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Structure and Conformation of Wild-Type Bacterial Lipopolysaccharide Layers at Air-Water Interfaces.

ABSTRACT: The outer membrane of Gram-negative bacteria is of great scientific interest because it mediates the action of antimicrobial agents. The membrane surface is composed of lipopolysaccharide (LPS) molecules with negatively charged oligosaccharide headgroups. To a certain fraction, LPSs additionally display linear polysaccharides termed O-side chains (OSCs). Structural studies on bacterial outer surfaces models, based on LPS monolayers at air-water interfaces, have so far dealt only with rough mutant LPSs lacking these OSCs. Here, we characterize monolayers of wild-type LPS from Escherichia coli O55:B5 featuring strain-specific OSCs in the presence of defined concentrations of monovalent and divalent ions. Pressure-area isotherms yield insight into in-plane molecular interactions and monolayer elastic moduli. Structural investigations by x-ray and neutron reflectometry reveal the saccharide conformation and allow quantifying the area per molecule and the fraction of LPS molecules carrying OSCs. The OSC conformation is satisfactorily described by the self-consistent field theory for end-grafted polymer brushes. The monolayers exhibit a significant structural response to divalent cations, which goes beyond generic electrostatic screening.

SUBMITTER: Micciulla S

PROVIDER: S-EPMC6451063 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Structure and Conformation of Wild-Type Bacterial Lipopolysaccharide Layers at Air-Water Interfaces.

Micciulla Samantha S Gerelli Yuri Y Schneck Emanuel E

Biophysical journal 20190228 7

The outer membrane of Gram-negative bacteria is of great scientific interest because it mediates the action of antimicrobial agents. The membrane surface is composed of lipopolysaccharide (LPS) molecules with negatively charged oligosaccharide headgroups. To a certain fraction, LPSs additionally display linear polysaccharides termed O-side chains (OSCs). Structural studies on bacterial outer surfaces models, based on LPS monolayers at air-water interfaces, have so far dealt only with rough mutan ...[more]

PMID: 30878200

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Project description:Air/water interfaces were modified by oppositely charged poly(sodium 4-styrenesulfonate) (NaPSS) and hexadecyltrimethylammonium bromide (CTAB) polyelectrolyte/surfactant mixtures and were studied on a molecular level with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry. In order to deduce structure property relations, our results on the interfacial molecular structure and lateral interactions of PSS-/CTA+ complexes were compared to the stability and structure of macroscopic foam as well as to bulk properties. For that, the CTAB concentration was fixed to 0.1 mM, while the NaPSS concentration was varied. At NaPSS monomer concentrations <0.1 mM, PSS-/CTA+ complexes start to replace free CTA+ surfactants at the interface and thus reduce the interfacial electric field in the process. This causes the O-H bands from interfacial H2O molecules in our SFG spectra to decrease substantially, which reach a local minimum in intensity close to equimolar concentrations. Once electrostatic repulsion is fully screened at the interface, hydrophobic PSS-/CTA+ complexes dominate and tend to aggregate at the interface and in the bulk solution. As a consequence, adsorbate layers with the highest film thickness, surface pressure, and dilatational elasticity are formed. These surface layers provide much higher stabilities and foamabilities of polyhedral macroscopic foams. Mixtures around this concentration show precipitation after a few days, while their surfaces to air are in a local equilibrium state. Concentrations >0.1 mM result in a significant decrease in surface pressure and a complete loss in foamability. However, SFG and surface dilatational rheology provide strong evidence for the existence of PSS-/CTA+ complexes at the interface. At polyelectrolyte concentrations >10 mM, air-water interfaces are dominated by an excess of free PSS- polyelectrolytes and small amounts of PSS-/CTA+ complexes which, however, provide higher foam stabilities compared to CTAB free foams. The foam structure undergoes a transition from wet to polyhedral foams during the collapse.

Project description:The structure of poly(sodium 4-styrenesulfonate) (NaPSS) polyelectrolytes at air-water interfaces was investigated with tensiometry, ellipsometry, and vibrational sum-frequency generation (SFG) in the presence of low and high CaCl2 concentrations. In addition, we have studied the foaming behavior of 20 mM NaPSS solutions to relate the PSS molecular structure at air-water interfaces to foam properties. PSS polyelectrolytes without additional salt exhibited significant surface activity, which can be tuned further by additions of CaCl2. The hydrophobicity of the backbone due to incomplete sulfonation during synthesis is one origin, whereas the effective charge of the polyelectrolyte chain is shown to play another major role. At low salt concentrations, we propose that the polyelectrolyte is forming a layered structure. The hydrophobic parts are likely to be located directly at the interface in loops, whereas the hydrophilic parts are at low concentrations stretched out into near-interface regions in tails. Increasing the Ca2+ concentration leads to ion condensation, a collapse of the tails, and likely to Ca2+ intra- and intermolecular bridges between polyelectrolytes at the interface. The increase in both surface excess and foam stability originates from changes in the polyelectrolyte's hydrophobicity due to Ca2+ condensation onto the PSS polyanions. Consequently, charge screening at the interface is enhanced and repulsive electrostatic interactions are reduced. Furthermore, SFG spectra of O-H stretching bands reveal a decrease in intensity of the low-frequency branch when c(Ca2+) is increased whereas the high-frequency branch of O-H stretching modes persists even for 1 M CaCl2. This originates from the remaining net charge of the PSS polyanions at the air-water interface that is not fully compensated by condensation of Ca2+ ions and leads to electric-field-induced contributions to the SFG spectra of interfacial H2O. A charge reversal of the PSS net charge at the air-water interface is not observed and is consistent with bulk electrophoretic mobility measurements.

Dataset Information

Structure and Conformation of Wild-Type Bacterial Lipopolysaccharide Layers at Air-Water Interfaces.

Publications

Structure and Conformation of Wild-Type Bacterial Lipopolysaccharide Layers at Air-Water Interfaces.

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