Lipopolysaccharide (LPS) is a major virulence determinant of the human bacterial
pathogen Haemophilus influenzae. A characteristic
feature of H. influenzae LPS is the extensive intra-
and inter-strain heterogeneity of glycoform structure which is key to the role of the
molecule in both commensal and disease-causing behaviour of the bacterium. The
chemical composition of non-typeable Haemophilus
influenzae (NTHi) LPS is highly diverse. It contains a number of
different monosaccharides (Neu5Ac, L-glycero-D-manno heptose, D-glycero
-D-manno heptose, Kdo, D-Glc, D-Gal, D-GlcNAc,
D-GalNAc) and non-carbohydrate substituents. Prominent non-carbohydrate components
are O-acetyl groups, glycine and phosphates. We now
know that sialic acid (N-acetylneuraminic acid or
Neu5Ac) and certain oligosaccharide extensions are important in the pathogenesis of
NTHi; however, the biological implications for many of the various features are still
unknown. Electrospray ionization mass spectrometry in combination with separation
techniques like CE and HPLC is an indispensable tool in profiling glycoform
populations in heterogeneous LPS samples. Mass spectrometry is characterized by its
extreme sensitivity. Trace amounts of glycoforms expressing important virulence
determinants can be detected and characterized on minute amounts of material. The
present review focuses on LPS structures and mass spectrometric methods which enable
us to profile these in complex mixtures.
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