Ion-Specific Water-Macromolecule Interactions at the Air/Aqueous Interface: An Insight into Hofmeister Effect

The specificity of ions in inducing conformational changes in macromolecules is introduced as the Hofmeister series; however, the detailed underlying mechanism is not comprehensible yet. We utilized surface-specific sum frequency generation (SFG) vibrational spectroscopy to explore the Hofmeister effect at the air/polyvinylpyrrolidone (PVP)/water interface. The spectral signature observed from the ssp polarization scheme reveals ion-specific ordering of water molecules following the Hofmeister series attributed to the ion–macromolecule interactions. Along with this, the presence of ions does not reflect any significant influence on the structure of the PVP macromolecule. However, the ppp-SFG spectra in the CH-stretch region reveal the impact of ions on the orientation angle of vinyl chain CH2-groups, which follows the Hofmeister series: SO42– > Cl– > NO3– > Br– > ClO4– > SCN–. The minimal orientation angle of CH2-groups indicates significant reordering in PVP vinyl chains in the presence of chaotropic anions ClO4–, and SCN–. The observation is attributed to the ion-specific water–macromolecule interactions at the air/aqueous interface. It is compelling to observe the signature of spectral blue shifts in the OH-stretch region in the ppp configuration in the presence of chaotropic anions. The origin of spectral blue shifts has been ascribed to the existence of weaker interactions between the interfacial water molecules and the backbone CH- and CH2-moieties of the PVP macromolecules. The ion-specific modulation in water–macromolecule interactions is endorsed by the relative propensity of anion’s adsorption toward the air/aqueous interface. The experimental findings highlight the existence and cooperative participation of ion-specific water–macromolecule interactions in the mechanism of the Hofmeister effect, along with the illustrious ion–water and ion–macromolecule interactions.