Photostability of Isolated and Paired Nucleobases: NH Dissociation of Adenine and Hydrogen Transfer in its Base Pairs Examined by Laser Spectroscopy

Hünig, Isabel; Plützer, Christian; Seefeld, Kai; Löwenich, Dennis; Nispel, Michael; Kleinermanns, Karl

doi:10.1002/cphc.200400142

Cited by 85 publications

(106 citation statements)

References 24 publications

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“…21,[24][25][26] A conical intersection to a quasi-dissociative πσ* may also play a role, 8,11 especially at higher excitation energies or in polarizable environments. 16,[27][28][29][30] Time-resolved photoelectron spectroscopy (TRPES) experiments comparing adenine with 9-methyl-substituted adenine 11 found the same biexponential time constants, 0.1 and 1.2 ps, as ion yield studies. 10,18 But different decay-associated photoelectron spectra of the 0.1 ps component were assigned to the participation of a πσ* state based on calculations of the FranckCondon spectra.…”

Section: Introductionmentioning

confidence: 88%

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

et al. 2007

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp076800eAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at Electronic structure of adenine and thymine base pairs studied by femtosecond electron-ion coincidence spectroscopy Gador, Niklas; Samoylova, Elena; Smith, Valoris Reid; Stolow, Albert; Rayner, David M.; Radloff, Wolfgang; Hertel, Ingolf Volker; Schultz, Thomas http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=db4ea838-d64b-464c-aa0b-a7edab815e24 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=db4ea838-d64b-464c-aa0b-a7edab815e24 Sciences, National Research Council, 100 Sussex DriVe, Ottawa, K1A 0R6 Canada, and Max Born Institute, 12489 Berlin-Adlershof, Germany ReceiVed: August 24, 2007; In Final Form: September 6, 2007 Femtosecond pump-probe spectroscopy was combined with photoelectron-photoion coincidence detection to investigate the electronic structure and dynamics of isolated adenine (A) and thymine (T) dimers and the adenine-thymine (AT) base pair. The photoelectron spectra show that ππ* and nπ* states are only weakly perturbed in the hydrogen-bound dimers as compared to the monomers. For cationic base pairs with internal energies greater than 1 eV, we observed considerable cluster fragmentation into protonated monomers. This process selectively removed signals from the nπ* f n -1 ionization channel in all dimers. The photoelectron spectra are compared to time-resolved mass spectra and confirm the assignment of short-lived ππ* and nπ* populations in the adenine, thymine, and mixed AT dimers.

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Section: Introductionmentioning

confidence: 88%

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

et al. 2007

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“…For 4-aminopyrimidine, surface hopping calculations identified two conical intersections (5,33,(80)(81)(82)(83)(84)(85)(86)(87)(88)(89)(90)(91)(92): deformation at the C2 position leads to deactivation of the excited state with a lifetime, τ*, of 1 ps and deformation at the C5=C6 bond with a τ* of 400 fs. Immobilizing the latter with a 5 membered ring forms adenine with a conical intersection due to the C2 deformation, τ* of 1 ps and dynamics similar to that in guanine.…”

Section: Excited State Dynamicsmentioning

confidence: 99%

Gas-Phase IR Spectroscopy of Nucleobases

Vries

2014

Topics in Current Chemistry

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Abstract.IR spectroscopy of nucleobases in the gas phase reflects simultaneous advances in both experimental and computational technique. Important properties, such as excited state dynamics, depend in subtle ways on structure variations, which can be followed by their infrared signatures. Isomer specific spectroscopy is a particularly powerful tool for studying the effects of nucleobase tautomeric form and base pair hydrogen bonding patterns.

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“…6 show an enhancement of the H + signal from uracil at the 243.1 nm (2 + 1) resonant wavelength for hydrogen MPI. 38 Jochims et al 21 assigned the m/z = 68 fragment ion to H loss from C 3 H 3 NO + on the basis of appearance energies and thermochemical calculations, although this is clearly not the only plausible pathway for neutral H production. We have a particular interest in CO as this is the neutral by-product of the mechanism that we associate with ion production at m/z = 84 (see Sec.…”

Section: Neutral Fragment Productionmentioning

confidence: 99%

Multi-photon ionization and fragmentation of uracil: Neutral excited-state ring opening and hydration effects

Barc

Ryszka

Spurrell

et al. 2013

The Journal of Chemical Physics

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Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S2(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C3H4N2O+ following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a CO group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C3H3NO+) but represses C3H4N2O+ production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.

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Photostability of Isolated and Paired Nucleobases: NH Dissociation of Adenine and Hydrogen Transfer in its Base Pairs Examined by Laser Spectroscopy

Cited by 85 publications

References 24 publications

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

Gas-Phase IR Spectroscopy of Nucleobases

Multi-photon ionization and fragmentation of uracil: Neutral excited-state ring opening and hydration effects

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