Reversed Hofmeister series—The rule rather than the exception

Over recent years, the supposedly universal Hofmeister series has been replaced by a diverse spectrum of direct, partially altered and reversed series. This review aims to provide a detailed understanding of the full spectrum by combining results from molecular dynamics simulations, Poisson–Boltzmann theory and AFM experiments. Primary insight into the origin of the Hofmeister series and its reversal is gained from simulation-derived ion–surface interaction potentials at surfaces containing non-polar, polar and charged functional groups for halide anions and alkali cations. In a second step, the detailed microscopic interactions of ions, water and functional surface groups are incorporated into Poisson–Boltzmann theory. This allows us to quantify ion-specific binding affinities to surface groups of varying polarity and charge, and to provide a connection to the experimentally measured long-ranged electrostatic forces that stabilize colloids, proteins and other particles against precipitation. Based on the stabilizing efficiency, the direct Hofmeister series is obtained for negatively charged hydrophobic surfaces. Hofmeister series reversal is induced by changing the sign of the surface charge from negative to positive, by changing the nature of the functional surface groups from hydrophobic to hydrophilic, by increasing the salt concentration, or by changing the pH. The resulting diverse spectrum reflects that alterations of Hofmeister series are the rule rather than the exception and originate from the variation of ion-surface interactions upon changing surface properties.