Abstract
The electronic spectroscopy and the electronic excited state dynamics of the three protonated aromatic amino acids (PAAAs) phenylalanine (Phe), tyrosine (Tyr) and tryptophan (Trp) are presented in this chapter. Ab-initio calculations combined with various experimental techniques such as coincidence experiments, pump-probe spectroscopy and photo-fragmentation of cold trapped ions have been implemented to work out the complex photophysical processes involved in these AAs. The results include photo-fragmentation spectra, excited-state lifetimes, full fragmentation patterns at fixed excitation energies and specific fragmentation channels as a function of the excitation energy. Fragmentation patterns depending on the electronic excited state are detailed.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Lakowicz, J.R.: Invited review on spectral relaxation in proteins. Photochem. Photobiol. 72, 421–437 (2000)
Lakowicz, J.R.: Principles of Fluorescence Spectroscopy, 2nd edn. Springer, New York (1999)
Schermann, J.-P.: Spectroscopy and Modelling of Biomolecular Building Blocks. Elsevier, Amsterdam (2008)
Katarzyna, G., Szabelsk, M., Rzeska, A., Karolczak, J., Sulowska, H., Wiesław, W.: Photophysical properties of tyrosine at low pH range. Chem. Phys. Lett. 362, 519–526 (2002)
Philips, L.A., Webb, S.P., Martinez, S.J., Fleming, G.R., Levy, D.H.: Time-resolved spectroscopy of tryptophan conformers in a supersonic jet. J. Am. Chem. Soc. 110, 1352–1355 (1988)
Robbins, R.J., Fleming, G.R., Beddard, G.S., Robinson, G.W., Thistlethwaite, P.J., Woolfe, G.J.: Photophysics of aqueous tryptophan: pH and temperature effects. J. Am. Chem. Soc. 102, 6271–6279 (1980)
Vivian, J.T., Callis, P.R.: Mechanisms of tryptophan fluorescence shifts in proteins. Biophys. J. 80, 2093–2109 (2001)
Callis, P.R., Petrenko, A., Muin, P.L., Tusell, J.R.: Ab initio prediction of tryptophan fluorescence quenching by protein electric field enabled electron transfer. J. Phys. Chem. B 111, 10335–10339 (2007)
Dedonder-Lardeux, C., Jouvet, C., Perun, S., Sobolewski, A.L.: External electric field effect on the lowest excited states of indole: ab initio and molecular dynamics study. Phys. Chem. Chem. Phys. 5, 5118–5127 (2003)
Marquezin, A., Hirata, I.Y., Juliano, L., Ito, A.S.: Tryptophan as a probe for acid–base equilibria in peptides. Biopolymers 71, 569–576 (2003)
Rizzo, T.R., Park, Y.D., Peteanu, L.A., Levy, D.H.: The electronic spectrum of the amino acid tryptophan in the gas phase. J. Chem. Phys. 84, 2534–2541 (1986)
Inokuchi, Y., Kobayashi, Y., Ito, T., Ebata, T.: Conformation of L-tyrosine studied by fluorescence-detected UV-UV and IR-UV double-resonance spectroscopy. J. Phys. Chem. A 111, 3209–3215 (2007)
Hünig, I., Seefeld, K.A., Kleinermanns, K.: REMPI and UV–UV double resonance spectroscopy of tryptophan ethylester and the dipeptides tryptophan–serine, glycine–tryptophan and proline–tryptophan. Chem. Phys. Lett. 369, 173–179 (2003)
Snoek, L.C., Kroemer, R.T., Hockridge, M.R., Simons, J.P.: Conformational landscapes of aromatic amino acids in the gas phase: infrared and ultraviolet ion dip spectroscopy of tryptophan. Phys. Chem. Chem. Phys. 3, 1819–1826 (2001)
Shimozono, Y., Yamada, K., Ishiuchi, S.-I., Tsukiyama, K., Fujii, M.: Revised conformational assignments and conformational evolution of tyrosine by laser desorption supersonic jet laser spectroscopy. Phys. Chem. Chem. Phys. 15, 5163–5175 (2013)
Mališ, M., Loquais, Y., Gloaguen, E., Biswal, H.S., Piuzzi, F., Tardivel, B., Brenner, V., Broquier, M., Jouvet, C., Mons, M., Došlić, N., Ljubić, I.: Unraveling the mechanisms of nonradiative deactivation in model peptides following photoexcitation of a phenylalanine residue. J. Am. Chem. Soc. 134, 20340–20351 (2012)
Sobolewski, A.L., Domcke, W., Dedonder-Lardeux, C., Jouvet, C.: Excited-state hydrogen detachment and hydrogen transfer driven by repulsive πσ* states: a new paradigm for nonradiative decay in aromatic biomolecules. Phys. Chem. Chem. Phys. 4, 1093–1100 (2002)
Stearns, J.A., Mercier, S., Seaiby, C., Guidi, M., Boyarkin, O.V., Rizzo, T.R.: Conformation-specific spectroscopy and photodissociation of cold, protonated tyrosine and phenylalanine. J. Am. Chem. Soc. 129, 11814–11820 (2007)
Nolting, D., Marian, C., Weinkauf, R.: Protonation effect on the electronic spectrum of tryptophan in the gas phase. Phys. Chem. Chem. Phys. 6, 2633–2640 (2004)
Talbot, F.O., Tabarin, T., Antoine, R., Broyer, M., Dugourd, P.: Photodissociation spectroscopy of trapped protonated tryptophan. J. Chem. Phys. 122, 074310 (2005)
Serrano-andres, L., Roos, B.O.: Theoretical study of the absorption and emission spectra of indole in the gas phase and in a solvent. J. Am. Chem. Soc. 25, 185–195 (1996)
Gindensperger, E., Haegy, A., Daniel, C., Marquardt, R.: Ab initio study of the electronic singlet excited-state properties of tryptophan in the gas phase: the role of alanyl side-chain conformations. Chem. Phys. 374, 104–110 (2010)
Blancafort, L., González, D., Olivucci, M., Robb, M.A.: Quenching of tryptophan 1 (π, π*) fluorescence induced by intramolecular hydrogen abstraction via an aborted decarboxylation mechanism. J. Am. Chem. Soc. 124, 6398–6406 (2002)
Grégoire, G., Jouvet, C., Dedonder, C., Sobolewski, A.L.: Ab initio study of the excited-state deactivation pathways of protonated tryptophan and tyrosine. J. Am. Chem. Soc. 129, 6223–6231 (2007)
Grégoire, G., Jouvet, C., Dedonder, C., Sobolewski, A.L.: On the role of dissociative (π, σ)* states in the photochemistry of protonated tryptamine and tryptophan: an ab initio study. Chem. Phys. 324, 398–404 (2006)
Hattig, C.: Geometry optimizations with the coupled-cluster model CC2 using the resolution identity approximation. J. Chem. Phys. 118, 7751–7761 (2003)
TURBOMOLE V6.2 2011, a development of U. of K. and; Forschungszentrum Karlsruhe GmbH, 1989–2007; TURBOMOLE GmbH, since 2007. http://www.turbomole.com
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. Phys. Chem. Chem. Phys. 7, 394–398 (2005)
Jochims, H.W., Baumgärtel, H., Leach, S.: Photoionization quantum yields of polycyclic aromatic hydrocarbons. Astron. Astrophys. 314, 1003–1009 (1996)
Andersen, J.U., Cederquist, H., Forster, J.S., Huber, B.A., Hvelplund, P., Jensen, J., Liu, B., Manil, B., Maunoury, L., Nielsen, S.B., Pedersen, U.V., Rangama, J., Schmidt, H.T., Tomita, S., Zettergren, H.: Photodissociation of protonated amino acids and peptides in an ion storage ring. Determination of Arrhenius parameters in the high-temperature limit. Phys. Chem. Chem. Phys. 6, 2676–2681 (2004)
Lepere, V., Lucas, B., Barat, M., Fayeton, J.A., Picard, Y.J., Jouvet, C., Çarçabal, P., Nielsen, I.B., Dedonder-Lardeux, C., Grégoire, G., Fujii, M.: Characterization of neutral fragments issued from the photodissociation of protonated tryptophane. Phys. Chem. Chem. Phys. 9, 5330–5334 (2007)
Lepere, V., Lucas, B., Barat, M., Fayeton, J.A., Picard, Y.J., Jouvet, C., Çarçabal, P., Nielsen, I.B., Dedonder-Lardeux, C., Grégoire, G., Fujii, M.: Comprehensive characterization of the photodissociation pathways of protonated tryptophan. J. Chem. Phys. 127, 134313 (2007)
Grégoire, G., Lucas, B., Barat, M., Fayeton, J.A., Dedonder-Lardeux, C., Jouvet, C.: UV photoinduced dynamics in protonated aromatic amino acid. Eur. Phys. J. D 51, 109–116 (2009)
Kang, H., Dedonder-Lardeux, C., Jouvet, C., Martrenchard, S., Grégoire, G., Desfrançois, 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. Phys. Chem. Chem. Phys. 6, 2628–2632 (2004)
Mercier, S.R., Boyarkin, O.V., Kamarioti, A., Guglielmi, M., Tavernelli, I., Cascella, M., Rothlisberger, U., Rizzo, T.R.: Microsolvation effects on the excited-state dynamics of protonated tryptophan. J. Am. Chem. Soc. 128, 16938–16943 (2006)
Boyarkin, O.V., Mercier, S.R., Kamariotis, A., Rizzo, T.R.: Electronic spectroscopy of cold protonated tryptophan and tyrosine. J. Am. Chem. Soc. 128, 2816–2817 (2006)
Rogalewicz, F., Hoppilliard, Y., Ohanessian, G.: Fragmentation mechanisms of alpha-amino acids protonated under electrospray ionization: a collisional activation and ab initio theoretical study. Int. J. Mass Spectrom. 195–196, 565–590 (2000)
Lioe, H., O’Hair, R.A.J., Reid, G.E.: Gas phase ion chemistry of biomolecules. Part 37 - Gas-phase reactions of protonated tryptophan. J. Am. Soc. Mass Spectrom. 15, 65–76 (2004)
Grewal, R.N., El Aribi, H., Harrison, A.G., Siu, K.W.M., Hopkinson, A.C.: Fragmentation of protonated tripeptides: the proline effect revisited. J. Phys. Chem. B 108, 4899–4908 (2004)
El Aribi, H., Orlova, G., Rodriquez, C.F., Almeida, D.R.P., Hopkinson, A.C., Siu, K.W.M.: Fragmentation mechanisms of product ions from protonated tripeptides. J. Phys. Chem. B 108, 18743–18749 (2004)
Lucas, B., Barat, M., Fayeton, J.A., Perot, M., Jouvet, C., Grégoire, G., Brøndsted Nielsen, S.: Mechanisms of photoinduced C-alpha-C-beta bond breakage in protonated aromatic amino acids. J. Chem. Phys. 128, 164302 (2008)
Svendsen, A., Lorenz, U.J., Boyarkin, O.V., Rizzo, T.R.: A new tandem mass spectrometer for photofragment spectroscopy of cold gas-phase molecular ions. Rev. Sci. Instrum. 81, 073107 (2010)
Wang, Y.S., Tsai, C.H., Lee, Y.T., Chang, H.C., Jiang, J.C., Asvany, O., Schlemmer, S., Gerlich, D.: Investigations of protonated and deprotonated water clusters using a low-temperature 22-pole ion trap. J. Phys. Chem. A 107, 4217–4225 (2003)
Wang, X.-B., Wang, L.-S.: Development of a low-temperature photoelectron spectroscopy instrument using an electrospray ion source and a cryogenically controlled ion trap. Rev. Sci. Instrum. 79, 073108 (2008)
Choi, C.M., Choi, D.H., Kim, N.J., Heo, J.: Effective temperature of protonated tyrosine ions in a cold quadrupole ion trap. Int. J. Mass Spectrom. 314, 18–21 (2012)
Fujihara, A., Matsumoto, H., Shibata, Y., Ishikawa, H., Fuke, K.: Photodissociation and spectroscopic study of cold protonated dipeptides. J. Phys. Chem. A 112, 1457–1463 (2008)
Fujihara, A., Noguchi, N., Yamada, Y., Ishikawa, H., Fuke, K.: Microsolvation and protonation effects on geometric and electronic structures of tryptophan and tryptophan-containing dipeptides. J. Phys. Chem. A 113, 8169–8175 (2009)
Rode, M., Sobolewski, A.L., Dedonder, C., Jouvet, C., Dopfer, O.: Computational study on the photophysics of protonated benzene. J. Phys. Chem. A 113, 5865–5873 (2009)
PGOPHER, a program for simulating rotational structure. C. M. Western, University of Bristol. http://pgopher.chm.bris.ac.uk
Send, R., Kühn, M., Furche, F.: Assessing excited state methods by adiabatic excitation energies. J. Chem. Theory Comput. 7, 2376–2386 (2011)
Grace, L.I., Cohen, R., Dunn, T.M., Lubman, D.M., De Vries, M.S.: The R2PI spectroscopy of tyrosine: a vibronic analysis. J. Mol. Spectrosc. 215, 204–219 (2002)
Grégoire, G., Kang, H., Dedonder-Lardeux, C., Jouvet, C., Desfrançois, C., Onidas, D., Lepere, V., Fayeton, J.: Statistical vs. non-statistical deactivation pathways in the UV photo-fragmentation of protonated tryptophan-leucine dipeptide. Phys. Chem. Chem. Phys. 8, 122–128 (2006)
Lucas, B., Barat, M., Fayeton, J.A., Jouvet, C., Çarçabal, P., Grégoire, G.: Statistical versus non-statistical photo-fragmentation of protonated GWG tri-peptide induced by UV excitation. Chem. Phys. 347, 324–330 (2008)
Kang, H., Dedonder-Lardeux, C., Jouvet, C., Grégoire, G., Desfrançois, C., Schermann, J.-P., Barat, M., Fayeton, J.A.: Control of bond-cleaving reactions of free protonated tryptophan ion by femtosecond laser pulses. J. Phys. Chem. A 109, 2417–2420 (2005)
Grégoire, G., Jouvet, C., Dedonder, C.: What is the meaning of lifetime measurement? http://hal.archives-ouvertes.fr/hal-00023586/fr/ (2006), 2–4
Fuke, K., Takasu, R., Misaizu, F.: Photoionization of hypervalent molecular clusters: electronic structure and stability of NH4(NH3)n. Chem. Phys. Lett. 229, 597–603 (1994)
Park, J.K.: Stability of the Rydberg H3O radical. Bull. Korean Chem. Soc. 20, 734–736 (1999)
Alata, I., Dedonder, C., Broquier, M., Marceca, E., Jouvet, C.: Role of the charge-transfer state in the electronic absorption of protonated hydrocarbon molecules. J. Am. Chem. Soc. 132, 17483–17489 (2010)
Rodriquez, C.F., Cunje, A., Shoeib, T., Chu, I.K., Hopkinson, A.C., Siu, K.W.M.: Proton migration and tautomerism in protonated triglycine. J. Am. Chem. Soc. 123, 3006–3012 (2001)
Nagornova, N.S., Rizzo, T.R., Boyarkin, O.V.: Highly resolved spectra of gas-phase gramicidin S: a benchmark for peptide structure calculations. J. Am. Chem. Soc. 132, 4040–4041 (2010)
Poulain, P.: Structure et dynamique de proteines isolees: approches statistiques. PhD Universite Claude Bernard -Lyon 1 (2006)
Nolting, D., Schultz, T., Hertel, I.V., Weinkauf, R.: Excited state dynamics and fragmentation channels of the protonated dipeptide H2N-Leu-Trp-COOH. Phys. Chem. Chem. Phys. 8, 5247–5254 (2006)
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2013 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Dedonder, C., Féraud, G., Jouvet, C. (2013). Excited-State Dynamics of Protonated Aromatic Amino Acids. In: Brøndsted Nielsen, S., Wyer, J. (eds) Photophysics of Ionic Biochromophores. Physical Chemistry in Action. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-40190-9_9
Download citation
DOI: https://doi.org/10.1007/978-3-642-40190-9_9
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-40189-3
Online ISBN: 978-3-642-40190-9
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)