Monosaccharides, microwave spectroscopy

Microwave spectroscopy can also quantify experimentally the relative proportions of the observed species. However, for some of the detected monosaccharides the correlation between the experimental populations and the calculated relative energies is not always obvious. This might reflect incomplete conformational cooling in the supersonic expansion which does not lead to a relaxed population reflecting the equilibrium at low temperature (and the potential energy surface of the system). Alternatively, the pre-expansion population (governed by the free energy surface at the vaporization temperature) may have been frozen early in the expansion, or the observed population may simply reflect the initial distribution of structures prior to vaporization in the solid sample. 

Nowadays, the combination of laser ablation with Fourier transform microwave spectroscopy techniques, in supersonic jets, has enabled the gas-phase study of such systems. In this chapter, these techniques, including broadband spectroscopy, as well as results of their application into the study of the conformational panorama and structure of biomolecular building blocks, such as amino acids, nucleic bases, and monosaccharides, are briefly discussed, and with them, the tools for conformational assignation - rotational constants, nuclear quadrupole coupling interaction, and dipole moment. 

Similar to 2DR, ribose (C5H5O5) is one of the most important monosaccharides since it constitutes a subunit of the backbone of RNA. NMR studies have shown that ribose in solution is a mixture of a- and p-pyranose and a- and p-furanose forms, the p-pyranose form being predominant. The recently settled crystal structures have shown that the a- and P-pyranose forms are present in the solid phase [239-243]. The structure in the gas phase has been experimentally investigated using a laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MBFTMW) technique [62]. The high resolution rotational spectrum has provided structural information on a total of six rotamers of ribose, three belonging to the a-pyranose forms and other three to the P-pyranose forms. Recently, D-ribose (m.p. 95°C) has been submitted to a laser ablation broadband (CP-FTMW) spectroscopic study and eight conformers (two new a-pyranose forms) have been identified. A broadband section of the spectra is shown in Fig. 35 and the detected conformers depicted in Fig. 36. 

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