Search results for "Hofmeister series"
showing 7 items of 7 documents
pKa at Quartz/Electrolyte Interfaces.
2016
Acidity of silanol sites at the crystalline quartz/aqueous electrolyte (NaCl, NaI, KCl) interfaces are calculated from ab initio molecular dynamics simulations. pKa’s are found to follow a combination of the cationic and anionic Hofmeister series in the order pKa(neat solution) < pKa(NaCl) < pKa(NaI) < pKa(KCl), in agreement with experimental measurements. Rationalization of this ranking is achieved in terms of the microscopic local solvation of the protonated silanols and their conjugated bases, the silanolates SiO–. The change in the pKa is the result of both water destructuring by alkali halides, as well as of the specific cation/SiO– interaction, depending on the electrolyte. M…
Observation of interaction forces by investigation of the influence of eluent additives on the retention behavior of aqueous nanoparticle dispersions…
2020
The investigation and subsequent understanding of the interactions of nanomaterials with components of their surrounding media is important to be able to evaluate both potential use cases as well as potential risks for human health and for the environment. To investigate such interactions, asymmetrical flow field-flow fractionation (AF4) is an interesting analytical tool. This statement grounds on the fact that interactions of the analyte with the membrane and with components of the eluent are crucial for the retention behavior of the analyte within the field-flow fractionation (FFF) channel. Therefore, the investigation of the retention behavior provides an insight in the nature of the int…
Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin
2015
Dodecaborate anions of the type B12X12(2-) and B12X11Y(2-) (X=H, Cl, Br, I and Y=OH, SH, NH3(+), NR3(+)) form strong (K(a) up to 10(6) L mol(-1), for B12Br12(2-)) inclusion complexes with γ-cyclodextrin (γ-CD). The micromolar affinities reached are the highest known for this native CD. The complexation exhibits highly negative enthalpies (up to -25 kcal mol(-1)) and entropies (TΔS up to -18.4 kcal mol(-1), both for B12I12(2-)), which position these guests at the bottom end of the well-known enthalpy-entropy correlation for CDs. The high driving force can be traced back to a chaotropic effect, according to which chaotropic anions have an intrinsic affinity to hydrophobic cavities in aqueous …
Effect of the Alkaline Cations on the Stability of the Model Polynucleotide Poly(dG-dC)·Poly(dG-dC)
2011
When the model polynucleotide poly(dG-dC)∙poly(dG-dC) [polyGC] is titrated with a strong acid (HCl) in unbuffered aqueous solutions containing the chlorides of the alkali metals in the concentration range 0.010 M-0.600 M, two transitions in the absorbance vs. pH plots are evidenced, characterized by the constants pK(a(₁)) and pK(a(₂)). The limiting values at infinite saline concentrations of these two constants, namely pK(∞)(a(₁)) and pK(∞)(a(₂)) obtained making use of the "one site saturation constant" equation or, in turn, of the double logarithmic plot: pK(a) vs. log([salt]⁻¹), exhibit a clear dependence on the nature of the cations. The effects of the different alkali cations on the pK(…
On the stability of the 24-meric hemocyanin from Eurypelma californicum.
1998
The stability of the 24-meric hemocyanin from Eurypelma californicum towards various denaturants (GdnHCl, urea, urea derivatives and salts of the Hofmeister series) indicates that the quaternary structure is stabilized by hydrophilic and polar forces. Thus, the interaction between the seven different subunit types of this cheliceratan hemocyanin is comparable with that of the closely related crustacean hemocyanins. In contrast, no significant influence of divalent ions such as Ca2+ and Mg2+ on the stability is observed at pH 8.0 and pH 8.5 but not at pH 7.0. Studies, both in the presence of urea and GdnHCl indicate that the denaturation process consists of a dissociation of the oligomeric s…
Hydrogen bond properties of saccharide matrices studied through Infrared Water Association Band
2010
Hydrogen bond properties of saccharide matrices studied through Infrared Water Association Band