Nos tutelles

CNRS

Rechercher





Accueil > English > Teams > H2M - Hydrogen Molecules Materials > Molecules > Proton transfer and protonated molecules

Protonated molecules

publié le , mis à jour le

Protonated hydrocarbon molecules denoted AH+ constitute a fundamental class of organic molecules. They play a role as short-lived intermediates in a broad range of environments, ranging from astrochemistry, jet engine gas exhaust and organic chemistry to biophysics. For example, AH+ species are widely accepted as intermediates in electrophilic aromatic substitution reactions, the most important reaction mechanism of aromatic molecules AH+ ions have been detected in various hydrocarbon plasma. AH+ ions are present in the interstellar space.

In addition, the effects of protonation on aromatic biomolecular building blocks is an interesting issue for models rationalizing the UV photostability of biological macromolecules, such as proteins and DNA

Despite their importance, surprisingly very little was known (only two papers in 1977) about the geometric and electronic structure, reactivity, and dynamics of even simple isolated AH+ ions This is mainly due to the difficulties encountered in the production of high concentrations of these reactive species in gas phase, which are required to probe their properties by spectroscopy. Recent advances in the development of efficient ion sources , sensitive IR spectroscopic detection and ion trapping techniques have allowed substantial progress in the characterization of the geometric structure of isolated and microsolvated AH+ ions in the gas phase

The goal of the project is the characterization of structures, dynamics, and electronic properties of protonated molecules, more specifically aromatic molecules, although the investigation of other protonated molecules is not excluded . Protonated hydrocarbon molecules constitute a fundamental class of organic molecules. They play a role as short-lived intermediates in a broad range of environments, ranging from astrochemistry, jet engine gas exhaust and organic chemistry to biophysics. While structure elucidation will be carried out using infrared (IR) spectroscopy, electronic structure as well as fragmentation and relaxation dynamics induced by electronic excitation will be investigated using ultraviolet (UV) spectroscopy with nanosecond, picosecond and femtosecond lasers. Protonated molecules can be detected in situ by mass spectrometry techniques but cannot be detected from outside through their optical properties due to the complete lack of information on their spectroscopy. The knowledge of their spectroscopic and optical properties would therefore allow their detection in inaccessible environments.

Publications

1. Pino, G. A. ; Feraud, G. ; Broquier, M. ; Grégoire, G. ; Soorkia, S. ; Dedonder, C. ; Jouvet, C., Non-radiative processes in protonated diazines, pyrimidine bases and an aromatic azine. Physical Chemistry Chemical Physics 2016.
2. Feraud, G. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Marceca, E., Photodissociation UV-Vis Spectra of Cold Protonated Azobenzene and 4-(Dimethylamino)azobenzene and Their Benzenediazonium Cation Fragment. The journal of physical chemistry. A 2016, 120, (22), 3897-905.
3. Broquier, M. ; Soorkia, S. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Theule, P. ; Gregoire, G., Twisted Intramolecular Charge Transfer in Protonated Amino Pyridine. Journal of Physical Chemistry A 2016, 120, (21), 3797-3809.
4. Taccone, M. I. ; Feraud, G. ; Berdakin, M. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Pino, G. A., Communication : UV photoionization of cytosine catalyzed by Ag+. Journal of Chemical Physics 2015, 143, (4).
5. Soorkia, S. ; Dehon, C. ; Kumar, S. S. ; Perot-Taillandier, M. ; Lucas, B. ; Jouvet, C. ; Barat, M. ; Fayeton, J. A., Ion-Induced Dipole Interactions and Fragmentation Times : C alpha-C beta Chromophore Bond Dissociation Channel. Journal of Physical Chemistry Letters 2015, 6, (11), 2070-2074.
6. Noble, J. A. ; Dedonder, C. ; Jouvet, C., The electronic spectra of protonated nitrogen-substituted polycyclic aromatic hydrocarbon molecules. Astronomy & Astrophysics 2015, 577.
7. Inokuchi, Y. ; Takeharu, H. ; Sekiya, R. ; Morishima, F. ; Dedonder, C. ; Féraud, G. ; Jouvet, C. ; Takayuki, E., UV photodissociation spectroscopy of cryogenic cooled gas phase host-guest complex ions of crown ethers. physical Chemistry Chemical Physics 2015, 17, 25925.
8. Feraud, G. ; Esteves-Lopez, N. ; Dedonder-Lardeux, C. ; Jouvet, C., UV spectroscopy of cold ions as a probe of the protonation site. Physical Chemistry Chemical Physics 2015, 17, (39), 25755-25760.
9. Feraud, G. ; Broquier, M. ; Dedonder, C. ; Jouvet, C. ; Gregoire, G. ; Soorkia, S., Excited State Dynamics of Protonated Phenylalanine and Tyrosine : Photo-Induced Reactions Following Electronic Excitation. Journal of Physical Chemistry A 2015, 119, (23), 5914-5924.
10. Feraud, G. ; Berdakin, M. ; Dedonder, C. ; Jouvet, C. ; Pino, G. A., Excited States of Proton-Bound DNA/RNA Base Homodimers : Pyrimidines. Journal of Physical Chemistry B 2015, 119, (6), 2219-2228.
11. Esteves-Lopez, N. ; Dedonder-Lardeux, C. ; Jouvet, C., Excited state of protonated benzene and toluene. Journal of Chemical Physics 2015, 143, (7).
12. Soorkia, S. ; Dehon, C. ; Kumar, S. S. ; Pedrazzani, M. ; Frantzen, E. ; Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Jouvet, C., UV Photofragmentation Dynamics of Protonated Cystine : Disulfide Bond Rupture. Journal of Physical Chemistry Letters 2014, 5, (7), 1110-1116.
13. Feraud, G. ; Dedonder-Lardeux, C. ; Soorkia, S. ; Jouvet, C., Photo-fragmentation spectroscopy of benzylium and 1-phenylethyl cations. Journal of Chemical Physics 2014, 140, (2).
14. Feraud, G. ; Dedonder, C. ; Jouvet, C. ; Inokuchi, Y. ; Haino, T. ; Sekiya, R. ; Ebata, T., Development of Ultraviolet-Ultraviolet Hole-Burning Spectroscopy for Cold Gas-Phase Ions. Journal of Physical Chemistry Letters 2014, 5, (7), 1236-1240.
15. Feraud, G. ; Broquier, M. ; Dedonder-Lardeux, C. ; Gregoire, G. ; Soorkia, S. ; Jouvet, C., Photofragmentation spectroscopy of cold protonated aromatic amines in the gas phase. Physical Chemistry Chemical Physics 2014, 16, (11), 5250-5259.
16. Dopfer, O. ; Patzer, A. ; Chakraborty, S. ; Alata, I. ; Omidyan, R. ; Broquier, M. ; Dedonder, C. ; Jouvet, C., Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H2O)(n <= 5)] H+ : Evidence for ground-state proton transfer to solvent for n >= 3. Journal of Chemical Physics 2014, 140, (12).
17. Dehon, C. ; Soorkia, S. ; Pedrazzani, M. ; Jouvet, C. ; Barat, M. ; Fayeton, J. A. ; Lucas, B., Photofragmentation at 263 nm of small peptides containing tyrosine : the role of the charge transfer on CO. Physical Chemistry Chemical Physics 2014, 15, (22), 8779-8788.
18. Berdakin, M. ; Feraud, G. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Pino, G. A., Excited states of protonated DNA/RNA bases. Physical Chemistry Chemical Physics 2014, 16, (22), 10643-10650.
19. Alata, I. ; Bert, J. ; Broquier, M. ; Dedonder, C. ; Feraud, G. ; Gregoire, G. ; Soorkia, S. ; Marceca, E. ; Jouvet, C., Electronic Spectra of the Protonated Indole Chromophore in the Gas Phase. Journal of Physical Chemistry A 2014, 117, (21), 4420-4427.
20. Patzer, A. ; Schutz, M. ; Jouvet, C. ; Dopfer, O., Experimental Observation and Quantum Chemical Characterization of the S-1 <- S-0 Transition of Protonated Naphthalene-Argon Clusters. Journal of Physical Chemistry A 2013, 117, (39), 9785-9793.
21. Dehon, C. ; Soorkia, S. ; Pedrazzani, M. ; Jouvet, C. ; Barat, M. ; Fayeton, J. A. ; Lucas, B., Photofragmentation at 263 nm of small peptides containing tyrosine : the role of the charge transfer on CO. Physical Chemistry Chemical Physics 2013, 15, (22), 8779-8788.
22. Alata, I. ; Bert, J. ; Broquier, M. ; Dedonder, C. ; Feraud, G. ; Gregoire, G. ; Soorkia, S. ; Marceca, E. ; Jouvet, C., Electronic Spectra of the Protonated Indole Chromophore in the Gas Phase. Journal of Physical Chemistry A 2013, 117, (21), 4420-4427.
23. Alata, I. ; Omidyan, R. ; Broquier, M. ; Dedonder, C. ; Jouvet, C., Protonated salicylaldehyde : Electronic properties. Chemical Physics 2012, 399, 224-231.
24. Alata, I. ; Broquier, M. ; Dedonder, C. ; Jouvet, C. ; Marceca, E., Electronic excited states of protonated aromatic molecules : Protonated Fluorene. Chemical Physics 2012, 393, (1), 25-31.
25. Patzer, A. ; Zimmermann, M. ; Alata, I. ; Jouvet, C. ; Dopfer, O., Electronic Spectra of Protonated Benzaldehyde Clusters with Ar and N-2 : Effect of pi pi* Excitation on the Intermolecular Potential. Journal of Physical Chemistry A 2010, 114, (48), 12600-12604.
26. Alata, I. ; Omidyan, R. ; Broquier, M. ; Dedonder, C. ; Dopfer, O. ; Jouvet, C., Effect of protonation on the electronic structure of aromatic molecules : naphthaleneH(+). Physical Chemistry Chemical Physics 2010, 12, (43), 14456-14458.
27. Alata, I. ; Dedonder, C. ; Broquier, M. ; Marceca, E. ; Jouvet, C., Role of the Charge-Transfer State in the Electronic Absorption of Protonated Hydrocarbon Molecules. Journal of the American Chemical Society 2010, 132, (49), 17483-17489.
28. Rode, M. F. ; Sobolewski, A. L. ; Dedonder, C. ; Jouvet, C. ; Dopfer, O., Computational Study on the Photophysics of Protonated Benzene. Journal of Physical Chemistry A 2009, 113, (20), 5865-5873.
29. Gregoire, G. ; Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Dedonder-Lardeux, C. ; Jouvet, C., UV photoinduced dynamics in protonated aromatic amino acid. European Physical Journal D 2009, 51, (1), 109-116.
30. Chakraborty, S. ; Omidyan, R. ; Alata, I. ; Nielsen, I. B. ; Dedonder, C. ; Broquier, M. ; Jouvet, C., Protonated Benzene Dimer : An Experimental and Ab Initio Study. Journal of the American Chemical Society 2009, 131, (31), 11091-11097.
31. Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Perot, M. ; Jouvet, C. ; Gregoire, G. ; Nielsen, S. B., Mechanisms of photoinduced C(alpha)-C(beta) bond breakage in protonated aromatic amino acids. Journal of Chemical Physics 2008, 128, (16).
32. Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Jouvet, C. ; Carcabal, P. ; Gregoire, G., Statistical versus non-statistical photo-fragmentation of protonated GWG tri-peptide induced by UV excitation. Chemical Physics 2008, 347, (1-3), 324-330.
33. Lepere, V. ; Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Picard, Y. J. ; Jouvet, C. ; Carcabal, P. ; Nielsen, I. ; Dedonder-Lardeux, C. ; Gregoire, G. ; Fujii, A., Characterization of neutral fragments issued from the photodissociation of protonated tryptophane. Physical Chemistry Chemical Physics 2007, 9, (39), 5330-5334.
34. Lepere, V. ; Lucas, B. ; Barat, M. ; Fayeton, J. A. ; Picard, V. J. ; Jouvet, C. ; Carcabal, P. ; Nielsen, I. ; Dedonder-Lardeux, C. ; Gregoire, G. ; Fujii, A., Comprehensive characterization of the photodissociation pathways of protonated tryptophan. Journal of Chemical Physics 2007, 127, (13).
35. Gregoire, G. ; Jouvet, C. ; Dedonder, C. ; Sobolewski, A. L., Ab initio study of the excited-state deactivation pathways of protonated tryptophan and tyrosine. Journal of the American Chemical Society 2007, 129, (19), 6223-6231.
36. Gregoire, G. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Desfrancois, C. ; Fayeton, J. A., Ultrafast excited state dynamics in protonated GWG and GYG tripeptides. Physical Chemistry Chemical Physics 2007, 9, (1), 78-82.
37. Gregoire, G. ; Kang, H. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Desfrancois, C. ; Onidas, D. ; Lepere, V. ; Fayeton, J. A., Statistical vs. non-statistical deactivation pathways in the UV photo-fragmentation of protonated tryptophan-leucine dipeptide. Physical Chemistry Chemical Physics 2006, 8, (1), 122-128.
38. Gregoire, G. ; Jouvet, C. ; Dedonder, C. ; Sobolewski, A. L., On the role of dissociative pi sigma* states in the photochemistry of protonated tryptamine and tryptophan : An ab initio study. Chemical Physics 2006, 324, (2-3), 398-404.
39. Antoine, R. ; Broyer, M. ; Chamot-Rooke, J. ; Dedonder, C. ; Desfrancois, C. ; Dugourd, P. ; Gregoire, G. ; Jouvet, C. ; Onidas, D. ; Poulain, P. ; Tabarin, T. ; van der Rest, G., Comparison of the fragmentation pattern induced by collisions, laser excitation and electron capture. Influence of the initial excitation. Rapid Communications in Mass Spectrometry 2006, 20, (11), 1648-1652.
40. Kang, H. ; Jouvet, C. ; Dedonder-Lardeux, C. ; Martrenchard, S. ; Gregoire, G. ; Desfrancois, C. ; Schermann, J. P. ; Barat, M. ; Fayeton, J. A., Ultrafast deactivation mechanisms of protonated aromatic amino acids following UV excitation. Physical Chemistry Chemical Physics 2005, 7, (2), 394-398.
41. Kang, H. ; Jouvet, C. ; Dedonder-Lardeux, C. ; Martrenchard, S. ; Charriere, C. ; Gregoire, G. ; Desfrancois, C. ; Schermann, J. P. ; Barat, M. ; Fayeton, J. A., Photoinduced processes in protonated tryptamine. Journal of Chemical Physics 2005, 122, (8).
42. Kang, H. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Gregoire, G. ; Desfrancois, C. ; Schermann, J. P. ; Barat, M. ; Fayeton, J. A., Control of bond-cleaving reactions of free protonated tryptophan ion by femtosecond laser pulses. Journal of Physical Chemistry A 2005, 109, (11), 2417-2420.
43. Kang, H. ; Dedonder-Lardeux, C. ; Jouvet, C. ; Martrenchard, S. ; Gregoire, G. ; Desfrancois, C. ; Schermann, J. P. ; Barat, M. ; Fayeton, J. A., Photo-induced dissociation of protonated tryptophan TrpH(+) : A direct dissociation channel in the excited states controls the hydrogen atom loss. Physical Chemistry Chemical Physics 2004, 6, (10), 2628-2632.