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Dissection of Fragmentation Pathways in Protonated N-Acetylhexosamines.

ABSTRACT: Structural characterization of carbohydrates by mass spectrometry necessitates a detailed understanding of their gas phase behavior, particularly for protonated carbohydrates that can undergo complex structural rearrangements during fragmentation. Here we utilize tandem mass spectrometry, isotopic labeling, gas-phase hydrogen/deuterium exchange, and ion mobility measurements to characterize structures of the various product ions of protonated N-acetylhexosamines. Following the facile loss of the reducing end hydroxyl group, we identify two primary fragmentation pathways. Detailed mapping of each step in the fragmentation pathway provides new insight into the mechanisms that drive collision-induced dissociation of protonated carbohydrates. Several of the smaller fragment ions are mixtures of structural isomers, and the relative distributions of these structures reveals information about the stereochemistry of the precursor molecule.

SUBMITTER: Mookherjee A

PROVIDER: S-EPMC6490963 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Dissection of Fragmentation Pathways in Protonated N-Acetylhexosamines.

Mookherjee Abhigya A Uppal Sanjit S SS Guttman Miklos M

Analytical chemistry 20180925 20

Structural characterization of carbohydrates by mass spectrometry necessitates a detailed understanding of their gas phase behavior, particularly for protonated carbohydrates that can undergo complex structural rearrangements during fragmentation. Here we utilize tandem mass spectrometry, isotopic labeling, gas-phase hydrogen/deuterium exchange, and ion mobility measurements to characterize structures of the various product ions of protonated N-acetylhexosamines. Following the facile loss of the ...[more]

PMID: 30216047

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Project description:Lipid A, the membrane-bound phosphoglycolipid component of bacteria, is held responsible for the clinical syndrome of gram-negative sepsis. In this study, the fragmentation behavior of a set of synthetic lipid A derivatives was studied by electrospray ionization multistage mass spectrometry (ESI-MSn), in conjunction with tandem mass spectrometry (MS/MS), using low-energy collision-induced dissociation (CID). Genealogical insight about the fragmentation pathways of the deprotonated 4'-monophosphoryl lipid A structural analogs led to proposals of a number of alternative dissociation routes that have not been reported previously. Each of the fragment ions was interpreted using various possible mechanisms, consistent with the principles of reactions described in organic chemistry. Specifically, the hypothesized mechanisms are: (i) cleavage of the C-3 primary fatty acid leaves behind an epoxide group attached to the reducing sugar; (ii) cleavage of the C-3' primary fatty acid (as an acid) generates a cyclic phosphate connected to the nonreducing sugar; (iii) cleavage of the C-2' secondary fatty acid occurs both in acid and ketene forms; iv) the C-2 and C-2' primary fatty acids are eliminated as an amide and ketene, respectively; (v) the 0,2A2 cross-ring fragment contains a four-membered ring (oxetanose); (vi) the 0,4A2 ion is consecutively formed from the 0,2A2 ion by retro-aldol, retro-cycloaddition, and transesterification; and (vii) formations of H2PO4- and PO3- are associated with the formation of sugar epoxide. An understanding of the relation between 0,2A2 and 0,4A2-type sugar fragments and the different cleavage mechanisms of the two ester-linked primary fatty acids is invaluable for distinguishing lipid A isomers with different locations of a single ester-linked fatty acid (i.e., at C-3 or C-3'). Thus, in addition to a better comprehension of lipid A fragmentation processes in mass spectrometers, our observations can be applied for a more precise elucidation of naturally occurring lipid A structures.

Dataset Information

Dissection of Fragmentation Pathways in Protonated N-Acetylhexosamines.

Publications

Dissection of Fragmentation Pathways in Protonated N-Acetylhexosamines.

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