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Effects of monovalent anions of the hofmeister series on DPPC lipid bilayers Part I: swelling and in-plane equations of state.

ABSTRACT: Aiming to improve understanding of the mechanisms behind specific anion effects in biological systems we have studied the effects of sodium salts of simple monovalent anions belonging to the Hofmeister series on the bilayers of the zwitterionic lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine using small-angle x-ray scattering and the osmotic stress technique. NaCl, NaBr, NaNO(3), NaI, and NaSCN were used in this investigation. The electrolytes were found to swell the bilayers and to increase the area per lipid headgroup at each value of the osmotic pressure, suggesting the association of anions with the bilayer-lipid interfaces. The effects follow the Hofmeister series with SCN(-) inducing the most pronounced changes. "Ion competition" experiments with mixed NaI/NaCl solutions at total salinity 0.1 and 0.5 M revealed that the effect of ions on the lipid equation-of-state is roughly linear at low concentrations, but strongly nonlinear at high concentrations. The experimental results are fitted in a companion article to provide "binding" or "partitioning" constants of anions in the lipid bilayers.

SUBMITTER: Aroti A

PROVIDER: S-EPMC1948043 | biostudies-literature | 2007 Sep

REPOSITORIES: biostudies-literature

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Effects of monovalent anions of the hofmeister series on DPPC lipid bilayers Part I: swelling and in-plane equations of state.

Aroti A A Leontidis E E Dubois M M Zemb T T

Biophysical journal 20070511 5

Aiming to improve understanding of the mechanisms behind specific anion effects in biological systems we have studied the effects of sodium salts of simple monovalent anions belonging to the Hofmeister series on the bilayers of the zwitterionic lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine using small-angle x-ray scattering and the osmotic stress technique. NaCl, NaBr, NaNO(3), NaI, and NaSCN were used in this investigation. The electrolytes were found to swell the bilayers and to increase t ...[more]

PMID: 17496051

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Project description:The effects of Hofmeister anions on the perpendicular and lateral equation-of-state (EOS) of the dipalmitoylphosphatidylcholine lamellar phase discussed in the companion article are here examined using appropriate free energy models for the intra- and interbilayer interactions. Minimizing the free energy with respect to the two basic geometrical parameters of the lamellar phase, which are the interbilayer water thickness, d(w), and the lipid headgroup area, a(L), provides the perpendicular (osmotic pressure balance) and lateral EOS. Standard models were used for the hydration, undulation, and Van der Waals attractive force between the bilayers in the presence of electrolytes whereas two alternative treatments of electrostatic interactions were used to obtain "binding" or "partitioning" constants of anions to the lipid bilayers both in the absence and in the presence of sodium binding. The computed binding constants depend on anion type and follow the Hofmeister series, but were found to increase with electrolyte concentration, implying that the local binding approximation cannot fit bilayer repulsion data. The partitioning model was also found inadequate at high electrolyte concentrations. The fitting attempts revealed two additional features worthy of future investigation. First, at maximum swelling in the presence of electrolytes the osmotic pressure of the bilayer system cannot be set equal to zero. Second, at high salt concentrations an additional repulsion appears to come into effect in the presence of strongly adsorbing anions such as I(-) or SCN(-). Both these phenomena may reflect an inconsistent treatment of the ion-surface interactions, which have an impact on the osmotic pressure. Alternatively, they may arise from bulk solution nonidealities that cannot be handled by the classical Poisson-Boltzmann formalism. The inability of current models to explain the "lateral" EOS by fitting the area per lipid headgroup as a function of salt type and concentration shows that current understanding of phospholipid-ion interactions is still very incomplete.

Dataset Information

Effects of monovalent anions of the hofmeister series on DPPC lipid bilayers Part I: swelling and in-plane equations of state.

Publications

Effects of monovalent anions of the hofmeister series on DPPC lipid bilayers Part I: swelling and in-plane equations of state.

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