Journal of Physical Chemistry B, Vol.119, No.10, 3931-3939, 2015
UV Resonance Raman Investigation of the Aqueous Solvation Dependence of Primary Amide Vibrations
We investigated the normal, niode composition and the aqueous solvation dependence of the primary amide vibrations of propanamide, Infrared, normal Raman, and UV resonance Raman (U, VRR) s-pectroscopy were applied in conjunction, with density functional theory (DFT) to, 'assign the vibrations ofxrystalline, propanamide. We examined the aqueous solvation dependence of the primary amide UVRR bands by measuring spectra in different acetonitrile/water mittures. As previously observed in the UVRR,spectra of Nmethylacetarinde, all of the resonance enhanced primary amide bands, except for the'AM, ide I (AmI), show increased tJVRR cross sections as the solvent becomes water-rich. These ectral trends are rationalized by a model wherein the hydrogen bonding and the high dielectric constant of water stabilizes the gr- Mind state dipolar O--C=NH2+ resonance structure over the neutral O=C-NH2 resonance structure. Thus, vibrations with large C N stretching show increased UVRR cfoss sections because the C N displacement between the electronic ground and excited state increases along the C N bond, In contrast, vibrations, dominated by C=O stretching, such as the Aml, show a decreased displacement between the electronic ground and excited State, which result in a decreased UVRR cross sectin upon aqueous solvatiOn. The UVRR primary amide vibrations can be used as sensitive Spectroscopic markers to study the local dielectric constant and hydrogen bonding environments of the primary amide side chains Of glutamine (GIn) and asparagirie (Mn).