Cations Bind Only Weakly to Amides in Aqueous Solutions
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Abstract
We investigated salt interactions
with butyramide as a simple mimic
of cation interactions with protein backbones. The experiments were
performed in aqueous metal chloride solutions using two spectroscopic
techniques. In the first, which provided information about contact
pair formation, the response of the amide I band to the nature and
concentration of salt was monitored in bulk aqueous solutions via
attenuated total reflection Fourier transform infrared spectroscopy.
It was found that molar concentrations of well-hydrated metal cations
(Ca<sup>2+</sup>, Mg<sup>2+</sup>, Li<sup>+</sup>) led to the rise
of a peak assigned to metal cation-bound amides (1645 cm<sup>–1</sup>) and a decrease in the peak associated with purely water-bound amides
(1620 cm<sup>–1</sup>). In a complementary set of experiments,
the effect of cation identity and concentration was investigated at
the air/butyramide/water interface via vibrational sum frequency spectroscopy.
In these studies, metal ion–amide binding led to the ordering
of the adjacent water layer. Such experiments were sensitive to the
interfacial partitioning of cations in either a contact pair with
the amide or as a solvent separated pair. In both experiments, the
ordering of the interactions of the cations was: Ca<sup>2+</sup> >
Mg<sup>2+</sup> > Li<sup>+</sup> > Na<sup>+</sup> ≈ K<sup>+</sup>. This is a direct cationic Hofmeister series. Even for Ca<sup>2+</sup>, however, the apparent equilibrium dissociation constant
of the
cation with the amide carbonyl oxygen was no tighter than ∼8.5
M. For Na<sup>+</sup> and K<sup>+</sup>, no evidence was found for
any binding. As such, the interactions of metal cations with amides
are far weaker than the analogous binding of weakly hydrated anions