross‐ring cleavage ions observed in negative‐ion mode are depicted according to Domon and Costello nomenclature on the scheme below …”

Section: Introductionmentioning

confidence: 99%

Negative electrospray ionization mass spectrometry: a method for sequencing and determining linkage position in oligosaccharides from branched hemicelluloses

et al. 2015

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Xyloglucans of apple, tomato, bilberry and tamarind were hydrolyzed by commercial endo β-1-4-D-endoglucanase. The xylo-gluco-oligosaccharides (XylGos) released were separated on CarboPac PA 200 column in less than 15 min, and, after purification, they were structurally characterized by negative electrospray ionization mass spectrometry using a quadrupole time-of-flight (ESI-Q-TOF), a hybrid linear ion trap (LTQ)/Orbitrap and a hybrid quadrupole Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers. In order to corroborate the fragmentation routes observed on XylGos, some commercial galacto-manno-oligosaccharides (GalMOs) and glucurono-xylo-oligosaccharides were also studied. The fragmentation pathways of the ionized GalMos were similar to those of XylGos ones. The product ion spectra were mainly characterized by prominent double cleavage (D) ions corresponding to the entire inner side chains. The directed fragmentation from the reducing end to the other end was observed for the main glycosylated backbone but also for the side-chains, allowing their complete sequencing. Relevant cross-ring cleavage ions from (0,2)X(j)-type revealed to be diagnostic of the 1-2-linked- glycosyl units from XylGos together with the 1-2-linked glucuronic acid unit from glucuronoxylans. Resonant activation in the LTQ Orbitrap allowed not only determining the type of all linkages but also the O-acetyl group location on fucosylated side-chains. Moreover, the fragmentation of the different side chains using the MS(n) capabilities of the LTQ/Orbitrap analyzer also allowed differentiating terminal arabinosyl and xylosyl substituents inside S and U side-chains of XylGos, respectively. The CID spectra obtained were very informative for distinction of isomeric structures differing only in their substitution pattern. These features together makes the fragmentation in negative ionization mode a relevant and powerful technique useful to highlight the subtle structural changes generally observed during the development of plant organs such as during fruit ripening and for the screening of cell wall mutants with altered hemicellulose structure.

show abstract

Fragmentation of neutral oligosaccharides using the MALDI LTQ Orbitrap

Cited by 15 publications

References 47 publications

Structural elucidation of two types of novel glycosphingolipids in three strains of Skeletonema by liquid chromatography coupled with mass spectrometry

Structural elucidation of two types of novel glycosphingolipids in three strains of Skeletonema by liquid chromatography coupled with mass spectrometry

Oligosaccharide Analysis by Mass Spectrometry: A Review of Recent Developments

Negative electrospray ionization mass spectrometry: a method for sequencing and determining linkage position in oligosaccharides from branched hemicelluloses

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