Elucidation of the intrinsic optical properties of hydrogen-bonded and protonated flavin chromophores by photodissociation action spectroscopy
| Autor: | Kasper Lincke, Andreas Østergaard Madsen, Louise J. Skov, Lars H. Andersen, Mogens Brøndsted Nielsen, Elisabeth Gruber, Hjalte V. Kiefer, Kurt V. Mikkelsen, Jeppe Langeland |
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| Rok vydání: | 2018 |
| Předmět: |
DYNAMICS
Hydrogen General Physics and Astronomy Ionic bonding chemistry.chemical_element Protonation Flavin group 010402 general chemistry Photochemistry 01 natural sciences RIBOFLAVIN 0103 physical sciences Physical and Theoretical Chemistry BLUE-LIGHT RECEPTOR FAD BLUF Quantitative Biology::Biomolecules 010304 chemical physics Hydrogen bond Photodissociation SENSOR ELECTROSTATIC STORAGE-RING Chromophore 0104 chemical sciences MODEL ABSORPTION-SPECTRUM SLR1694 chemistry Intramolecular force PHOTOPHYSICS |
| Zdroj: | Lincke, K, Langeland, J, Madsen, A O, Kiefer, H V, Skov, L, Gruber, E, Mikkelsen, K V, Andersen, L H & Nielsen, M B 2018, ' Elucidation of the intrinsic optical properties of hydrogen-bonded and protonated flavin chromophores by photodissociation action spectroscopy ', Physical Chemistry Chemical Physics, vol. 20, no. 45, pp. 28678-28684 . https://doi.org/10.1039/c8cp05368e |
| ISSN: | 1463-9084 |
| DOI: | 10.1039/c8cp05368e |
| Popis: | A model system of the flavin chromophore was synthesized and investigated for its intrinsic optical properties by gas phase action spectroscopy using an ion storage ring. An ammonium group was anchored to this flavin chromophore to allow its transfer to the gas phase by electrospray ionization and for studying the influence of hydrogen bonding and a nearby positive charge. According to calculations one of the hydrogen atoms of the ammonium group favorably forms an intramolecular ionic hydrogen bond to one of the oxygen atoms of the flavin chromophore, and this interaction was found to cause a blueshift of the S-0 S-1 transition and a redshift of the S-0 S-2 transition. For comparison, the S-0 S-1 transition shows little solvent dependence (only in regard to the degree of fine structure). In addition, the influence of protonation of the flavin chromophore was elucidated by experimental and theoretical studies of a simple flavin system. While the position of the S-0 S-1 absorption was at identical positions in the gas phase for the intramolecularly hydrogen-bonded and protonated flavin systems, the S-0 S-2 absorption was further redshifted for the protonated species. This redshift resulting from protonation was also observed in solution. |
| Databáze: | OpenAIRE |
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