Ultraviolet photoelectron studies of the ground-state electronic structure and gas-phase tautomerism of hypoxanthine and guanine

Lin, J.; Cheng, Yu; Peng, S.; Akiyama, I.; Li, K.; Lee, Li Kao; Lebreton, Pierre

doi:10.1021/j100446a015

Cited by 130 publications

(142 citation statements)

References 12 publications

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“…Thus, the distinct low-energy band in the spectrum of dGMP Ϫ is caused by ionization of the guanine base, whereas the onset of the spectra for dAMP Ϫ , dCMP Ϫ , and dTMP Ϫ is caused by electron detachment from the phosphate. Among the four free nucleic acid bases, guanine is known to possess the lowest IP (9,10). The current results show that the low IP of guanine is fully displayed in the intact mononucleotides even when dGMP Ϫ is in the anti conformation (as seen in Table 2).…”

Section: Figmentioning

confidence: 49%

“…In most cases, guanine is the initial oxidation site, or the electron-loss center ultimately moves through the DNA stack to end up at a guanine base (7). This observation is attributed to the low ionization potential (IP) of guanine relative to the other DNA bases (8)(9)(10). Thus, the electronic structure of nucleotides and their ionization properties are essential for understanding the mechanism of DNA damage.…”

Section: Dna Oxidation ͉ Nucleotidementioning

confidence: 99%

“…Extensive experimental and theoretical studies have focused on these topics (11)(12)(13)(14)(15)(16)(17)(18)(19). In particular, LeBreton and coworkers (9,(20)(21)(22)(23)(24) have investigated the ionization of nucleic acid bases, sugar residue, and the phosphate in the gas phase by using UV photoelectron spectroscopy (PES) and then combining these studies and molecular orbital calculations to address the electronic structure of the nucleotides. Gas-phase studies probe the intrinsic electronic properties of the nucleotides and provide important experimental data to compare with and verify theoretical results and methods.…”

Section: Dna Oxidation ͉ Nucleotidementioning

confidence: 99%

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Direct experimental observation of the low ionization potentials of guanine in free oligonucleotides by using photoelectron spectroscopy

Yang

Wang

Vorpagel

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

144

208

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Photodetachment photoelectron spectroscopy is used to probe the electronic structure of mono-, di-, and trinucleotide anions in the gas phase. A weak and well defined threshold band was observed in the photoelectron spectrum of 2 -deoxyguanosine 5 -monophosphate at a much lower ionization energy than the other three mononucleotides. Density function theory calculations revealed that this unique spectral feature is caused by electron-detachment from a orbital of the guanine base on 2 -deoxyguanosine 5 -monophosphate, whereas the lowest ionization channel for the other three mononucleotides takes place from the phosphate group. This low-energy feature was shown to be a ''fingerprint'' in all the spectra of dinucleotides and trinucleotides that contain the guanine base. The current experiment provides direct spectroscopic evidence that the guanine base is the site with the lowest ionization potential in oligonucleotides and DNA and is consistent with the fact that guanine is most susceptible to oxidation to give the guanine cation in DNA damage. DNA oxidation ͉ nucleotideT he ionization of nucleotide plays very important roles in the chemistry and biology of DNA. Induced by electrophiles or ionizing radiation, the electron-deficient site (hole) on the nucleotide and its migration may lead directly to DNA damage (1-6). In most cases, guanine is the initial oxidation site, or the electron-loss center ultimately moves through the DNA stack to end up at a guanine base (7). This observation is attributed to the low ionization potential (IP) of guanine relative to the other DNA bases (8-10). Thus, the electronic structure of nucleotides and their ionization properties are essential for understanding the mechanism of DNA damage. Extensive experimental and theoretical studies have focused on these topics (11)(12)(13)(14)(15)(16)(17)(18)(19). In particular, LeBreton and coworkers (9,[20][21][22][23][24] have investigated the ionization of nucleic acid bases, sugar residue, and the phosphate in the gas phase by using UV photoelectron spectroscopy (PES) and then combining these studies and molecular orbital calculations to address the electronic structure of the nucleotides. Gas-phase studies probe the intrinsic electronic properties of the nucleotides and provide important experimental data to compare with and verify theoretical results and methods.Matrix-assisted laser desorption ionization (25) and electrospray ionization (26) techniques provide powerful tools for characterizing biological molecules in the gas phase. The gasphase conformations of a series of free mononucleotide, dinucleotide, and trinucleotide ions were investigated by using matrix-assisted laser desorption ionization and ion-mobility experiment by Bowers and coworkers (27-30). Our group has developed an experimental technique that couples an electrospray ionization source with a magnetic-bottle photoelectron spectrometer (31) to investigate multiply charged anions and solution species in the gas phase (32, 33). Here, we report a PES study on a series of s...

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Section: Figmentioning

confidence: 49%

Section: Dna Oxidation ͉ Nucleotidementioning

confidence: 99%

Section: Dna Oxidation ͉ Nucleotidementioning

confidence: 99%

See 1 more Smart Citation

Direct experimental observation of the low ionization potentials of guanine in free oligonucleotides by using photoelectron spectroscopy

Yang

Wang

Vorpagel

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

144

208

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“…The differences may be due to different light sources used in two sets of photoelectron spectroscopy experiments [14,26]. Different populations of tautomers can also alter the spectrum.…”

Section: Franck-condon Factors For the S 0 -D 0 Transition In Thyminementioning

confidence: 99%

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

et al. 2010

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We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed us-

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“…This suggests that at the G 0 W 0 level VB states in the latter four bases are energetically more stable than the DB ones. Experimental valence photoemission spectra extends into deep valence states 8,37,38 , allowing us to further evaluate our G 0 W 0 results at a broader energy range. The DFT-PBE and G 0 W 0 densities of states (DOS) for all five bases, neglecting any oscillator strength effect, are compared to valence photoemission spectra in Fig.…”

Section: Convergence Benchmarkmentioning

confidence: 99%

Photoelectron properties of DNA and RNA bases from many-body perturbation theory

2011

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The photoelectron properties of DNA and RNA bases are studied using many-body perturbation theory within the GW approximation, together with a recently developed Lanczos-chain approach. Calculated vertical ionization potentials, electron affinities, and total density of states are in good agreement with experimental values and photoemission spectra. Convergence benchmark demonstrates the importance of using an optimal polarizability basis in the GW calculations. A detailed analysis of the role of exchange and correlation in both many-body and density-functional theory calculations shows that while self-energy corrections are strongly orbital-dependent, they nevertheless remain almost constant for states that share the same bonding character. Finally, we report on the inverse lifetimes of DNA and RNA bases, that are found to depend linearly on quasi-particle energies for all deep valence states. In general, our G0W0-Lanczos approach provides an efficient yet accurate and fully-converged description of quasiparticle properties of five DNA and RNA bases.

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Ultraviolet photoelectron studies of the ground-state electronic structure and gas-phase tautomerism of hypoxanthine and guanine

Cited by 130 publications

References 12 publications

Direct experimental observation of the low ionization potentials of guanine in free oligonucleotides by using photoelectron spectroscopy

Direct experimental observation of the low ionization potentials of guanine in free oligonucleotides by using photoelectron spectroscopy

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

Photoelectron properties of DNA and RNA bases from many-body perturbation theory

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