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A Major Step in Opening the Black Box of High-Molecular-Weight Dissolved Organic Nitrogen by Isotopic Labeling of Synechococcus and Multibond Two-Dimensional NMR

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    A Major Step in Opening the Black Box of High-Molecular-Weight Dissolved Organic Nitrogen by Isotopic Labeling of Synechococcus and Multibond Two-Dimensional NMR
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    † Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02453, United States
    ‡ Department of Ocean, Earth and Atmospheric Sciences, Old Dominion University, 4600 Elkhorn Avenue, Norfolk, Virginia 23529, United States
    § Department of Chemistry and Biochemistry, Old Dominion University, 4541 Hampton Boulevard, Norfolk, Virginia 23529, United States
    ∥ Biology and Chemistry Department, Morningside College, 1501 Morningside Avenue, Sioux City, Iowa 51106, United States
    *E-mail: [email protected]
    *E-mail: [email protected]
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    Analytical Chemistry

    Cite this: Anal. Chem. 2017, 89, 22, 11990–11998
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    https://doi.org/10.1021/acs.analchem.7b02335
    Published October 30, 2017
    Copyright © 2017 American Chemical Society
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    Abstract

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    Dissolved organic nitrogen (DON) comprises the largest pool of fixed N in the surface ocean, yet its composition has remained poorly constrained. Knowledge of the chemical composition of this nitrogen pool is crucial for understanding its biogeochemical function and reactivity in the environment. Previous work has suggested that high-molecular-weight (high-MW) DON exists only in two closely related forms, the secondary amides of peptides and of N-acetylated hexose sugars. Here, we demonstrate that the chemical structures of high-MW DON may be much more diverse than previously thought. We couple isotopic labeling of cyanobacterially derived dissolved organic matter with advanced two-dimensional NMR spectroscopy to open the “black box” of uncharacterized high-MW DON. Using multibond NMR correlations, we have identified novel N-methyl-containing amines and amides, primary amides, and novel N-acetylated sugars, which together account for nearly 50% of cyanobacterially derived high-MW DON. This study reveals unprecedented compositional details of the previously uncharacterized DON pool and outlines the means to further advance our understanding of this biogeochemically and globally important reservoir of organic nitrogen.

    Copyright © 2017 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.analchem.7b02335.

    • More details on Synechococcus cultures and isolation of high-MW DOM by ultrafiltration, possible origins of primary amides, N-acetyl-galactosamine, distinctive sugars without N, a conceptual graph explaining the multibond NMR approach, 13C spectra obtained as partial projections from 2D 15N–13C spectra, identification of carbon–carbon pairs and nearby carbons, carbons bonded to tertiary nitrogen, structural information from 13C(═O)–13CH(−OH) spin pairs, primary amide structures, proximity of C-containing moieties, and 15N NMR spectra of extracellular DON and natural water DON (PDF)

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    Analytical Chemistry

    Cite this: Anal. Chem. 2017, 89, 22, 11990–11998
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.analchem.7b02335
    Published October 30, 2017
    Copyright © 2017 American Chemical Society
    Request reuse permissions

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