title: Anharmonic simulations of the vibrational spectrum of sulfated compounds: application to the glycosaminoglycan fragment glucosamine 6-sulfate.
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.
authors.affiliation: Université de Lyon, F-69622, Lyon, France. isabelle.compagnon@univ-lyon1.fr.
authors.forename: Loïc
authors.initials: L
authors.lastname: Barnes
authors.forename: Baptiste
authors.initials: B
authors.lastname: Schindler
authors.forename: Abdul-Rahman
authors.initials: AR
authors.lastname: Allouche
authors.forename: Daniel
authors.initials: D
authors.lastname: Simon
authors.forename: Stéphane
authors.initials: S
authors.lastname: Chambert
authors.forename: Jos
authors.initials: J
authors.lastname: Oomens
authors.forename: Isabelle
authors.initials: I
authors.lastname: Compagnon
mesh_terms: D003198:Computer Simulation; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D005944:Glucosamine / Q000737:chemistry*; D008958:Models, Molecular; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000379:methods; D013431:Sulfates / Q000737:chemistry; D013450:Sulfones / Q000737:chemistry; D013458:Sulfur Dioxide / Q000737:chemistry
chemical_list: D013431:Sulfates; D013450:Sulfones; D013458:Sulfur Dioxide; C025910:dimethyl sulfone; D005944:Glucosamine; D004121:Dimethyl Sulfoxide