title: Optical properties of a visible push-pull chromophore covalently bound to carbohydrates: solution and gas-phase spectroscopy combined to theoretical investigations.
abstract: The use of visible absorbing and fluorescent tags for sensing and structural analysis of carbohydrates is a promising route in a variety of medical, diagnostic, and therapeutic contexts. Here we report an easy method for covalent attachment of nonfluorescent push-pull chromophores based on the 4-cyano-5-dicyanomethylene-2-oxo-3-pyrroline ring to carbohydrate moieties. The impact of sugar grafting on the optical properties of the push-pull chromophore in the gas phase and in solution was investigated by absorption and action spectroscopy and theoretical methods. The labeled sugars efficiently absorb photons in the visible range, as demonstrated by their intense photodissociation in a quadrupole ion trap. A strong blue shift (-70 nm) of the gas-phase photodissociation intensity maximum is observed upon sugar grafting, whereas no such effect is visible on the solution absorption spectra. Molecular dynamics simulations of labeled maltose in the gas phase describe strong interactions between the sulfonated chromophore and the carbohydrate, which lead to cyclic conformations. These are not observed in the simulations with explicit solvation. Time-dependent density functional theory (TD-DFT) calculations on model molecules permit us to attribute the observed shift to the formation of such cyclic conformations and to the displacement of the negative charge relative to the aromatic moiety of the chromophore.
authors.affiliation: Université de Lyon, Lyon, France.
authors.forename: Quentin
authors.initials: Q
authors.lastname: Enjalbert
authors.forename: Amandine
authors.initials: A
authors.lastname: Racaud
authors.forename: Jérôme
authors.initials: J
authors.lastname: Lemoine
authors.forename: Sébastien
authors.initials: S
authors.lastname: Redon
authors.forename: Mehmet Menaf
authors.initials: MM
authors.lastname: Ayhan
authors.forename: Chantal
authors.initials: C
authors.lastname: Andraud
authors.forename: Stéphane
authors.initials: S
authors.lastname: Chambert
authors.forename: Yann
authors.initials: Y
authors.lastname: Bretonnière
authors.forename: Claire
authors.initials: C
authors.lastname: Loison
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Antoine
authors.forename: Philippe
authors.initials: P
authors.lastname: Dugourd
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D008320:Maltose / Q000737:chemistry; D008962:Models, Theoretical; D056004:Molecular Dynamics Simulation; D012996:Solutions / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D002241:Carbohydrates; D005740:Gases; D012996:Solutions; D008320:Maltose