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AQUEOUS SOLUTIONS

Hydration determines anion accumulation

Nature Chemistry volume 14, pages 8–10 (2022)Cite this article

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Why do bulky anions solubilize macromolecules in water but precipitate out the corresponding monomers? The answer lies in the differences in local water structure. Polymers have now been shown to disrupt water structure more than their monomers, leading to an accumulation of anions near the polymers that increases their solubility.

The celebrated Hofmeister series organizes ions according to their ability to precipitate proteins from aqueous solutions1. Bulky anions that are weakly hydrated, such as iodide or thiocyanate, appear at the bottom of the Hofmeister series because they are drawn to non-polar surfaces, and can weaken hydrophobic interactions, enabling them to solubilize proteins. Interestingly, in contrast to their solubilizing effect on macromolecules2, weakly hydrated anions tend to precipitate out non-ionic small molecules3. In fact, weakly hydrated anions can enhance the solubility of certain polymers, but suppress the solubility of their monomeric building blocks. Now, writing in Nature Chemistry, Cremer and colleagues resolve this apparent paradox by showing that weakly hydrated anions affect polymers and monomers in different ways due to subtle differences in how the solutes perturb water structure4.

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Fig. 1: Solute hydration determines the accumulation of weakly hydrated anions and their influence on solubility.

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  1. Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, PA, USA

    Aniket U. Thosar & Amish J. Patel

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  1. Aniket U. Thosar
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  2. Amish J. Patel
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Correspondence to Amish J. Patel.

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Thosar, A.U., Patel, A.J. Hydration determines anion accumulation. Nat. Chem. 14, 8–10 (2022). https://doi.org/10.1038/s41557-021-00864-2

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