The Hofmeister series or lyotropic series is a classification of ions in order of their lyotrophic properties, which is the ability to salt out or salt in proteins. The effects of these changes were first worked out by Franz Hofmeister, who studied the effects of cations and anions on the solubility of proteins.
Kosmotropes and chaotropes Highly charged ions interact strongly with water, breaking hydrogen bonds and inducing electrostatic structuring of nearby water, and are thus called "structure-makers" or "kosmotropes". Conversely, weak ions can disrupt the structure of water, and are thus called "structure-breakers" or "chaotropes". The order of the tendency of ions to make or break water structure is the basis of the Hofmeister series. Hofmeister discovered a series of salts that have consistent effects on the solubility of proteins and, as it was discovered later, on the stability of their secondary and tertiary structures. Anions appear to have a larger effect than cations, and are usually ordered as follows:
(kosmotropic) : C i t r a t e 3 − > F − > P O 4 3 − > S O 4 2 − > O A c − > M e S O 4 − > C l − > B r − > I − > B F 4 − > S C N − {\displaystyle \mathrm {Citrate^{3-}>F^{-}>PO_{4}^{3-}>SO_{4}^{2-}>OAc^{-}>MeSO_{4}^{-}>Cl^{-}>Br^{-}>I^{-}>BF_{4}^{-}>SCN^{-}} } (chaotropic) This is a partial list as many more salts have been studied, which applies to cations as well. The order of cations is usually given as:
(kosmotropic) : ( C H 3 ) 4 N + > N H 4 + > K + > N a + > C s + > L i + > M g 2 + > C a 2 + > B a 2 + > G u a n i d i n i u m + {\displaystyle \mathrm {(CH_{3})_{4}N^{+}>NH_{4}^{+}>K^{+}>Na^{+}>Cs^{+}>Li^{+}>Mg^{2+}>Ca^{2+}>Ba^{2+}>Guanidinium^{+}} } (chaotropic) When oppositely charged kosmotropic cations and anions are in solution together, they are attracted to each other, rather than to water, and the same can be said for chaotropic cations and anions. Thus, the preferential associations of oppositely charged ions can be ordered as:
kosmotrope-kosmotrope > kosmotrope-water > water-water > chaotrope-water > chaotrope-chaotrope Combining kosmotropic anions with kosmotropic cations reduces the kosmotropic effect of these ions because they are pairing to each other too strongly to be structuring water. Kosmotropic anions do not readily pair with chaotropic cations. The combination of kosmotropic anions with chaotropic cations is the best ion combination to stabilize proteins.
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