Fourier Transform Infrared Spectroscopy and Broadband Dielectric Spectroscopy are combined to trace kinetics of mutarotation in L-fucose. After quenching molten samples down to temperatures between T = 313 K and 328 K, the concentrations of two anomeric species change according to a simple exponential time dependence, as seen by an increase in absorbance of specific IR-vibrations. In contrast, the dielectric spectra reveal a slowing down of the structural (α-) relaxation process according to a stretched exponential time dependence (stretching exponent of 1.5 ± 0.2). The rates of change in the IR absorption for α- and β-fucopyranose are (at T = 313 K) nearly one decade faster than that of the intermolecular interactions as measured by the shift of the α-relaxation. This reflects the fact that the α-relaxation monitors the equilibration at a mesoscopic length scale, resulting from fluctuations in the anomeric composition.
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At
$T_{\protect \text{eq}}$
several effects are observed in the T-dependent BDS and FTIR data. The interested reader is referred to the molecular dynamics section of Ref. 37.45.
This activation energy roughly agrees with
$E_{\protect \text{a}}=124\pm 9$
kJ/mol, as estimated earlier by some of us.27 © 2014 AIP Publishing LLC.
2014
AIP Publishing LLC
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