Anionic and cationic Hofmeister effects are non-additive for guanidinium salts.

To understand specific ion effects on a molecular level we explore the effect of salts on the rotational mobility of a model amide using dielectric spectroscopy. Based on our previous studies on the effect of strong denaturing anions or cations, here we study the additivity of the anionic and cationic effect. Using salts consisting of denaturing spherical anions and spherical cations we find such salts to affect the amide according to what one expects based on the additive activity of the individual ions. The guanidinium (Gdm+) cation appears to be a notable exception, as our results suggest that GdmI (and accordingly GdmSCN) is less efficient in hindering the rotation of the amide than KI or GdmCl.

• Publication year

  2017

• Venue

  Physical Chemistry, Chemical Physics - PCCP

• Publication date

  2017-04-12

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1039/c7cp00790fPMID 28361132
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Correction: Quantifying transient interactions between amide groups and the guanidinium cation.

  2016cited by this paper
• Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

  2016cited by this paper
• Quantifying transient interactions between amide groups and the guanidinium cation.

  2015cited by this paper
• Guanidinium-Induced Denaturation by Breaking of Salt Bridges.

  2015cited by this paper
• Beyond Hofmeister.

  2014cited by this paper
• Kinetic dielectric decrement revisited: phenomenology of finite ion concentrations.

  2014cited by this paper
• Models and mechanisms of Hofmeister effects in electrolyte solutions, and colloid and protein systems revisited.

  2014cited by this paper
• Extreme surface propensity of halide ions in water

  2014cited by this paper
• Reversal of the hofmeister series: specific ion effects on peptides.

  2013cited by this paper
• A conductance study of guanidinium chloride, thiocyanate, sulfate, and carbonate in dilute aqueous solutions: ion-association and carbonate hydrolysis effects.

  2013cited by this paper
• Effects of End Group Termination on Salting-Out Constants for Triglycine.

  2013cited by this paper
• Cations bind only weakly to amides in aqueous solutions.

  2013cited by this paper
• Guanidinium Cations Pair with Positively Charged Arginine Side Chains in Water

  2011cited by this paper
• Unfolding of hydrophobic polymers in guanidinium chloride solutions.

  2010cited by this paper
• Are nanoscale ion aggregates present in aqueous solutions of guanidinium salts?

  2010cited by this paper
• Chemistry of Hofmeister anions and osmolytes.

  2010cited by this paper
• Surface tensions, surface potentials, and the Hofmeister series of electrolyte solutions.

  2010cited by this paper
• Specific Ion Effects

  2009cited by this paper
• What can be learnt from dielectric relaxation spectroscopy about ion solvation and association?

  2008cited by this paper
• Ions at aqueous interfaces: from water surface to hydrated proteins.

  2008cited by this paper
• Interactions between hydrophobic and ionic solutes in aqueous guanidinium chloride and urea solutions: lessons for protein denaturation mechanism.

  2007cited by this paper
• Relation between dielectric and low-frequency Raman spectra of hydrogen-bond liquids.

  2005cited by this paper
• Is there an anionic Hofmeister effect on water dynamics? Dielectric spectroscopy of aqueous solutions of NaBr, NaI, NaNO3, NaClO4, and NaSCN.

  2005cited by this paper
• ‘Zur Lehre von der Wirkung der Salze’ (about the science of the effect of salts): Franz Hofmeister's historical papers

  2004cited by this paper
• Complexity in "simple" electrolyte solutions: Ion pairing in MgSO4(aq)

  2004cited by this paper
• Dielectric relaxation of aqueous NaCl solutions

  1999cited by this paper
• Dielectric relaxation in aqueous solutions of urea and some of its derivatives

  1986cited by this paper
• The Hofmeister effect and the behaviour of water at interfaces

  1985cited by this paper
• Kinetic polarization deficiency in electrolyte solutions.

  1977cited by this paper
• Zur Lehre von der Wirkung der Salze

  1891cited by this paper

• Deciphering Spectroscopic Signatures of Competing Ca2+ - Peptide Interactions

  2024cites this paper
• Strong adsorption of guanidinium cations to the air–water interface

  2024cites this paper
• Deciphering the guanidinium cation: Insights into thermal diffusion.

  2024cites this paper
• Charge transport in protic ionic liquids: Effect of protonation state in 1-methylimidazolium – acetate/trifluoroacetate mixtures

  2023cites this paper
• Ion-specific binding of cations to the carboxylate and of anions to the amide of alanylalanine

  2022cites this paper
• Imprinting the complex dielectric permittivity of liquids into the spintronic terahertz emission

  2021cites this paper
• The cation effect on the solubility of glycylglycine and N-acetylglycine in aqueous solution: Experimental and molecular dynamics studies

  2020cites this paper
• Effect of Salts and Organic Osmolytes is Due to Conservative Forces

  2020cites this paper
• Consistent description of ion-specificity in bulk and at interfaces by solvent implicit simulations and mean-field theory.

  2020cites this paper
• Activity Coefficient of Solution Components and Salts as Special Osmolyte from Kirkwood-Buff Theoretical Perspective

  2019cites this paper
• Nonadditive Ion Effects Drive Both Collapse and Swelling of Thermoresponsive Polymers in Water.

  2019cites this paper
• Specific Ion Effects on an Oligopeptide: Bidentate Binding Matters for the Guanidinium Cation.

  2018cites this paper
• Cation-specific interactions of protein surface charges in dilute aqueous salt solutions: a combined study using dielectric relaxation spectroscopy and Raman spectroscopy.

  2018cites this paper
• Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation.

  2018cites this paper
• Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view

  2018cites this paper
• Spezifische Ionen-Effekte am Beispiel eines Oligopeptids: die Rolle zweizähniger Koordination beim Guanidinium-Kation

  2018cites this paper