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Differentiation of O-acetyl and O-carbamoyl

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Journal of the American Society for Mass Spectrometry

Abstract

Nod factors are substituted N-acyl chito-oligomers secreted by plant symbiotic bacteria of the Rhizobium family. Substitutions on the oligosaccharide core specify their recognition by host plants. A method using tandem mass spectrometry is proposed to locate the O-acetyl and O-carbamoyl substituents on the nonreducing terminal residue of the chito-oligomers. As model compounds, all the positional isomers of monoacetyl and monocarbamoyl esters of 1-O-methyl-N-acetyl-α-D-glucosamine were synthesized. Oxonium ions (MH − CH3OH)+ were generated by liquid secondary ion mass spectrometry (LSIMS) and their decomposition was recorded on a tandem magnetic instrument. Large differences were observed in the relative abundances of ions resulting from elimination of water and of the O-ester substituent from metastable oxonium ions. Deuterium exchange reactions indicated parallel elimination pathways involving either exchangeable or carbon-linked hydrogens. The intensity ratios of some of the ions generated by collisions with helium atoms allowed the isomers to be distinguished. The main dissociation routes were identified. Metastable and collision-induced decomposition of the B1 ions from Nod factors of Sinorhizobium meliloti and Azorhizobium caulinodans resembled that of the 6-O-substituted N-acetylglucosamine models. Decomposition of the B1 ion from Mesorhizobium loti and Rhizobium etli Nod factors, was similar to that of 3-O-carbamoyl N-acetyl-glucosamine and different to that of the 4-O isomer. 6-O- and 3-O-carbamoylation specified by the nodU and nolO genes, respectively, of Rhizobium. sp. NGR234 were confirmed.

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Author notes

  1. Myriam Ferro

    Present address: Institut de Biologie Structurale, UPR 9015, 41 rue des Martyrs, 38027, Grenoble Cedex 1, France

Authors and Affiliations

  1. Laboratoire des IMRCP, UPS, 118 Route de Narbonne, 31062, Toulouse-Cedex, France

    Michel Treilhou, Myriam Ferro, Candida Monteiro, Verena Poinsot, Claire Kanony, Danielle Promé & Jean-Claude Promé

  2. Laboratoire de Biologie Moleculaire des Plantes Supérieures, Geneva, Switzerland

    Said Jabbouri

  3. Ecole Nationale de Formation Agronomique, BP 87, 31326, Castanet-Tolosan, France

    Michel Treilhou

Authors
  1. Michel Treilhou
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  2. Myriam Ferro
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  3. Candida Monteiro
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  5. Said Jabbouri
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  8. Jean-Claude Promé
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Correspondence to Jean-Claude Promé.

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Treilhou, M., Ferro, M., Monteiro, C. et al. Differentiation of O-acetyl and O-carbamoyl. J Am Soc Mass Spectrom 11, 301–311 (2000). https://doi.org/10.1016/S1044-0305(99)00152-X

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  • DOI: https://doi.org/10.1016/S1044-0305(99)00152-X

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