Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules.

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Ionic Liquids at Electrified Interfaces

Electrostatic correlations play an important role in physics, chemistry and biology. In plasmas they result in thermodynamic instability similar to the liquid–gas phase transition of simple molecular fluids. For charged colloidal suspensions the electrostatic correlations are responsible for screening and colloidal charge renormalization. In aqueous solutions containing multivalent counterions they can lead to charge inversion and flocculation. In biological systems the correlations account for the organization of cytoskeleton and the compaction of genetic material. In spite of their ubiquity, the true importance of electrostatic correlations has come to be fully appreciated only quite recently. In this paper, we will review the thermodynamic consequences of electrostatic correlations in a variety of systems ranging from classical plasmas to molecular biology.

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Electrostatic correlations: from plasma to biology

I Basics- 1 The Physical Nature of Planar Bilayer Membranes- 2 Ion Channel Electrostatics and the Shapes of Channel Proteins- 3 Superoxide Dismutase as a Model Ion Channel- 4 Single-Channel Enzymology- 5 How to Set Up a Bilayer System- 6 Fusion of Liposomes to Planar Bilayers- 7 Incorporation of Ion Channels by Fusion- II Nicotinic Acetylcholine Receptor- 8 The Reconstituted Acetylcholine Receptor- 9 Immunologic Analysis of the Acetylcholine Receptor- 10 Function of Acetylcholine Receptors in Reconstituted Liposomes- III Sodium Channel- 11 Skeletal Muscle Sodium Channels: Isolation and Reconstitution- 12 Reconstitution of the Sodium Channel from Electrophorus electricus- 13 The Reconstituted Sodium Channel from Brain- 14 Gating of Batrachotoxin-Activated Sodium Channels in Lipid Bilayers- 15 Ion Conduction Through Sodium Channels in Planar Lipid Bilayers- 16 Blocking Pharmacology of Batrachotoxin-Activated Sodium Channels- IV Other Channels in Model Membranes- 17 The Large Calcium-Activated Potassium Channel- 18 The Sarcoplasmic Reticulum Potassium Channel: Lipid Effects- 19 Characterization of Dihydropyridine-Sensitive Calcium Channels from Purified Skeletal Muscle Transverse Tubules- 20 Calcium Channels- 21 Phosphorylation of a Reconstituted Potassium Channel- 22 Voltage Gating in VDAC: Toward a Molecular Mechanism- 23 Analysis and Chemical Modification of Bacterial Porins

Ion Channel Reconstitution

A theoretical analysis of the sum frequency generation spectrum of the water surface

Ionization of phospholipids and phospholipid-supported interfacial lateral diffusion of protons in membrane model systems

This paper reports grand canonical Monte Carlo computations on the diffuse double layer in an ionic system next to a uniformly charged plane surface. The boundary conditions and the grand canonical techniques are discussed. Calculations were carried out for the 1:1 restricted primitive model at several concentrations and over a range of surface charge densities. The results are compared with the modified Gouy–Chapman theory, and some remarks are also possible with respect to the modified Poisson–Boltzmann and the hypernetted chain approaches. At high concentrations and surface charge densities the counterions are packed closely at the surface and begin to show a layered structure. This results in a large electrostatic potential drop, but only very slight charge oscillations are observed in the solution. None of the theories seems able to describe this behavior.

J. P. Valleau

Papers

Electrical double layers. I. Monte Carlo study of a uniformly charged surface