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  • Title: Determination of fatty acid positions in native lipid A by positive and negative electrospray ionization mass spectrometry.
    Author: Sforza S, Silipo A, Molinaro A, Marchelli R, Parrilli M, Lanzetta R.
    Journal: J Mass Spectrom; 2004 Apr; 39(4):378-83. PubMed ID: 15103651.
    Abstract:
    Lipid A is the endotoxic principle of the lipopolysaccharide fraction from Gram-negative bacteria. It is involved in the elicitation of cytokine production that leads to massive inflammation and to septic shock as a lethal consequence. For this reason, the structural elucidation of lipopolysaccharides from toxic Gram-negative bacteria is an important and complicated task, mainly owing to its natural heterogeneity. Here, a new methodology to infer the distribution of the primary and secondary acyl residues is described, based on electrospray ionization mass spectrometry (ESI-MS) of intact lipid A under high cone voltage in order to achieve in-source fragmentation. Under these conditions, acyl fragmentation is induced and a different regioselective cleavage of secondary fatty acids is observed in positive and negative ESI-MS, allowing the rapid identification of the lipid A structure.
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