The Raman optical activity of β-D-xylose: where experiment and theory meet

Zielinski, Francois, Mutter, Shaun T. ORCID logoORCID:, Johannessen, Christian, Blanch, Ewan W. and Popelier, Paul L. A. (2015) The Raman optical activity of β-D-xylose: where experiment and theory meet. Physical Chemistry Chemical Physics, 17 (4) . pp. 21755-22456. ISSN 1463-9076 [Article] (doi:10.1039/c5cp02969d)

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Besides its applications in bioenergy and biosynthesis, β-D-xylose is a very simple monosaccharide that exhibits relatively high rigidity. As such, it provides the best basis to study the impact of different solvation shell radii on the computation of its Raman optical activity (ROA) spectrum. Indeed, this chiroptical spectroscopic technique provides exquisite sensitivity to stereochemistry, and benefits much from theoretical support for interpretation. Our simulation approach combines density functional theory (DFT) and molecular dynamics (MD) in order to efficiently account for the crucial hydration effects in the simulation of carbohydrates and their spectroscopic response predictions. Excellent agreement between the simulated spectrum and the experiment was obtained with a solvation radius of 10 Å. Vibrational bands have been resolved from the computed ROA data, and compared with previous results on different monosaccharides in order to identify specific structure–spectrum relationships and to investigate the effect of the solvation environment on the conformational dynamics of small sugars. From the comparison with ROA analytical results, a shortcoming of the classical force field used for the MD simulations has been identified and overcome, again highlighting the complementary role of experiment and theory in the structural characterisation of complex biomolecules. Indeed, due to unphysical puckering, a spurious ring conformation initially led to erroneous conformer ratios, which are used as weights for the averaging of the spectral average, and only by removing this contribution was near perfect comparison between theory and experiment achieved.

Item Type: Article
Research Areas: A. > School of Science and Technology > Natural Sciences
Item ID: 26150
Notes on copyright: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence
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Depositing User: Shaun Mutter
Date Deposited: 07 Feb 2019 17:48
Last Modified: 29 Nov 2022 22:30

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