Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy

Raman spectroscopy of glyoxal oligomers in aqueous solutions.

PMID 23099158


Raman microscopy and Attenuated Total Reflection infrared spectroscopy were utilized to facilitate investigations of equilibria between various hydrated and oligomeric forms of glyoxal in aqueous glyoxal solution droplets. The assignment of spectra is obtained with the assistance of B3LYP density functional quantum chemical calculations of vibrational wavenumbers, Raman activities, and infrared intensities. Several forms of glyoxal derivatives with similar functional groups, e.g., hydroxyl and dioxolane rings, are found to be present. The absence of a Raman spectral peak corresponding to the vibrational carbonyl stretch provides evidence that both carbonyl groups of a glyoxal molecule become hydrated in solutions of a broad concentration range. The presence of bands corresponding to deformation vibrations of the dioxolane ring indicates that dihydrated glyoxal oligomers are formed in glyoxal solutions with concentrations of 1 M and higher. Under typical ambient temperature and humidity conditions, concentrated glyoxal solution droplets undergo evaporation with incomplete water loss. Our results suggest that formation of crystalline glyoxal trimer dihydrate from concentrated solutions droplets is hindered by the high viscosity of the amorphous trimer and requires dry conditions that could rarely be achieved in the atmosphere. However, crystallization may be possible for droplets of low initial glyoxal concentrations, such as those produced by evaporating cloud droplets.