Chemoselective detection and discrimination of carbonyl-containing compounds in metabolite mixtures by 1H-detected 15N nuclear magnetic resonance

Andrew N. Lane, Sengodagounder Arumugam, Pawel K. Lorkiewicz, Richard M. Higashi, Sébastien Laulhé, Michael H. Nantz, Hunter N.B. Moseley, Teresa W.M. Fan

Research output: Contribution to journalArticlepeer-review

23 Scopus citations


NMR spectra of mixtures of metabolites extracted from cells or tissues are extremely complex, reflecting the large number of compounds that are present over a wide range of concentrations. Although multidimensional NMR can greatly improve resolution as well as improve reliability of compound assignments, lower abundance metabolites often remain hidden. We have developed a carbonyl-selective aminooxy probe that specifically reacts with free keto and aldehyde functions, but not carboxylates. By incorporating 15N in the aminooxy functional group, 15N-edited NMR was used to select exclusively those metabolites that contain a free carbonyl function while all other metabolites are rejected. Here, we demonstrate that the chemical shifts of the aminooxy adducts of ketones and aldehydes are very different, which can be used to discriminate between aldoses and ketoses, for example. Utilizing the 2-bond or 3-bond 15N-1H couplings, the 15N-edited NMR analysis was optimized first with authentic standards and then applied to an extract of the lung adenocarcinoma cell line A549. More than 30 carbonyl-containing compounds at NMR-detectable levels, six of which we have assigned by reference to our database. As the aminooxy probe contains a permanently charged quaternary ammonium group, the adducts are also optimized for detection by mass spectrometry. Thus, this sample preparation technique provides a better link between the two structural determination tools, thereby paving the way to faster and more reliable identification of both known and unknown metabolites directly in crude biological extracts.

Original languageEnglish
Pages (from-to)337-343
Number of pages7
JournalMagnetic Resonance in Chemistry
Issue number5
StatePublished - May 1 2015

Bibliographical note

Publisher Copyright:
Copyright © 2015 John Wiley & Sons, Ltd.


  • N-edited H NMR
  • aldehydes
  • aminooxy derivatives
  • chemoselection
  • ketones
  • metabolomics

ASJC Scopus subject areas

  • General Chemistry
  • General Materials Science


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