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1. (Article ID: 6156)
Vitiello G, Oliva R, Petraccone L, Vecchio PD, Heenan RK, Molinaro A, Silipo A, D'Errico G, Paduano L
Covalently bonded hopanoid-Lipid A from Bradyrhizobium: The role of unusual molecular structure and calcium ions in regulating the lipid bilayers organization
Journal of Colloid and Interface Science 594 (2021)
891-901
Lipopolysaccharides (LPS) are complex amphiphilic macromolecules forming the external leaflet of the outer membrane of Gram-negative bacteria. The LPS glycolipid portion, named Lipid A, is characterized by a disaccharide backbone carrying multiple acyl chains. Some Lipid A bear very-long-chain-fatty-acids (VLCFA), biosynthesized to span the entire lipid membrane profile. The synbiontic Bradyrhizobium BTAi1 strain carries an unique Lipid A specie, named HoLA, in which VLCFA terminus is covalently-bonded to hopanoid, a triterpenoid displaying structural similarity with eukaryotic sterols. Here, we investigate the role of HoLA in regulating self-assembly, microstructure and thermotropicity of lipid membranes composed by 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine and 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-1'-rac-glycerol. DLS and SANS indicated the formation of multilamellar aggregates whose size increases when the hopanoid is present in the bilayer. EPR and DSC showed that HoLA induced a more rigid and ordered organization among the lipids in the bilayer, evocative of a mechanical strengthening. Notably, the presence of calcium ions promote an increase of the bilayer thickness and vesicles size, leading to low curvature aggregates. These results highlight the key role of the hopanoid covalently-linked to VLCFA in defining the physico-chemical properties of bacterial envelope, thus offering a robust scientific basis for the interpretation of the biological activity of the considered strain.
lipopolysaccharides, lipid A, liposomes, Gram-negative bacteria, lipids, Bradyrhizobium, bacterial membranes, hopanoid
NCBI PubMed ID: 33799122Publication DOI: 10.1016/j.jcis.2021.03.072Journal NLM ID: 43125Publisher: Orlando, FL: Academic Press
Correspondence: G. Vitiello
unina.it>; L. Paduano unina.it>
Institutions: Department of Chemical, Materials and Production Engineering (DICMaPI), University of Naples Federico II, Piazzale V. Tecchio 80, 80125 Naples, Italy, CSGI, Center for Colloid and Surface Science, via della Lastruccia 3, Sesto Fiorentino (FI), Italy, Department of Chemical Sciences, University of Naples Federico II, via Cintia 4, 80126 Naples, Italy, ISIS Facility, Science & Technology Facilities Council, Rutherford Appleton Laboratory, Chilton, Oxon OX11 0QX, United Kingdom
Methods: EPR, DLS, SANS, DCS
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