The Hofmeister series, which originally described the specific ion effects on the solubility of macromolecules in aqueous solutions, has been a long-standing unsolved and exceptionally challenging mystery in chemistry. The complexity of specific ion effects has prevented a unified theory from emerging. Accumulating research has suggested that the interactions among ions, water and various solutes play roles. However, among these interactions, the binding between ions and solutes is receiving most of the attention, whereas the effects of ions on the hydrogen-bond structure in liquid water have been deemed to be negligible. In this study, attenuated-total-reflectance Fourier transform infrared spectroscopy is used to study the infrared spectra of salt solutions. The results show that the red- and blue-shifts of the water bending band are in excellent agreement with the characteristic Hofmeister series, which suggests that the ions' effects on water structure might be the key role in the Hofmeister phenomenon.
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http://dx.doi.org/10.1002/cphc.201600551 | DOI Listing |
Molecules
January 2025
Department of Chemistry "Ugo Schiff" and CSGI, University of Florence, 50019 Sesto Fiorentino, Italy.
Specific ion effects are widespread and have been studied for over a century, yet they remain poorly understood. Terms like "kosmotropes" and "chaotropes" are convenient rules of thumb but the frequent reversal of the Hofmeister series implies their limitations. Polarizability is often used to classify ions, with kosmotropes considered low in polarizability and chaotropes high.
View Article and Find Full Text PDFAnal Chem
January 2025
School of Chemical Engineering, The University of Adelaide, North Terrace, Adelaide 5005, Australia.
The rise in the popularity of lipid nanoparticle (LNP)-based formulations necessitates the need for screening tools to quickly predict their colloidal stability in the presence of common excipients. Protein chemists have employed the diffusion interaction parameter () determined using dynamic light scattering as an indicator of formulation stability, yet this approach has not been applied to particulate systems. Herein, measurements of LNPs revealed behavior dissimilar to that of proteins.
View Article and Find Full Text PDFMacromolecules
January 2025
Department of Materials Science & Engineering, Texas A&M University, College Station, Texas 77840, United States.
This work explored solution properties of linear and star poly(methacrylic acids) with four, six, and eight arms (PMAA, 4PMAA, PMAA, and 8PMAA, respectively) of matched molecular weights in a wide range of pH, salt, and polymer concentrations. Experimental measurements of self-diffusion were performed by fluorescence correlation spectroscopy (FCS), and the results were interpreted using the scaling theory of polyelectrolyte solutions. While all PMAAs were pH sensitive and showed an increase in hydrodynamic radius ( ) with pH in the dilute regime, the of star polymers (measured at basic pH values) was significantly smaller for the star polyacids due to their more compact structure.
View Article and Find Full Text PDFLangmuir
January 2025
School of Advanced Engineering, Kogakuin University, Tokyo 192-0015, Japan.
Arsenocholine-containing methacrylate (MTAsB) inspired by marine organisms was synthesized by the reaction of 2-bromoethyl methacrylate and trimethylarsine to investigate its polymerization behavior and the fundamental properties of the resulting polymer. Controlled radical polymerization of MTAsB proceeded in the presence of a copper catalyst and imidazolium chloride at 60 °C for 8 h to give a water-soluble polycation with a 94% yield. The smaller amount of nonfreezing water and intermediate water of poly(MTAsB) was observed compared with that of the ammonium-containing polycations.
View Article and Find Full Text PDFEur J Pharm Biopharm
February 2025
BASF SE, Carl-Bosch-Strasse 38, 67056 Ludwigshafen am Rhein, Germany. Electronic address:
Poloxamer 338 is used as versatile thermo-responsive gelling agent in topical and sub-cutaneous applications. Due to application specific needs a gel point below body or even below room temperature is required. The influence of inorganic salts and active pharmaceutical ingredients (APIs) on the gel point was investigated using oscillatory rheology to identify the driving forces and predictors for gel point alteration.
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