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Journal Article

Protons and Hydroxide Ions in Aqueous Systems


Campen,  R. Kramer
Physical Chemistry, Fritz Haber Institute, Max Planck Society;


Thämer,  Martin
Physical Chemistry, Fritz Haber Institute, Max Planck Society;
Department of Chemistry, Institute for Biophysical Dynamics, and James Franck Institute, The University of Chicago;

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Agmon, N., Bakker, H. J., Campen, R. K., Henchman, R. H., Pohl, P., Roke, S., et al. (2016). Protons and Hydroxide Ions in Aqueous Systems. Chemical Reviews, 116(13), 7642-7672. doi:10.1021/acs.chemrev.5b00736.

Cite as: http://hdl.handle.net/11858/00-001M-0000-002A-FB27-0
Understanding the structure and dynamics of water’s constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid–base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.