Optical Properties of a Visible Push–Pull Chromophore Covalently Bound to Carbohydrates: Solution and Gas-Phase Spectroscopy Combined to Theoretical Investigations

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-cya...

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Published in:The journal of physical chemistry. B 2012-01, Vol.116 (2), p.841-851
Main Authors: Enjalbert, Quentin, Racaud, Amandine, Lemoine, Jérôme, Redon, Sébastien, Ayhan, Mehmet Menaf, Andraud, Chantal, Chambert, Stéphane, Bretonnière, Yann, Loison, Claire, Antoine, Rodolphe, Dugourd, Philippe
Format: Article
Language:English
Subjects:
Analytical chemistry
B: Statistical Mechanics, Thermodynamics, Medium Effects
Carbohydrates
Carbohydrates - chemistry
Chemical Sciences
Chromophores
Computer simulation
Gases - chemistry
Grafting
Maltose - chemistry
Mathematical models
Models, Theoretical
Molecular Dynamics Simulation
or physical chemistry
Photodissociation
Solutions - chemistry
Spectrophotometry, Ultraviolet
Spectroscopy
Sugars
Theoretical and
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Summary: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.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp2099015