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Issue 39, 2015
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Anharmonic simulations of the vibrational spectrum of sulfated compounds: application to the glycosaminoglycan fragment glucosamine 6-sulfate

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Abstract

Mid-infrared spectroscopy coupled with mass spectrometry is an appealing tool for the sequencing and structural elucidation of functional modifications in biopolymers, as it offers direct spectroscopic identification of the functionality where the traditional mass spectrometric approach is insufficient. Whereas the gas phase vibrational spectroscopy of peptides (and to a lesser extent saccharides) has been widely investigated, sulfation has attracted much less attention, despite its prevalence in natural polymers. The simulation of the vibrational spectra of such functionalized compounds is however notoriously challenging, which impairs the interpretation of spectroscopic data in terms of structure. Driven by a striking case of such a failure for a sulfated glycosaminoglycan fragment, we elaborate on an original hybrid GVPT2 anharmonic approach. This strategy offers a significantly improved accuracy in the description of the sulfate modes, without the recourse to empirical scaling factors, and with a greatly reduced computational cost which is otherwise prohibitive for molecules of this size. Alternatively, we propose a selection of reasonably accurate harmonic methods with adequate scaling factors optimized on a set of benchmark compounds.

Graphical abstract: Anharmonic simulations of the vibrational spectrum of sulfated compounds: application to the glycosaminoglycan fragment glucosamine 6-sulfate

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Publication details

The article was received on 09 Apr 2015, accepted on 22 Jun 2015 and first published on 22 Jun 2015


Article type: Communication
DOI: 10.1039/C5CP02079D
Citation: Phys. Chem. Chem. Phys., 2015,17, 25705-25713
  • Open access: Creative Commons BY-NC license
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    Anharmonic simulations of the vibrational spectrum of sulfated compounds: application to the glycosaminoglycan fragment glucosamine 6-sulfate

    L. Barnes, B. Schindler, A. Allouche, D. Simon, S. Chambert, J. Oomens and I. Compagnon, Phys. Chem. Chem. Phys., 2015, 17, 25705
    DOI: 10.1039/C5CP02079D

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