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    Negative electron transfer dissociation of glycosaminoglycans

    Author
    Wolff, J.; Leach, F.; Laremore, T.; Kaplan, D.; Easterling, M.; Linhardt, Robert J.; Amster, J.
    ORCID
    https://orcid.org/0000-0003-2219-5833
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    NEGATIVE ELECTRON TRANSFER DISSOCIATION OF.pdf (891.9Kb)
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    Date Issued
    2010
    Subject
    Biology; Chemistry and chemical biology; Chemical and biological engineering; Biomedical engineering
    Degree
    Terms of Use
    In Copyright : this Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s). https://rightsstatements.org/page/InC/1.0/;
    Full Citation
    Negative electron transfer dissociation of glycosaminoglycans, J. Wolff, F. Leach, T. Laremore, D. Kaplan, M. Easterling, R. J. Linhardt, J. Amster, Analytical Chemistry, 82, 3460-3466, 2010.
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    URI
    https://hdl.handle.net/20.500.13015/5254; https://doi.org/10.1021/ac100554a
    Abstract
    Structural characterization of glycosaminoglycans (GAGs) has been a challenge in the field of mass spectrometry, and the application of electron detachment dissociation (EDD) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) has shown great promise to GAG oligosaccharide characterization in a single tandem mass spectrometry experiment. In this work, we apply the technique of negative electron transfer dissociation (NETD) to GAGs on a commercial ion trap mass spectrometer. NETD of GAGs, using fluoranthene or xenon as the reagent gas, produces fragmentation very similar to previously observed EDD fragmentation. Using fluoranthene or xenon, both glycosidic and cross-ring cleavages are observed, as well as even- and odd-electron products. The loss of SO3 can be minimized and an increase in cross-ring cleavages is observed if a negatively-charged carboxylate is present during NETD, which can be controlled by the charge state or the addition of sodium. NETD effectively dissociates GAGs up to eight saccharides in length, but the low resolution of the ion trap makes assigning product ions difficult. Similar to EDD, NETD is also able to distinguish the epimers iduronic acid from glucuronic acid in heparan sulfate tetrasaccharides and suggests that a radical intermediate plays an important role in distinguishing these epimers. These results demonstrate that NETD is effective at characterizing GAG oligosaccharides in a single tandem mass spectrometry experiment on a widely available mass spectrometry platform.;
    Description
    Analytical Chemistry, 82, 3460-3466; Note : if this item contains full text it may be a preprint, author manuscript, or a Gold OA copy that permits redistribution with a license such as CC BY. The final version is available through the publisher’s platform.
    Department
    The Linhardt Research Labs.; The Shirley Ann Jackson, Ph.D. Center for Biotechnology and Interdisciplinary Studies (CBIS);
    Publisher
    American Chemical Society (ACS)
    Relationships
    The Linhardt Research Labs Online Collection; Rensselaer Polytechnic Institute, Troy, NY; https://harc.rpi.edu/;
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    A full text version is available in DSpace@RPI;
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