Structures of Biomolecules in the gas phase

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Sugars and oligosaccharides

Introduction

Carbohydrates constitute one of the four major classes of biomolecules, along with proteins, nucleic acids and lipids. They can be found as polysaccharides, or bound to proteins and/or lipids, or as part of the structural framework of the nucleic acids - but they are not normally found in the gas phase! They make up most of the organic matter on Earth and have multiple functions in living systems: They serve as energy stores, fuels, and metabolic intermediates, they are parts of cell walls and play a key role in molecular recognition at the cell’s surface.

Current research projects 

A model monosaccharide, phenyl-b-D-glucopyranoside, has been investigated spectroscopically and with ab initio computation.  Comparison with ab initio predictions of unsubstituted b-D-glucopyranose indicates that the addition of a phenyl substituent at position 1 on the pyranoside ring has very little effect on the low energy region of the conformational landscape.
Figure 1. Low-lying conformers of phenyl-b-D-glucopyranoside. Relative energies are in kJ/mol. 

3 conformers are observed. Assuming all three conformers have the same oscillator strength, these intensities then correspond to population percentages of 68:25:7 %, for A:B:X.
 
Figure 2. 

The IR spectra allow an unambiguous assignment of species ‘X’ to the trans conformer ttttTg+. Species ‘A’ and ‘B’ correspond
to the two gauche conformers, and are tentatively assign to the ttttG+g- and ttttG-g+ conformers respectively. The liquid-phase population of 50:50:0 % for gauche:gauche:trans does not reflect our gas-phase population of 68:25:7%, which encourages the investigation of the water clusters...
 
Figure 3. 

Near future 

An investigation of phenylgalactose will be the second step toward the investigation of lactose (Gal-Glc).

Collaborations 

Professor George Fleet (Dyson Perrins Laboratory for Organic Chemistry, Oxford)
Professor Raymond Dwek, Dr. Mark Wormald (Oxford Glycobiology Institute)

References

  • Sugars in the gas phase: the spectroscopy and structure of jet-cooled Phenyl b-D-Glucopyranoside, F.O. Talbot and J.P. Simons, Phys. Chem. Chem. Phys., 2002, 4, 3562-3565.



  • Neurotransmitters  |  Sugars  |  Amino acids, peptides  |  Protonated species  | Circular Dichroism spectroscopy

    Last updated 08/10/2002 by Lavina Snoek